Intriguing Morphology Evolution from Noncrosslinked Poly(tert-butyl acrylate) Seeds with Polar Functional Groups in Soap-Free Emulsion Polymerization of Styrene.

PubMed

Wang, Lu; Pan, Mingwang; Song, Shaofeng; Zhu, Lei; Yuan, Jinfeng; Liu, Gang

2016-08-09

Herein, we demonstrate a facile approach to prepare anisotropic poly(tert-butyl acrylate)/polystyrene (PtBA/PS) composite particles with controllable morphologies by soap-free seeded emulsion polymerization (SSEP). In the first step, noncrosslinked PtBA seeds with self-stabilizing polar functional groups (e.g., ester groups and radicals) are synthesized by soap-free emulsion polymerization. During the subsequent SSEP of styrene (St), PS bulges are nucleated on the PtBA seeds due to the microphase separation confined in the latex particles. The morphology evolution of PtBA/PS composite particles is tailored by varying the monomer/seed feed ratio, polymerization time, and polymerization temperature. Many intriguing morphologies, including hamburger-like, litchi-like, mushroom-like, strawberry-like, bowl-like, and snowman-like, have been acquired for PtBA/PS composite particles. The polar groups on the PtBA seed surface greatly influence the formation and further merging of PS/St bulges during the polymerization. A possible formation mechanism is proposed on the basis of experimental results. These complex composite particles are promising for applications in superhydrophobic coatings.

Oligopeptides and copeptides of homochiral sequence, via beta-sheets, from mixtures of racemic alpha-amino acids, in a one-pot reaction in water; relevance to biochirogenesis.

PubMed

Illos, Roni A; Bisogno, Fabricio R; Clodic, Gilles; Bolbach, Gerard; Weissbuch, Isabelle; Lahav, Meir

2008-07-09

As part of our studies on the biochirogenesis of peptides of homochiral sequence during early evolution, the formation of oligopeptides composed of 14-24 residues of the same handedness in the polymerization of dl-leucine (Leu), dl-phenylalanine (Phe), and dl-valine (Val) in aqueous solutions, by activation with N, N'-carbonyldiimidazole and then initiation with a primary amine, in a one-pot reaction, was demonstrated by MALDI-TOF MS using deuterium enantio-labeled alpha-amino acids. The formation of long isotactic peptides is rationalized by the following steps occurring in tandem: (i) creation of a library of short diasteroisomeric oligopeptides containing isotactic peptides in excess in comparison to a binomial kinetics, as a result of an asymmetric induction exerted by the N-terminal residue of a given handedness; (ii) precipitation of the less soluble racemic isotactic penta- and hexapeptides in the form of beta-sheets that are delineated by homochiral rims; (iii) regio-enantiospecific chain elongation occurring heterogeneously at the beta-sheets/solution interface. Polymerization of l-Leu with l-isoleucine (Ile) or l-Phe with l- (1) N-Me-histidine yielded mixtures of copeptides containing both residues. In contrast, in the polymerization of the corresponding mixtures of l- + d-alpha-amino acids, the long oligopeptides were composed mainly from oligo- l-Leu and oligo- d-Ile in the first system and oligo- d-Phe in the second. Furthermore, in the polymerization of mixtures of hydrophobic racemic alpha-amino acids dl-Leu, dl-Val, and dl-Phe and with added racemic dl-alanine and dl-tyrosine, copeptides of homochiral sequences are most dominantly represented. Possible routes for a spontaneous "mirror-symmetry breaking" process of the racemic mixtures of homochiral peptides are presented.

In vitro comparison of autoclave polymerization on the transverse strength of denture base resins.

PubMed

Durkan, Rukiye; Ozel, Mehmet Birol; Bağiş, Bora; Usanmaz, Ali

2008-07-01

The aim of this study was to determine the effect of autoclave polymerization on the transverse strength of denture base polymers. To this end, 30 rectangular test specimens were fabricated of two heat-polymerized denture base polymers. The test groups were: (I) control, i.e., conventional water bath to polymerize resins by heat at 100 degrees C for 30 minutes; (II) autoclave polymerization at 60 degrees C for 30 minutes followed by 130 degrees C for 10 minutes; and (III) autoclave polymerization at 60 degrees C for 30 minutes followed by 130 degrees C for 20 minutes. The specimens were tested with three-point bending test at a crosshead speed of 5 mm/min. It was revealed that the transverse strength of specimens increased with statistical significance when the autoclave was used for polymerization.

Influence of Al(III) on biofilm and its extracellular polymeric substances in sequencing batch biofilm reactors.

PubMed

Hu, Xuewei; Yang, Lei; Lai, Xinke; Yao, Qi; Chen, Kai

2017-10-03

This paper presented the influence of Al(III) on biodegradability, micromorphology, composition and functional groups characteristics of the biofilm extracellular polymeric substances (EPS) during different growth phases. The sequencing batch biofilm reactors were developed to cultivate biofilms under different Al(III) dosages. The results elucidated that Al(III) affected biofilm development adversely at the beginning of biofilm growth, but promoted the biofilm mass and improved the biofilm activity with the growth of the biofilm. The micromorphological observation indicated that Al(III) led to a reduction of the filaments and promotion of the EPS secretion in growth phases of the biofilm, also Al(III) could promote microorganisms to form larger colonies for mature biofilm. Then, the analysis of EPS contents and components suggested that Al(III) could increase the protein (PN) of tightly bound EPS (TB-EPS) which alleviated the metal toxicity inhibition on the biofilm during the initial phases of biofilm growth. The biofilm could gradually adapt to the inhibition caused by Al(III) at the biofilm maturation moment. Finally, through the Fourier transform infrared spectroscopy, it was found that Al(III) was beneficial for the proliferation and secretion of TB-EPS functional groups, especially the functional groups of protein and polysaccharides.

Pentacoordinate and Hexacoordinate Mn(III) Complexes of Tetradentate Schiff-Base Ligands Containing Tetracyanidoplatinate(II) Bridges and Revealing Uniaxial Magnetic Anisotropy.

PubMed

Nemec, Ivan; Herchel, Radovan; Trávníček, Zdeněk

2016-12-08

Crystal structures and magnetic properties of polymeric and trinuclear heterobimetallic Mn III ···Pt II ···Mn III coordination compounds, prepared from the Ba[Pt(CN)₄] and [Mn(L4A/B)(Cl)] ( 1a / b ) precursor complexes, are reported. The polymeric complex [{Mn(L4A)}₂{μ⁴-Pt(CN)₄}] n ( 2a ), where H₂L4A = N , N '-ethylene-bis(salicylideneiminate), comprises the {Mn(L4A)} moieties covalently connected through the [Pt(CN)₄] 2- bridges, thus forming a square-grid polymeric structure with the hexacoordinate Mn III atoms. The trinuclear complex [{Mn(L4B)}₂{μ-Pt(CN)₄}] ( 2b ), where H₂L4B = N , N '-benzene-bis(4-aminodiethylene-salicylideneiminate), consists of two [{Mn(L4B)} moieties, involving pentacoordinate Mn III atoms, bridged through the tetracyanidoplatinate (II) bridges to which they are coordinated in a trans fashion. Both complexes possess uniaxial type of magnetic anisotropy, with D (the axial parameter of zero-field splitting) = -3.7(1) in 2a and -2.2(1) cm -1 in 2b . Furthermore, the parameters of magnetic anisotropy 2a and 2b were also thoroughly studied by theoretical complete active space self-consistent field (CASSCF) methods, which revealed that the former is much more sensitive to the ligand field strength of the axial ligands.

Polymeric hydrogels for novel contact lens-based ophthalmic drug delivery systems: a review.

PubMed

Xinming, Li; Yingde, Cui; Lloyd, Andrew W; Mikhalovsky, Sergey V; Sandeman, Susan R; Howel, Carol A; Liewen, Liao

2008-04-01

Only about 5% of drugs administrated by eye drops are bioavailable, and currently eye drops account for more than 90% of all ophthalmic formulations. The bioavailability of ophthalmic drugs can be improved by a soft contact lens-based ophthalmic drug delivery system. Several polymeric hydrogels have been investigated for soft contact lens-based ophthalmic drug delivery systems: (i) polymeric hydrogels for conventional contact lens to absorb and release ophthalmic drugs; (ii) polymeric hydrogels for piggyback contact lens combining with a drug plate or drug solution; (iii) surface-modified polymeric hydrogels to immobilize drugs on the surface of contact lenses; (iv) polymeric hydrogels for inclusion of drugs in a colloidal structure dispersed in the lens; (v) ion ligand-containing polymeric hydrogels; (vi) molecularly imprinted polymeric hydrogels which provide the contact lens with a high affinity and selectivity for a given drug. Polymeric hydrogels for these contact lens-based ophthalmic drug delivery systems, their advantages and drawbacks are critically analyzed in this review.

Luminescent and triboluminescent properties of europium(III) complex with cinnamic acid

NASA Astrophysics Data System (ADS)

Kalinovskaya, I. V.; Mirochnik, A. G.; Nagornyi, I. G.

2014-10-01

An intensely emitting crystalline europium(III) complex with cinnamic acid [Eu(Cin)3] n and exhibiting triboluminescent properties is synthesized. It is established that the measured photo- and triboluminescence spectra are identical for the above polymeric non-centrosymmetric complex and are determined by the characteristic f-f luminescence of the europium(III) ion.

Polymeric trileaflet prosthetic heart valves: evolution and path to clinical reality

PubMed Central

Claiborne, Thomas E; Slepian, Marvin J; Hossainy, Syed; Bluestein, Danny

2013-01-01

Present prosthetic heart valves, while hemodynamically effective, remain limited by progressive structural deterioration of tissue valves or the burden of chronic anticoagulation for mechanical valves. An idealized valve prosthesis would eliminate these limitations. Polymeric heart valves (PHVs), fabricated from advanced polymeric materials, offer the potential of durability and hemocompatibility. Unfortunately, the clinical realization of PHVs to date has been hampered by findings of in vivo calcification, degradation and thrombosis. Here, the authors review the evolution of PHVs, evaluate the state of the art of this technology and propose a pathway towards clinical reality. In particular, the authors discuss the development of a novel aortic PHV that may be deployed via transcatheter implantation, as well as its optimization via device thrombogenicity emulation. PMID:23249154

DNA-Templated Polymerization of Side-Chain-Functionalized Peptide Nucleic Acid Aldehydes

PubMed Central

Kleiner, Ralph E.; Brudno, Yevgeny; Birnbaum, Michael E.; Liu, David R.

2009-01-01

The DNA-templated polymerization of synthetic building blocks provides a potential route to the laboratory evolution of sequence-defined polymers with structures and properties not necessarily limited to those of natural biopolymers. We previously reported the efficient and sequence-specific DNA-templated polymerization of peptide nucleic acid (PNA) aldehydes. Here, we report the enzyme-free, DNA-templated polymerization of side-chain-functionalized PNA tetramer and pentamer aldehydes. We observed that the polymerization of tetramer and pentamer PNA building blocks with a single lysine-based side chain at various positions in the building block could proceed efficiently and sequence-specifically. In addition, DNA-templated polymerization also proceeded efficiently and in a sequence-specific manner with pentamer PNA aldehydes containing two or three lysine side chains in a single building block to generate more densely functionalized polymers. To further our understanding of side-chain compatibility and expand the capabilities of this system, we also examined the polymerization efficiencies of 20 pentamer building blocks each containing one of five different side-chain groups and four different side-chain regio- and stereochemistries. Polymerization reactions were efficient for all five different side-chain groups and for three of the four combinations of side-chain regio- and stereochemistries. Differences in the efficiency and initial rate of polymerization correlate with the apparent melting temperature of each building block, which is dependent on side-chain regio- and stereochemistry, but relatively insensitive to side-chain structure among the substrates tested. Our findings represent a significant step towards the evolution of sequence-defined synthetic polymers and also demonstrate that enzyme-free nucleic acid-templated polymerization can occur efficiently using substrates with a wide range of side-chain structures, functionalization positions within each building block, and functionalization densities. PMID:18341334

Neodymium(III) Complexes of Dialkylphosphoric and Dialkylphosphonic Acids Relevant to Liquid-Liquid Extraction Systems

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

Lumetta, Gregg J.; Sinkov, Sergey I.; Krause, Jeanette A.

2016-01-27

The complexes formed during the extraction of neodymium(III) into hydrophobic solvents containing acidic organophosphorus extractants were probed by single-crystal X-ray diffractometry, visible spectrophotometry, and Fourier-transform infrared spectroscopy. The crystal structure of the compound Nd(DMP)3 (1, DMP = dimethyl phosphate) revealed a polymeric arrangement in which each Nd(III) center is surrounded by six DMP oxygen atoms in a pseudo-octahedral environment. Adjacent Nd(III) ions are bridged by (MeO)2POO– anions, forming the polymeric network. The diffuse reflectance visible spectrum of 1 is nearly identical to that of the solid that is formed when an n-dodecane solution of di-(2-ethylhexyl)phosphoric acid (HA) is saturated withmore » Nd(III), indicating a similar coordination environment around the Nd center in the NdA3 solid. The visible spectrum of the HA solution fully loaded with Nd(III) is very similar to that of the NdA3 material, both displaying hypersensitive bands characteristic of an pseudo-octahedral coordination environment around Nd. These spectral characteristics persisted across a wide range of organic Nd concentrations, suggesting that the pseudo-octahedral coordination environment is maintained from dilute to saturated conditions.« less

Neodymium(III) Complexes of Dialkylphosphoric and Dialkylphosphonic Acids Relevant to Liquid-Liquid Extraction Systems.

PubMed

Lumetta, Gregg J; Sinkov, Sergey I; Krause, Jeanette A; Sweet, Lucas E

2016-02-15

The complexes formed during the extraction of neodymium(III) into hydrophobic solvents containing acidic organophosphorus extractants were probed by single-crystal X-ray diffractometry, visible spectrophotometry, and Fourier-transform infrared spectroscopy. The crystal structure of the compound Nd(DMP)3 (1, DMP = dimethyl phosphate) revealed a polymeric arrangement in which each Nd(III) center is surrounded by six DMP oxygen atoms in a pseudo-octahedral environment. Adjacent Nd(III) ions are bridged by (MeO)2POO(-) anions, forming the polymeric network. The diffuse reflectance visible spectrum of 1 is nearly identical to that of the solid that is formed when an n-dodecane solution of di(2-ethylhexyl)phosphoric acid (HA) is saturated with Nd(III), indicating a similar coordination environment around the Nd center in the NdA3 solid. The visible spectrum of the HA solution fully loaded with Nd(III) is very similar to that of the NdA3 material, both displaying hypersensitive bands characteristic of an pseudo-octahedral coordination environment around Nd. These spectral characteristics persisted across a wide range of organic Nd concentrations, suggesting that the pseudo-octahedral coordination environment is maintained from dilute to saturated conditions.

Prebiotic Oxidative Polymerization of 2,3 Dimercaptopropanol on the Surface of Iron(III) Hydroxide Oxide

NASA Technical Reports Server (NTRS)

Weber, Arthur L.

1994-01-01

The oxidation of 2,3-Dimercapto-1-propanol by ferric ions on the surface of iron (III) hydroxide oxide yielded polydisulfide polymers. This polymerization occured readily at low dithiol concentration under mild aqueous conditions. Polydisulfide polymers up to the 15-mer were synthesized from 1 mM dithiol in 5 ml water reacted with iron (III) hydroxide oxide (20 mg, 160 micro mole Fe) for 3 days under anaerobic conditions at 40 C and pH 4. About 91% of the dithiol was converted to short soluble oligomers and 9% to insoluble larger oligomers that were isolated with the mineral phase. Reactions at higher dithiol concentrations with the same ratio of dithiol to mineral gave a higher yield of the larger insoluble oligomers. The relationship of these results to prebiotic polymer synthesis will be discussed.

Preparation, Physical-Chemical Characterization, and Cytocompatibility of Polymeric Calcium Phosphate Cements

PubMed Central

Khashaba, Rania M.; Moussa, Mervet; Koch, Christopher; Jurgensen, Arthur R.; Missimer, David M.; Rutherford, Ronny L.; Chutkan, Norman B.; Borke, James L.

2011-01-01

Aim. Physicochemical mechanical and in vitro biological properties of novel formulations of polymeric calcium phosphate cements (CPCs) were investigated. Methods. Monocalcium phosphate, calcium oxide, and synthetic hydroxyapatite were combined with either modified polyacrylic acid, light activated polyalkenoic acid, or polymethyl vinyl ether maleic acid to obtain Types I, II, and III CPCs. Setting time, compressive and diametral strength of CPCs was compared with zinc polycarboxylate cement (control). Specimens were characterized using X-ray diffraction, scanning electron microscopy, and infrared spectroscopy. In vitro cytotoxicity of CPCs and control was assessed. Results. X-ray diffraction analysis showed hydroxyapatite, monetite, and brushite. Acid-base reaction was confirmed by the appearance of stretching peaks in IR spectra of set cements. SEM revealed rod-like crystals and platy crystals. Setting time of cements was 5–12 min. Type III showed significantly higher strength values compared to control. Type III yielded high biocompatibility. Conclusions. Type III CPCs show promise for dental applications. PMID:21941551

The β2 clamp in the Mycobacterium tuberculosis DNA polymerase III αβ2ε replicase promotes polymerization and reduces exonuclease activity

PubMed Central

Gu, Shoujin; Li, Wenjuan; Zhang, Hongtai; Fleming, Joy; Yang, Weiqiang; Wang, Shihua; Wei, Wenjing; Zhou, Jie; Zhu, Guofeng; Deng, Jiaoyu; Hou, Jian; Zhou, Ying; Lin, Shiqiang; Zhang, Xian-En; Bi, Lijun

2016-01-01

DNA polymerase III (DNA pol III) is a multi-subunit replication machine responsible for the accurate and rapid replication of bacterial genomes, however, how it functions in Mycobacterium tuberculosis (Mtb) requires further investigation. We have reconstituted the leading-strand replication process of the Mtb DNA pol III holoenzyme in vitro, and investigated the physical and functional relationships between its key components. We verify the presence of an αβ2ε polymerase-clamp-exonuclease replicase complex by biochemical methods and protein-protein interaction assays in vitro and in vivo and confirm that, in addition to the polymerase activity of its α subunit, Mtb DNA pol III has two potential proofreading subunits; the α and ε subunits. During DNA replication, the presence of the β2 clamp strongly promotes the polymerization of the αβ2ε replicase and reduces its exonuclease activity. Our work provides a foundation for further research on the mechanism by which the replication machinery switches between replication and proofreading and provides an experimental platform for the selection of antimicrobials targeting DNA replication in Mtb. PMID:26822057

Water-Free Rare Earth-Prussian Blue Type Analogues: Synthesis, Structure, Computational Analysis, and Magnetic Data of {Ln[superscript III](DMF)[subscript 6]Fe[superscript III](CN)[subcsript 6]}[subscript infinity] (Ln = Rare Earths Excluding Pm)

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

Wilson, Duane C.; Liu, Shengming; Chen, Xuenian

2009-11-04

Water-free rare earth(III) hexacyanoferrate(III) complexes, {l_brace}Ln(DMF){sub 6}({mu}-CN){sub 2}Fe(CN){sub 4}{r_brace}{sub {infinity}} (DMF = N,N-dimethylformamide; Ln = Sm, 1; Eu, 2; Gd, 3; Tb, 4; Dy, 5; Ho, 6; Er, 7; Tm, 8; Yb, 9; Lu, 10; Y, 11; La, 12; Ce, 13; Pr, 14; Nd, 15), were synthesized in dry DMF through the metathesis reactions of [(18-crown-6)K]{sub 3}Fe(CN){sub 6} with LnX{sub 3}(DMF){sub n} (X = Cl or NO{sub 3}). Anhydrous DMF solutions of LnX{sub 3}(DMF){sub n} were prepared at room temperature from LnCl{sub 3} or LnX{sub 3} {center_dot} nH{sub 2}O under a dynamic vacuum. All compounds were characterized by IR, X-raymore » powder diffraction (except for 10), and single crystal X-ray diffraction (except for 2, 7, 10). Infrared spectra reveal that a monotonic, linear relationship exists between the ionic radius of the lanthanide and the {nu}{sub {mu}-CN} stretching frequency of 1-10, 12-15 while 11 deviates slightly from the ionic radius relationship. X-ray powder diffraction data are in agreement with powder patterns calculated from single crystal X-ray diffraction results, a useful alternative for bulk sample confirmation when elemental analysis data are difficult to obtain. Eight-coordinate Ln(III) metal centers are observed for all structures. trans-cyanide units of [Fe(CN){sub 6}]{sup 3-} formed isocyanide linkages to Ln(III) resulting in one-dimensional polymeric chains. Structures of compounds 1-9 and 11 are isomorphous, crystallizing in the space group C2/c. Structures of compounds 12-15 are also isomorphous, crystallizing in the space group P2/n. One unique polymeric chain exists in the structures of 1-9 and 11 while two unique polymeric chains exist in structures of 12-15. One of the polymeric chains of 12-15 is similar to that observed for 1-9, 11 while the other is more distorted and has a shorter Ln-Fe distance. Magnetic susceptibility measurements for compounds 3-6, 8, 11 were performed on polycrystalline samples of the compounds.« less

Polymerization of amino acids under high-pressure conditions: Implication to chemical evolution on the early Earth

NASA Astrophysics Data System (ADS)

Kakegawa, T.; Ohara, S.; Ishiguro, T.; Abiko, H.; Nakazawa, H.

2008-12-01

Prebiotic polymerization of amino acids is the most fundamental reaction to promote the chemical evolution for origin of life. Polymerization of amino acids is the dehydration reaction. This questions as to if submarine hydrothermal conditions, thus hydrated enironments, were appropreate for peptide formations. Our previous experiments implied that non-aqueous and high-pressure environments (more than 20 MPa) would be suitable for polymerization of amino acids (Ohara et al., 2006). This leads to the hypothesis that the first peptides may have formed in the Hadean oceanic crustal environments, where dehydration proceeded with availability of appropriate temperatures and pressures. In the present study, experiments simulating the crustal conditions were performed with various pressures (1-175 MPa) and temperatures (100- 200 C degree) using autoclaves. Purified powders (100 mg) of alanine, glycine, valine and aspartic acid were used in the experiments without mixing water in order to examine the solid-solid reactions. The products were analyzed using HPLC and LC-MS. Results indicate that: (1) longer time is required to form peptide compared to those of previous aqueous experiments; (2) pressure has a role to limit the production of melanoidine and cyclic amino acids, which are inhibitors for elongation of peptides; (3) glycine was polymerized up to 11-mer, which was not formed in any previous experiments without catalyses; (4) valine was polymerized up to 3-mer; and (5) aspartic acid was polymerized to 4-mer, accompanied with production of other amino acids. It is noteworthy that high-pressure environments favor all examined polymerization reactions. Such situations would have happened inside of deep oceanic crusts of the early Earth.

LACTB is a filament-forming protein localized in mitochondria

PubMed Central

Polianskyte, Zydrune; Peitsaro, Nina; Dapkunas, Arvydas; Liobikas, Julius; Soliymani, Rabah; Lalowski, Maciej; Speer, Oliver; Seitsonen, Jani; Butcher, Sarah; Cereghetti, Grazia M.; Linder, Matts D.; Merckel, Michael; Thompson, James; Eriksson, Ove

2009-01-01

LACTB is a mammalian active-site serine protein that has evolved from a bacterial penicillin-binding protein. Penicillin-binding proteins are involved in the metabolism of peptidoglycan, the major bacterial cell wall constituent, implying that LACTB has been endowed with novel biochemical properties during eukaryote evolution. Here we demonstrate that LACTB is localized in the mitochondrial intermembrane space, where it is polymerized into stable filaments with a length extending more than a hundred nanometers. We infer that LACTB, through polymerization, promotes intramitochondrial membrane organization and micro-compartmentalization. These findings have implications for our understanding of mitochondrial evolution and function. PMID:19858488

Monolithic porous graphitic carbons obtained through catalytic graphitization of carbon xerogels

NASA Astrophysics Data System (ADS)

Kiciński, Wojciech; Norek, Małgorzata; Bystrzejewski, Michał

2013-01-01

Pyrolysis of organic xerogels accompanied by catalytic graphitization and followed by selective-combustion purification was used to produce porous graphitic carbons. Organic gels impregnated with iron(III) chloride or nickel(II) acetate were obtained through polymerization of resorcinol and furfural. During the pyrolysis stage graphitization of the gel matrix occurs, which in turn develops mesoporosity of the obtained carbons. The evolution of the carbon into graphitic structures is strongly dependent on the concentrations of the transition metal. Pyrolysis leads to monoliths of carbon xerogel characterized by substantially enhanced mesoporosity resulting in specific surface areas up to 400 m2/g. Removal of the amorphous carbon by selective-combustion purification reduces the xerogels' mesoporosity, occasionally causing loss of their mechanical strength. The graphitized carbon xerogels were investigated by means of SEM, XRD, Raman scattering, TG-DTA and N2 physisorption. Through this procedure well graphitized carbonaceous materials can be obtained as bulk pieces.

Bifunctional phenyl monophosphonic/sulfonic acid ion exchange resin and process for using the same

DOEpatents

Alexandratos, Spiro; Shelley, Christopher A.; Horwitz, E. Philip; Chiarizia, Renato

2001-01-01

A cross-linked water-insoluble ion exchange resin comprised of polymerized monomers having a phenyl ring is disclosed. A contemplated resin contains (i) polymerized phenyl ring-containing monomers having a phosphonic acid ligand linked to the phenyl ring, (ii) about 2 to about 5 millimoles per gram (mmol/g) of phosphorus as phosphonic acid ligands, and (iii) a sufficient amount of a sulfonic acid ligand such that the ratio of mmol/g of phosphonic acid to mmol/g sulfonic acid is up to 3:1. A process for removing polyvalent metal cations from aqueous solution, and a process for removing iron(III) cations from acidic copper(II) cation-containing solutions that utilize the contemplated resin or other resins are disclosed.

Bifunctional phenyl monophosphonic/sulfonic acid ion exchange resin and process for using the same

DOEpatents

Alexandratos, Spiro; Shelley, Christopher A.; Horwitz, E. Philip; Chiarizia, Renato; Gula, Michael J.; Xue, Sui; Harvey, James T.

2002-01-01

A cross-linked water-insoluble ion exchange resin comprised of polymerized monomers having a phenyl ring is disclosed. A contemplated resin contains (i) polymerized phenyl ring-containing monomers having a phosphonic acid ligand linked to the phenyl ring, (ii) about 2 to about 5 millimoles per gram (mmol/g) of phosphorus as phosphonic acid ligands, and (iii) a sufficient amount of a sulfonic acid ligand such that the ratio of mmol/g of phosphonic acid to mmol/g sulfonic acid is up to 3:1. A process for removing polyvalent metal cations from aqueous solution, and a process for removing iron(III) cations from acidic copper(II) cation-containing solutions that utilize the contemplated resin or other resins are disclosed.

Importance of Extracellular Polymeric Substances from Thiobacillus ferrooxidans for Bioleaching

PubMed Central

Gehrke, Tilman; Telegdi, Judit; Thierry, Dominique; Sand, Wolfgang

1998-01-01

Leaching bacteria such as Thiobacillus ferrooxidans attach to pyrite or sulfur by means of extracellular polymeric substances (EPS) (lipopolysaccharides). The primary attachment to pyrite at pH 2 is mediated by exopolymer-complexed iron(III) ions in an electrochemical interaction with the negatively charged pyrite surface. EPS from sulfur cells possess increased hydrophobic properties and do not attach to pyrite, indicating adaptability to the substrate or substratum. PMID:9647862

Catalysts and methods for ring opening metathesis polymerization

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

Schrock, Richard Royce; Autenrieth, Benjamin

The present invention, among other things, provides highly syndiotactic poly(dicyclopentadiene) and/or hydrogenated poly(dicyclopentadiene), compositions thereof, and compounds and methods for preparing the same. In some embodiments, a provided compound is a compound of formula I, II or III. In some embodiments, a provided method comprises providing a compound of formula I, II or III.

Polymethacrylate Polymers with Appended Aluminum(III)-Tetraphenylporphyrins: Synthesis, Characterization and Evaluation as Macromolecular Ionophores for Electrochemical and Optical Fluoride Sensors

PubMed Central

Wang, Lin; Meyerhoff, Mark E.

2008-01-01

The synthesis and characterization of a novel polymethacylate polymer with covalently linked Al(III)-tetraphenylporphyrin (Al(III)-TPP) groups is reported. The new polymer is examined as a potential macromolecular ionophore for the preparation of polymeric membrane-based potentiometric and optical fluoride selective sensors. To prepare the polymer, an Al(III) porphyrin monomer modified with a methacrylate functionality is synthesized, allowing insertion into a polymethacrylate block copolymer (methyl methacrylate and decyl methacrylate) backbone. The resulting polymer can then be incorporated, along with appropriate additives, into conventional plasticized poly(vinyl chloride) films for testing electrochemical and optical fluoride response properties. The covalent attachment of the Al(III)-TPP ionophore to the copolymer matrix provides potentiometric sensors that exhibit significant selectivity for fluoride ion with extended lifetimes (compared to ion-selective membrane electrodes formulated with conventional free Al(III)-TPP structure). However, quite surprisingly, the attachment of the ionophore to the polymer does not eliminate the interaction of Al(III)-TPP structures to form dimeric species within the membrane phase in the presence of fluoride ion. Such interactions are confirmed by UV/visible spectroscopy of the blended polymeric films. Use of the new polymer-Al(III)-TPP conjugates to prepare optical fluoride sensors by co-incorporating a lipophilic pH indicator (4’,5’-dibromofluorescein octadecyl ester; ETH7075) is also examined and the resulting optical sensing films are shown to exhibit excellent selectivity for fluoride, with the potential for prolonged operational lifetime. PMID:18298973

Humic acids facilitated microbial reduction of polymeric Pu(IV) under anaerobic conditions.

PubMed

Xie, Jinchuan; Liang, Wei; Lin, Jianfeng; Zhou, Xiaohua; Li, Mei

2018-01-01

Flavins and humic substances have been extensively studied with emphasis on their ability to transfer extracellular electrons to insoluble metal oxides. Nevertheless, whether the low-solubility Pu(IV) polymers are microbially reduced to aqueous Pu(III) remains uncertain. Experiments were conducted under anaerobic and slightly alkaline conditions to study the difference between humic acids and flavins to transport extracellular electrons to Pu(IV) polymers. Our study demonstrates that Shewanella putrefaciens was unable to directly reduce polymeric Pu(IV) with a notably low reduction rate (3.4×10 -12 mol/L Pu(III) aq within 144h). The relatively high redox potential of flavins reveals the thermodynamically unfavorable reduction: E h (PuO 2 (am)/Pu 3+ )

Highly selective optical fluoride ion sensor with submicromolar detection limit based on aluminum(III) octaethylporphyrin in thin polymeric film.

PubMed

Badr, Ibrahim H A; Meyerhoff, Mark E

2005-04-20

A highly selective, sensitive, and reversible fluoride optical sensing film based on aluminum(III)octaethylporphyrin as a fluoride ionophore and a lipophilic pH indicator as the optical transducer is described. The fluoride optical sensing films exhibit a submicromolar detection limit and high discrimination for fluoride over several lipophilic anions such as nitrate, perchlorate, and thiocyanate.

Generation of Synthetic Copolymer Libraries by Combinatorial Assembly on Nucleic Acid Templates.

PubMed

Kong, Dehui; Yeung, Wayland; Hili, Ryan

2016-07-11

Recent advances in nucleic acid-templated copolymerization have expanded the scope of sequence-controlled synthetic copolymers beyond the molecular architectures witnessed in nature. This has enabled the power of molecular evolution to be applied to synthetic copolymer libraries to evolve molecular function ranging from molecular recognition to catalysis. This Review seeks to summarize different approaches available to generate sequence-defined monodispersed synthetic copolymer libraries using nucleic acid-templated polymerization. Key concepts and principles governing nucleic acid-templated polymerization, as well as the fidelity of various copolymerization technologies, will be described. The Review will focus on methods that enable the combinatorial generation of copolymer libraries and their molecular evolution for desired function.

A master equation approach to actin polymerization applied to endocytosis in yeast.

PubMed

Wang, Xinxin; Carlsson, Anders E

2017-12-01

We present a Master Equation approach to calculating polymerization dynamics and force generation by branched actin networks at membranes. The method treats the time evolution of the F-actin distribution in three dimensions, with branching included as a directional spreading term. It is validated by comparison with stochastic simulations of force generation by actin polymerization at obstacles coated with actin "nucleation promoting factors" (NPFs). The method is then used to treat the dynamics of actin polymerization and force generation during endocytosis in yeast, using a model in which NPFs form a ring around the endocytic site, centered by a spot of molecules attaching the actin network strongly to the membrane. We find that a spontaneous actin filament nucleation mechanism is required for adequate forces to drive the process, that partial inhibition of branching and polymerization lead to different characteristic responses, and that a limited range of polymerization-rate values provide effective invagination and obtain correct predictions for the effects of mutations in the active regions of the NPFs.

A master equation approach to actin polymerization applied to endocytosis in yeast

PubMed Central

Wang, Xinxin

2017-01-01

We present a Master Equation approach to calculating polymerization dynamics and force generation by branched actin networks at membranes. The method treats the time evolution of the F-actin distribution in three dimensions, with branching included as a directional spreading term. It is validated by comparison with stochastic simulations of force generation by actin polymerization at obstacles coated with actin “nucleation promoting factors” (NPFs). The method is then used to treat the dynamics of actin polymerization and force generation during endocytosis in yeast, using a model in which NPFs form a ring around the endocytic site, centered by a spot of molecules attaching the actin network strongly to the membrane. We find that a spontaneous actin filament nucleation mechanism is required for adequate forces to drive the process, that partial inhibition of branching and polymerization lead to different characteristic responses, and that a limited range of polymerization-rate values provide effective invagination and obtain correct predictions for the effects of mutations in the active regions of the NPFs. PMID:29240771

Silicon and aluminum doping effects on the microstructure and properties of polymeric amorphous carbon films

NASA Astrophysics Data System (ADS)

Liu, Xiaoqiang; Hao, Junying; Xie, Yuntao

2016-08-01

Polymeric amorphous carbon films were prepared by radio frequency (R.F. 13.56 MHz) magnetron sputtering deposition. The microstructure evolution of the deposited polymeric films induced by silicon (Si) and aluminum(Al) doping were scrutinized through infrared spectroscopy, multi-wavelength Raman spectroscopy, scanning electron microscopy (SEM) and high resolution transmission electron microscopy (HRTEM). The comparative results show that Si doping can enhance polymerization and Al doping results in an increase in the ordered carbon clusters. Si and Al co-doping into polymeric films leads to the formation of an unusual dual nanostructure consisting of cross-linked polymer-like hydrocarbon chains and fullerene-like carbon clusters. The super-high elasticity and super-low friction coefficients (<0.002) under a high vacuum were obtained through Si and Al co-doping into the films. Unconventionally, the co-doped polymeric films exhibited a superior wear resistance even though they were very soft. The relationship between the microstructure and properties of the polymeric amorphous carbon films with different elements doping are also discussed in detail.

The unusual dynamics of parasite actin result from isodesmic polymerization

PubMed Central

Skillman, Kristen M.; Ma, Christopher I.; Fremont, Daved H.; Diraviyam, Karthikeyan; Cooper, John A.; Sept, David; Sibley, L. David

2013-01-01

Previous reports have indicated that parasite actins are short and inherently unstable, despite being required for motility. Here, we re-examine the polymerization properties of actin in Toxoplasma gondii (TgACTI), unexpectedly finding that it exhibits isodesmic polymerization in contrast to the conventional nucleation-elongation process of all previously studied actins from both eukaryotes and bacteria. TgACTI polymerization kinetics lacks both a lag phase and critical concentration, normally characteristic of actins. Unique among actins, the kinetics of assembly can be fit with a single set of rate constants for all subunit interactions, without need for separate nucleation and elongation rates. This isodesmic model accurately predicts the assembly, disassembly, and the size distribution of TgACTI filaments in vitro, providing a mechanistic explanation for actin dynamics in vivo. Our findings expand the repertoire of mechanisms by which actin polymerization is governed and offer clues about the evolution of self-assembling, stabilized protein polymers. PMID:23921463

Direct Detection of Fe(II) in Extracellular Polymeric Substances (EPS) at the Mineral-Microbe Interface in Bacterial Pyrite Leaching

PubMed Central

Mitsunobu, Satoshi; Zhu, Ming; Takeichi, Yasuo; Ohigashi, Takuji; Suga, Hiroki; Jinno, Muneaki; Makita, Hiroko; Sakata, Masahiro; Ono, Kanta; Mase, Kazuhiko; Takahashi, Yoshio

2016-01-01

We herein investigated the mechanisms underlying the contact leaching process in pyrite bioleaching by Acidithiobacillus ferrooxidans using scanning transmission X-ray microscopy (STXM)-based C and Fe near edge X-ray absorption fine structure (NEXAFS) analyses. The C NEXAFS analysis directly showed that attached A. ferrooxidans produces polysaccharide-abundant extracellular polymeric substances (EPS) at the cell-pyrite interface. Furthermore, by combining the C and Fe NEXAFS results, we detected significant amounts of Fe(II), in addition to Fe(III), in the interfacial EPS at the cell-pyrite interface. A probable explanation for the Fe(II) in detected EPS is the leaching of Fe(II) from the pyrite. The detection of Fe(II) also indicates that Fe(III) resulting from pyrite oxidation may effectively function as an oxidizing agent for pyrite at the cell-pyrite interface. Thus, our results imply that a key role of Fe(III) in EPS, in addition to its previously described role in the electrostatic attachment of the cell to pyrite, is enhancing pyrite dissolution. PMID:26947441

Photoreactivity of ETS-10.

PubMed

Howe, R F; Krisnandi, Y K

2001-09-07

Irradiation of H-ETS-10 in the presence of adsorbed methanol or ethene causes photoreduction of Ti(IV) to Ti(III); photoreduction does not occur for Na, K-ETS-10, but a photoinduced polymerization of ethene is observed.

An exactly solvable model of polymerization

NASA Astrophysics Data System (ADS)

Lushnikov, A. A.

2017-08-01

This paper considers the evolution of a polydisperse polymerizing system comprising g1,g2 … - mers carrying ϕ1,ϕ2 … functional groups reacting with one another and binding the g-mers together. In addition, the g-mers are assumed to be added at random by one at a time with a known rate depending on their mass g and functionality ϕ . Assuming that the rate of binding of two g-mers is proportional to the product of the numbers of nonreacted functional groups the kinetic equation for the distribution of clusters (g-mers) over their mass and functionalities is formulated and then solved by applying the generating function method. In contrast to existing approaches this kinetic equation operates with the efficiencies proportional to the product of the numbers of active functional groups in the clusters rather than to the product of their masses. The evolution process is shown to reveal a phase transition: the emergence of a giant linked cluster (the gel) whose mass is comparable to the total mass of the whole polymerizing system. The time dependence of the moments of the distribution of linked components over their masses and functionalities is investigated. The polymerization process terminates by forming a residual spectrum of sol particles in addition to the gel.

Deducing multiple interfacial dynamics during polymeric foaming.

PubMed

Chandan, Mohammed Rehaan; Naskar, Nilanjon; Das, Anuja; Mukherjee, Rabibrata; Harikrishnan, Gopalakrishna Pillai

2018-06-15

Several interfacial phenomena are active during polymeric foaming, the dynamics of which significantly influence terminal stability, cell structure and in turn the thermo-mechanical properties of temporally evolved foam. Understanding these dynamics is important in achieving desired foam properties. Here, we introduce a method to simultaneously portray the time evolution of bubble growth, lamella thinning and Plateau border drainage, occurring during reactive polymeric foaming. In this method, we initially conduct bulk and surface shear rheology under polymerizing and non-foaming conditions. In a subsequent step, foaming experiments were conducted in a rheometer. The microscopic structural dimensions pertaining to the terminal values of the dynamics of each interfacial phenomena are then measured using a combination of scanning electron microscopy, optical microscopy and imaging ellipsometry, after the foaming is over. The measured surface and bulk rheological parameters are incorporated in time evolution equations that are derived from mass and momentum transport occurring when a model viscoelastic fluid is foamed by gas dispersion. Analytical and numerical solutions to these equations portray the dynamics. We demonstrate this method for a series of reactive polyurethane foams generated from different chemical sources. The effectiveness of our method is in simultaneously obtaining these dynamics that are difficult to directly monitor due to short active durations over multiple length scales.

Effects of humic acid concentration on the microbially-mediated reductive solubilization of Pu(IV) polymers.

PubMed

Xie, Jinchuan; Han, Xiaoyuan; Wang, Weixian; Zhou, Xiaohua; Lin, Jianfeng

2017-10-05

The role of humic acid concentration in the microbially-mediated reductive solubilization of Pu(IV) polymers remains unclear until now. The effects of humic concentration (0-150.5mg/L) on the rate and extent of reduction of polymeric Pu(IV) were studied under anaerobic and pH 7.2 conditions. The results show that Shewanella putrefaciens, secreting flavins as endogenous electron shuttles, cannot notably stimulate the reduction of polymeric Pu(IV). In the presence of humic acids, the reduction rate of polymeric Pu(IV) increased with increasing humic concentrations (0-15.0mg/L): e.g., a 102-fold increase from 4.1×10 -15 (HA=0) to 4.2×10 -13 mol Pu(III) aq /h (HA=15.0mg/L). The bioreduced humic acids by S. putrefaciens facilitated the extracellular electron transfer to Pu(IV) polymers and thus the reduction of polymeric Pu(IV) to Pu(III) aq became thermodynamically favorable. However, the reduction rate did not increase but decrease with increasing humic concentrations from 15.0 to 150.5mg/L. Humic coatings formed on the polymer surfaces at relatively high humic concentrations limited the electron transfer to the polymers and thus decreased the reduction rate. The finding of the dynamic role of humic acids in the bioreductive solubilization may be helpful in evaluating Pu mobility in the geosphere. Copyright © 2017 Elsevier B.V. All rights reserved.

Comparative Effect of Different Polymerization Techniques on the Flexural and Surface Properties of Acrylic Denture Bases.

PubMed

Gad, Mohammed M; Fouda, Shaimaa M; ArRejaie, Aws S; Al-Thobity, Ahmad M

2017-05-22

Polymerization techniques have been modified to improve physical and mechanical properties of polymethylmethacrylate (PMMA) denture base, as have the laboratory procedures that facilitate denture construction techniques. The purpose of the present study was to investigate the effect of autoclave polymerization on flexural strength, elastic modulus, surface roughness, and the hardness of PMMA denture base resins. Major Base and Vertex Implacryl heat-polymerized acrylic resins were used to fabricate 180 specimens. According to the polymerization technique, tested groups were divided into: group I (water-bath polymerization), group II (short autoclave polymerization cycle, 60°C for 30 minutes, then 130°C for 10 minutes), and group III (long autoclave polymerization cycle, 60°C for 30 minutes, then 130°C for 20 minutes). Each group was divided into two subgroups based on the materials used. Flexural strength and elastic modulus were determined by a three-point bending test. Surface roughness and hardness were evaluated with a profilometer and Vickers hardness (VH) test, respectively. One-way ANOVA and the Tukey-Kramer multiple-comparison test were used for results analysis, which were statistically significant at p ≤ 0.05. Autoclave polymerization showed a significant increase in flexural strength and hardness of the two resins (p < 0.05). The elastic modulus showed a significant increase in the major base resin, while a significant decrease was seen for Vertex Implacryl in all groups (p < 0.05); however, there was no significant difference in surface roughness between autoclave polymerization and water-bath polymerization (p > 0.05). Autoclave polymerization significantly increased the flexural properties and hardness of PMMA denture bases, while the surface roughness was within acceptable clinical limits. For a long autoclave polymerization cycle, it could be used as an alternative to water-bath polymerization. © 2017 by the American College of Prosthodontists.

Curing of a Bisphenol-E Based Cyanate Ester using Magnetic Nanoparticles as an Internal Heat Source through Induction Heating

DTIC Science & Technology

2013-11-01

magnetic field as a heat source for the polymerization avoids some of these difficulties. EXPERIMENTAL SECTION Iron (III) chloride hexahydrate (ACS...reagent, 97%), iron (II) chloride tetrahydrate (ReagentPlus®, 98%), tetramethylammonium hydroxide solution (25 wt. % in water), and oleic acid (technical...Edwards Air Force Base and used without further purification. Preparation of Iron Oxide Magnetic Nanoparticles.51 Iron (III) chloride hexahydrate (11.75

Chain-Growth Methods for the Synthesis of High Molecular Weight Conducting and Semiconducting Polymers

DTIC Science & Technology

2013-08-25

to produce the desired polymerization in analogy to the well-known “super glue ” anionic polymerization. Although there are abundant examples of...light (a) and UV light (b). 5 are further functionalized and block polymers formed with polynorborene have elastomeric properties. The...top) and UV (bottom) light show the evolution of the band gap of the polymer with increasing molecular weight. The plot on the right shows the

The Moon as a recorder of organic evolution in the early solar system: a lunar regolith analog study.

PubMed

Matthewman, Richard; Court, Richard W; Crawford, Ian A; Jones, Adrian P; Joy, Katherine H; Sephton, Mark A

2015-02-01

The organic record of Earth older than ∼3.8 Ga has been effectively erased. Some insight is provided to us by meteorites as well as remote and direct observations of asteroids and comets left over from the formation of the Solar System. These primitive objects provide a record of early chemical evolution and a sample of material that has been delivered to Earth's surface throughout the past 4.5 billion years. Yet an effective chronicle of organic evolution on all Solar System objects, including that on planetary surfaces, is more difficult to find. Fortunately, early Earth would not have been the only recipient of organic matter-containing objects in the early Solar System. For example, a recently proposed model suggests the possibility that volatiles, including organic material, remain archived in buried paleoregolith deposits intercalated with lava flows on the Moon. Where asteroids and comets allow the study of processes before planet formation, the lunar record could extend that chronicle to early biological evolution on the planets. In this study, we use selected free and polymeric organic materials to assess the hypothesis that organic matter can survive the effects of heating in the lunar regolith by overlying lava flows. Results indicate that the presence of lunar regolith simulant appears to promote polymerization and, therefore, preservation of organic matter. Once polymerized, the mineral-hosted newly formed organic network is relatively protected from further thermal degradation. Our findings reveal the thermal conditions under which preservation of organic matter on the Moon is viable.

Structural basis of reverse nucleotide polymerization

PubMed Central

Nakamura, Akiyoshi; Nemoto, Taiki; Heinemann, Ilka U.; Yamashita, Keitaro; Sonoda, Tomoyo; Komoda, Keisuke; Tanaka, Isao; Söll, Dieter; Yao, Min

2013-01-01

Nucleotide polymerization proceeds in the forward (5′-3′) direction. This tenet of the central dogma of molecular biology is found in diverse processes including transcription, reverse transcription, DNA replication, and even in lagging strand synthesis where reverse polymerization (3′-5′) would present a “simpler” solution. Interestingly, reverse (3′-5′) nucleotide addition is catalyzed by the tRNA maturation enzyme tRNAHis guanylyltransferase, a structural homolog of canonical forward polymerases. We present a Candida albicans tRNAHis guanylyltransferase-tRNAHis complex structure that reveals the structural basis of reverse polymerization. The directionality of nucleotide polymerization is determined by the orientation of approach of the nucleotide substrate. The tRNA substrate enters the enzyme’s active site from the opposite direction (180° flip) compared with similar nucleotide substrates of canonical 5′-3′ polymerases, and the finger domains are on opposing sides of the core palm domain. Structural, biochemical, and phylogenetic data indicate that reverse polymerization appeared early in evolution and resembles a mirror image of the forward process. PMID:24324136

Dense Carbon Monoxide to 160 GPa: Stepwise Polymerization to Two-Dimensional Layered Solid

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

Ryu, Young-Jay; Kim, Minseob; Lim, Jinhyuk

Carbon monoxide (CO) is the first molecular system found to transform into a nonmolecular “polymeric” solid above 5.5 GPa, yet been studied beyond 10 GPa. Here, we show a series of pressure-induced phase transformations in CO to 160 GPa: from a molecular solid to a highly colored, low-density polymeric phase I to translucent, high-density phase II to transparent, layered phase III. The properties of these phases are consistent with those expected from recently predicted 1D P2 1/m, 3D I2 12 12 1, and 2D Cmcm structures, respectively. Thus, the present results advocate a stepwise polymerization of CO triple bonds tomore » ultimately a 2D singly bonded layer structure with an enhanced ionic character.« less

Aminonitriles - Possible role in chemical evolution

NASA Technical Reports Server (NTRS)

Chadha, M. S.; Molton, P. M.; Ponnamperuma, C.

1975-01-01

The formation of HCN, ammonium cyanide, alkylnitriles, aminoacetonitrile and its C- and N-methyl homologs was demonstrated earlier in a simulated Jovian atmosphere. The polymeric material resulting in these experiments was shown to give glycine, alanine, sarcosine, aspartic acid and some imino dibasic acids on acid hydrolysis, suggesting thereby the participation of the monomeric nitriles in the formation of the polymeric product(s). Further examination of products resulting from semicorona and arc discharge through a mixture of methane and ammonia has provided evidence for the formation of alkylaminopropionitriles as a complex mixture and also some pyridyl and pyrimidyl type heterocyclic compounds. A gas chromatograph/mass spectrometer examination of the heterocyclics showed resemblance with those found in some carbonaceous chondrites. The significance of these findings in relation to chemical evolution is discussed.

LACCASE Is Necessary and Nonredundant with PEROXIDASE for Lignin Polymerization during Vascular Development in Arabidopsis[C][W

PubMed Central

Zhao, Qiao; Nakashima, Jin; Chen, Fang; Yin, Yanbin; Fu, Chunxiang; Yun, Jianfei; Shao, Hui; Wang, Xiaoqiang; Wang, Zeng-Yu; Dixon, Richard A.

2013-01-01

The evolution of lignin biosynthesis was critical in the transition of plants from an aquatic to an upright terrestrial lifestyle. Lignin is assembled by oxidative polymerization of two major monomers, coniferyl alcohol and sinapyl alcohol. Although two recently discovered laccases, LAC4 and LAC17, have been shown to play a role in lignin polymerization in Arabidopsis thaliana, disruption of both genes only leads to a relatively small change in lignin content and only under continuous illumination. Simultaneous disruption of LAC11 along with LAC4 and LAC17 causes severe plant growth arrest, narrower root diameter, indehiscent anthers, and vascular development arrest with lack of lignification. Genome-wide transcript analysis revealed that all the putative lignin peroxidase genes are expressed at normal levels or even higher in the laccase triple mutant, suggesting that lignin laccase activity is necessary and nonredundant with peroxidase activity for monolignol polymerization during plant vascular development. Interestingly, even though lignin deposition in roots is almost completely abolished in the lac11 lac4 lac17 triple mutant, the Casparian strip, which is lignified through the activity of peroxidase, is still functional. Phylogenetic analysis revealed that lignin laccase genes have no orthologs in lower plant species, suggesting that the monolignol laccase genes diverged after the evolution of seed plants. PMID:24143805

Polymeric Coatings for Combating Biocorrosion

NASA Astrophysics Data System (ADS)

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

2018-03-01

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

Synthesis and redox activity of "clicked" triazolylbiferrocenyl polymers, network encapsulation of gold and silver nanoparticles and anion sensing.

PubMed

Rapakousiou, Amalia; Deraedt, Christophe; Irigoyen, Joseba; Wang, Yanlan; Pinaud, Noël; Salmon, Lionel; Ruiz, Jaime; Moya, Sergio; Astruc, Didier

2015-03-02

The design of redox-robust polymers is called for in view of interactions with nanoparticles and surfaces toward applications in nanonetwork design, sensing, and catalysis. Redox-robust triazolylbiferrocenyl (trzBiFc) polymers have been synthesized with the organometallic group in the side chain by ring-opening metathesis polymerization using Grubbs-III catalyst or radical polymerization and with the organometallic group in the main chain by Cu(I) azide alkyne cycloaddition (CuAAC) catalyzed by [Cu(I)(hexabenzyltren)]Br. Oxidation of the trzBiFc polymers with ferricenium hexafluorophosphate yields the stable 35-electron class-II mixed-valent biferrocenium polymer. Oxidation of these polymers with Au(III) or Ag(I) gives nanosnake-shaped networks (observed by transmission electron microscopy and atomic force microscopy) of this mixed-valent Fe(II)Fe(III) polymer with encapsulated metal nanoparticles (NPs) when the organoiron group is located on the side chain. The factors that are suggested to be synergistically responsible for the NP stabilization and network formation are the polymer bulk, the trz coordination, the nearby cationic charge of trzBiFc, and the inter-BiFc distance. For instance, reduction of such an oxidized trzBiFc-AuNP polymer to the neutral trzBiFc-AuNP polymer with NaBH4 destroys the network, and the product flocculates. The polymers easily provide modified electrodes that sense, via the oxidized Fe(II)Fe(III) and Fe(III)Fe(III) polymer states, respectively, ATP(2-) via the outer ferrocenyl units of the polymer and Pd(II) via the inner Fc units; this recognition works well in dichloromethane, but also to a lesser extent in water with NaCl as the electrolyte.

The potential for chemical evolution on Titan

NASA Technical Reports Server (NTRS)

Beauchamp, P. M.; Lunine, J. I.; Welch, C.

2002-01-01

Sampling of organics to determine oxygen content, extent of acetylene polymerization, existence of chiral molecules and enantiomeric excesses, and searches for specific polymer products, would be of interest in assessing how organic chemistry evolves toward biochemistry. Such efforts would require fairly sophisticated chemical analyses from landed missions. This paper examines this chemistry and the potential instruments that could distinguish chemical evolution.

Nucleotide Selectivity in Abiotic RNA Polymerization Reactions.

PubMed

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

2017-09-01

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

Nucleotide Selectivity in Abiotic RNA Polymerization Reactions

NASA Astrophysics Data System (ADS)

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

2017-09-01

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

Role of metal oxides in chemical evolution

NASA Astrophysics Data System (ADS)

Kamaluddin

2013-06-01

Steps of chemical evolution have been designated as formation of biomonomers followed by their polymerization and then to modify in an organized structure leading to the formation of first living cell. Formation of small molecules like amino acids, organic bases, sugar etc. could have occurred in the reducing atmosphere of the primitive Earth. Polymerization of these small molecules could have required some catalyst. In addition to clay, role of metal ions and metal complexes as prebiotic catalyst in the synthesis and polymerization of biomonomers cannot be ruled out. Metal oxides are important constituents of Earth crust and that of other planets. These oxides might have adsorbed organic molecules and catalyzed the condensation processes, which may have led to the formation of first living cell. Different studies were performed in order to investigate the role of metal oxides (especially oxides of iron and manganese) in chemical evolution. Iron oxides (goethite, akaganeite and hematite) as well as manganese oxides (MnO, Mn2O3, Mn3O4 and MnO2) were synthesized and their characterization was done using IR, powder XRD, FE-SEM and TEM. Role of above oxides was studied in the adsorption of ribose nucleotides, formation of nucleobases from formamide and oligomerization of amino acids. Above oxides of iron and manganese were found to have good adsorption affinity towards ribose nucleotides, high catalytic activity in the formation of several nucleobases from formamide and oligomerization of glycine and alanine. Characterization of products was performed using UV, IR, HPLC and ESI-MS techniques. Presence of hematite-water system on Mars has been suggested to be a positive indicator in the chemical evolution on Mars.

The Moon as a Recorder of Organic Evolution in the Early Solar System: A Lunar Regolith Analog Study

PubMed Central

Court, Richard W.; Crawford, Ian A.; Jones, Adrian P.; Joy, Katherine H.; Sephton, Mark A.

2015-01-01

Abstract The organic record of Earth older than ∼3.8 Ga has been effectively erased. Some insight is provided to us by meteorites as well as remote and direct observations of asteroids and comets left over from the formation of the Solar System. These primitive objects provide a record of early chemical evolution and a sample of material that has been delivered to Earth's surface throughout the past 4.5 billion years. Yet an effective chronicle of organic evolution on all Solar System objects, including that on planetary surfaces, is more difficult to find. Fortunately, early Earth would not have been the only recipient of organic matter–containing objects in the early Solar System. For example, a recently proposed model suggests the possibility that volatiles, including organic material, remain archived in buried paleoregolith deposits intercalated with lava flows on the Moon. Where asteroids and comets allow the study of processes before planet formation, the lunar record could extend that chronicle to early biological evolution on the planets. In this study, we use selected free and polymeric organic materials to assess the hypothesis that organic matter can survive the effects of heating in the lunar regolith by overlying lava flows. Results indicate that the presence of lunar regolith simulant appears to promote polymerization and, therefore, preservation of organic matter. Once polymerized, the mineral-hosted newly formed organic network is relatively protected from further thermal degradation. Our findings reveal the thermal conditions under which preservation of organic matter on the Moon is viable. Key Words: Moon—Regolith—Organic preservation—Biomarkers. Astrobiology 15, 154–168. PMID:25615648

Cobalt-Mediated Radical Polymerization of Vinyl Acetate and Acrylonitrile in Supercritical Carbon Dioxide.

PubMed

Kermagoret, Anthony; Chau, Ngoc Do Quyen; Grignard, Bruno; Cordella, Daniela; Debuigne, Antoine; Jérôme, Christine; Detrembleur, Christophe

2016-03-01

Cobalt-mediated radical polymerization (CMRP) of vinyl acetate (VAc) is successfully achieved in supercritical carbon dioxide (scCO2). CMRP of VAc is conducted using an alkyl-cobalt(III) adduct that is soluble in scCO2. Kinetics studies coupled to visual observations of the polymerization medium highlight that the melt viscosity and PVAc molar mass (Mn) are key parameters that affect the CMRP in scCO2. It is noticed that CMRP is controlled for Mn up to 10 000 g mol(-1), but loss of control is progressively observed for higher molar masses when PVAc precipitates in the polymerization medium. Low molar mass PVAc macroinitiator, prepared by CMRP in scCO2, is then successfully used to initiate the acrylonitrile polymerization. PVAc-b-PAN block copolymer is collected as a free flowing powder at the end of the process although the dispersity of the copolymer increases with the reaction time. Although optimization is required to decrease the dispersity of the polymer formed, this CMRP process opens new perspectives for macromolecular engineering in scCO2 without the utilization of fluorinated comonomers or organic solvents. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Optimizing tooth form with direct posterior composite restorations.

PubMed

Raghu, Ramya; Srinivasan, Raghu

2011-10-01

Advances in material sciences and technology have provided today's clinicians the strategies to transform the mechanistic approach of operative dentistry into a biologic philosophy. In the last three decades, composite resins have gone from being just an esthetically pleasing way of restoring Class III and Class IV cavities to become the universal material for both anterior and posterior situations as they closely mimic the natural esthetics while restoring the form of the human dentition. In order to enhance their success, clinicians have to rethink their protocol instead of applying the same restorative concepts and principles practiced with metallic restorations. Paralleling the evolution of posterior composite resin materials, cavity designs, restorative techniques and armamentarium have also developed rapidly to successfully employ composite resins in Class II situations. Most of the earlier problems with posterior composites such as poor wear resistance, polymerization shrinkage, postoperative sensitivity, predictable bonding to dentin, etc., have been overcome to a major extent. However, the clinically relevant aspect of achieving tight contacts in Class II situations has challenged clinicians the most. This paper reviews the evolution of techniques and recent developments in achieving predictable contacts with posterior composites. A Medline search was performed for articles on "direct posterior composite contacts." The keywords used were "contacts and contours of posterior composites." The reference list of each article was manually checked for additional articles of relevance.

Interaction of Metal Oxides with Biomolecules: Implication in Astrobiology

NASA Astrophysics Data System (ADS)

Kamaluddin; Iqubal, Md. Asif

2014-08-01

Steps of chemical evolution have been designated as formation of biomonomers followed by their polymerization and then to modify in an organized structure leading to the formation of first living cell. Polymerization of biomonomers could have required some catalyst. In addition to clay, role of metal ions and metal complexes as prebiotic catalyst in the synthesis and polymerization of biomonomers cannot be ruled out. Metal oxides are important constituents of Earth crust and that of other planets. These oxides might have adsorbed organic molecules and catalyzed the condensation processes, which may have led to the formation of first living cell. Different studies were performed in order to investigate the role of metal oxides (especially oxides of iron and manganese) in chemical evolution. Iron oxides (goethite, akaganeite and hematite) as well as manganese oxides (MnO, Mn2O3, Mn3O4 and MnO2) were synthesized and their characterization was done using IR, powder XRD, FE-SEM and TEM. Role of above oxides was studied in the adsorption of ribose nucleotides, formation of nucleobases from formamide and oligomerization of amino acids. Above oxides of iron and manganese were found to have good adsorption affinity towards ribose nucleotides, high catalytic activity in the formation of several nucleobases from formamide and oligomerization of glycine and alanine. Characterization of products was performed using UV, IR, HPLC and ESI-MS techniques. Presence of hematite-water system on Mars has been suggested to be a positive indicator in the chemical evolution on Mars.

Complexity in modeling of residual stresses and strains during polymerization of bone cement: effects of conversion, constraint, heat transfer, and viscoelastic property changes.

PubMed

Gilbert, Jeremy L

2006-12-15

Aseptic loosening of cemented joint prostheses remains a significant concern in orthopedic biomaterials. One possible contributor to cement loosening is the development of porosity, residual stresses, and local fracture of the cement that may arise from the in-situ polymerization of the cement. In-situ polymerization of acrylic bone cement is a complex set of interacting processes that involve polymerization reactions, heat generation and transfer, full or partial mechanical constraint, evolution of conversion- and temperature-dependent viscoelastic material properties, and thermal and conversion-driven changes in the density of the cement. Interactions between heat transfer and polymerization can lead to polymerization fronts moving through the material. Density changes during polymerization can, in the presence of mechanical constraint, lead to the development of locally high residual strain energy and residual stresses. This study models the interactions during bone cement polymerization and determines how residual stresses develop in cement and incorporates temperature and conversion-dependent viscoelastic behavior. The results show that the presence of polymerization fronts in bone cement result in locally high residual strain energies. A novel heredity integral approach is presented to track residual stresses incorporating conversion and temperature dependent material property changes. Finally, the relative contribution of thermal- and conversion-dependent strains to residual stresses is evaluated and it is found that the conversion-based strains are the major contributor to the overall behavior. This framework provides the basis for understanding the complex development of residual stresses and can be used as the basis for developing more complex models of cement behavior.

Self-assembled lipid--polymer hybrid nanoparticles: a robust drug delivery platform.

PubMed

Zhang, Liangfang; Chan, Juliana M; Gu, Frank X; Rhee, June-Wha; Wang, Andrew Z; Radovic-Moreno, Aleksandar F; Alexis, Frank; Langer, Robert; Farokhzad, Omid C

2008-08-01

We report the engineering of a novel lipid-polymer hybrid nanoparticle (NP) as a robust drug delivery platform, with high drug encapsulation yield, tunable and sustained drug release profile, excellent serum stability, and potential for differential targeting of cells or tissues. The NP comprises three distinct functional components: (i) a hydrophobic polymeric core where poorly water-soluble drugs can be encapsulated; (ii) a hydrophilic polymeric shell with antibiofouling properties to enhance NP stability and systemic circulation half-life; and (iii) a lipid monolayer at the interface of the core and the shell that acts as a molecular fence to promote drug retention inside the polymeric core, thereby enhancing drug encapsulation efficiency, increasing drug loading yield, and controlling drug release. The NP is prepared by self-assembly through a single-step nanoprecipitation method in a reproducible and predictable manner, making it potentially suitable for scale-up.

Self-Assembled Lipid-Polymer Hybrid Nanoparticles: A Robust Drug Delivery Platform

PubMed Central

Zhang, Liangfang; Chan, Juliana M; Gu, Frank X; Rhee, June-Wha; Wang, Andrew Z; Radovic-Moreno, Aleksandar F; Alexis, Frank; Langer, Robert; Farokhzad, Omid C

2014-01-01

We report the engineering of a novel lipid-polymer hybrid nanoparticle (NP) as a robust drug delivery platform, with high drug encapsulation yield, tunable and sustained drug release profile, excellent serum stability, and potential for differential targeting of cells or tissues. The NP is comprised of three distinct functional components: i) a hydrophobic polymeric core where poorly water-soluble drugs can be encapsulated; ii) a hydrophilic polymeric shell with anti-biofouling properties to enhance NP stability and systemic circulation half-life; and iii) a lipid monolayer at the interface of the core and the shell that acts as a molecular fence to promote drug retention inside the polymeric core, thereby enhancing drug encapsulation efficiency, increasing drug loading yield, and controlling drug release. The NP is prepared by self-assembly through a single-step nanoprecipitation method in a reproducible and predictable manner, making it potentially suitable for scale-up PMID:19206374

21 CFR 178.3790 - Polymer modifiers in semirigid and rigid vinyl chloride plastics.

Code of Federal Regulations, 2014 CFR

2014-04-01

...), (ii), and (iii) of this section; provided that no chemical reactions, other than addition reactions... their polymerization with butadiene-styrene copolymers; provided that no chemical reactions, other than addition reactions, occur when they are combined. Such combined polymers may contain 50 weight-percent or...

Dynamic evolution of the oscillatory Belousov--Zhabotinsky reaction upon addition of a non-ionic polymer

NASA Astrophysics Data System (ADS)

Sciascia, Luciana; Lombardo, Renato; Turco Liveri, Maria Liria

2006-10-01

The dynamic evolution of the oscillatory Belousov-Zhabotinsky reaction upon addition of increasing amount of the non-ionic polymer polypropylene glycol with molecular weight 425 g mol -1 (PPG-425) was investigated in a stirred-batch reactor by monitoring the Ce(IV) absorbance changes. The oscillatory parameters are significantly altered by the presence of the polymer. The findings obtained in the present work revealed that the PPG-425 is not only more effective, than other polymer previously [R. Lombardo, C. Sbriziolo, M.L. Turco Liveri, K. Pelle, M. Wittmann, Z. Noszticzius, in: J.A. Pojman, Q. Tran-Cong-Miyata (Eds.), Nonlinear Dynamics in Polymeric Systems, American Chemical Society, Washington, DC, 869 (2004) 292] studied, in perturbing the BZ systems but also more capable of producing key radical species, which in turn can be exploited for the preparation of new polymeric materials.

New oxalate-bridged CrIII-MnII polymeric network incorporating a spin-crossover [Co(terpy)2]2+ cation.

PubMed

Kou, Hui-Zhong; Sato, Osamu

2007-11-12

The reaction of Mn2+ with [Cr(ox)3]3- in the presence of the spin-crossover [Co(terpy)2]2+ cation gives rise to a 1D [Co(terpy)2][Mn(H2O)ClCr(ox)3].H2O.0.5MeOH (1) or a 2D [Co(terpy)2][Mn(H2O)Cr(ox)3]2.5H2O.0.5MeOH (2). The trimetallic complexes display dominant ferromagnetic behavior, and spin-crossover of [Co(terpy)2]2+ is suppressed by the chemical pressure of the polymeric oxalate-bridged network.

Investigation of metal ligand affinities of atom transfer radical polymerization catalysts with a quadrupole ion trap.

PubMed

di Lena, Fabio; Matyjaszewski, Krzysztof

2009-11-07

An electrospray ionization mass spectrometer equipped with a quadrupole ion trap as the mass analyzer provided a powerful tool for the investigation of metal ligand affinities of catalysts for atom transfer radical polymerization. It allowed, in particular, (i) the identification, in a library of ligands, of the most stable, and thus active, copper catalysts; (ii) the assessment of the effects of the reaction medium on the relative stabilities of the catalyst complexes; and (iii) the evaluation of the influence of the nature of the ligand on both the complex halogenophilicity and the metal-ligand stabilities in the gas-phase.

Gd-DTPA L-cystine bisamide copolymers as novel biodegradable macromolecular contrast agents for MR blood pool imaging.

PubMed

Kaneshiro, Todd L; Ke, Tianyi; Jeong, Eun-Kee; Parker, Dennis L; Lu, Zheng-Rong

2006-06-01

The purpose of this study was to synthesize biodegradable Gd-DTPA L-cystine bisamide copolymers (GCAC) as safe and effective, macromolecular contrast agents for magnetic resonance imaging (MRI) and to evaluate their biodegradability and efficacy in MR blood pool imaging in an animal model. Three new biodegradable GCAC with different substituents at the cystine bisamide [R = H (GCAC), CH2CH2CH3 (Gd-DTPA L-cystine bispropyl amide copolymers, GCPC), and CH(CH3)2 (Gd-DTPA cystine bisisopropyl copolymers, GCIC)] were prepared by the condensation copolymerization of diethylenetriamine pentaacetic acid (DTPA) dianhydride with cystine bisamide or bisalkyl amides, followed by complexation with gadolinium triacetate. The degradability of the agents was studied in vitro by incubation in 15 microM cysteine and in vivo with Sprague-Dawley rats. The kinetics of in vivo contrast enhancement was investigated in Sprague-Dawley rats on a Siemens Trio 3 T scanner. The apparent molecular weight of the polydisulfide Gd(III) chelates ranged from 22 to 25 kDa. The longitudinal (T1) relaxivities of GCAC, GCPC, and GCIC were 4.37, 5.28, and 5.56 mM(-1) s(-1) at 3 T, respectively. The polymeric ligands and polymeric Gd(III) chelates readily degraded into smaller molecules in incubation with 15 microM cysteine via disulfide-thiol exchange reactions. The in vitro degradation rates of both the polymeric ligands and macromolecular Gd(III) chelates decreased as the steric effect around the disulfide bonds increased. The agents readily degraded in vivo, and the catabolic degradation products were detected in rat urine samples collected after intravenous injection. The agents showed strong contrast enhancement in the blood pool, major organs, and tissues at a dose of 0.1 mmol Gd/kg. The difference of their in vitro degradability did not significantly alter the kinetics of in vivo contrast enhancement of the agents. These novel GCAC are promising contrast agents for cardiovascular and tumor MRI, which are later cleaved into low molecular weight Gd(III) chelates and rapidly cleared from the body.

Highly efficient and selective pressure-assisted photon-induced polymerization of styrene

NASA Astrophysics Data System (ADS)

Guan, Jiwen; Song, Yang

2016-06-01

The polymerization process of condensed styrene to produce polystyrene as an industrially important polymeric material was investigated using a novel approach by combining external compression with ultraviolet radiation. The reaction evolution was monitored as a function of time and the reaction products were characterized by in situ Fourier transform infrared spectroscopy. By optimizing the loading pressures, we observed highly efficient and selective production of polystyrene of different tacticities. Specifically, at relatively low loading pressures, infrared spectra suggest that styrene monomers transform to amorphous atactic polystyrene (APS) with minor crystalline isotactic polystyrene. In contrast, APS was found to be the sole product when polymerization occurs at relatively higher loading pressures. The time-dependent reaction profiles allow the examination of the polymerization kinetics by analyzing the rate constant and activation volume as a function of pressure. As a result, an optimized pressure condition, which allows a barrierless reaction to proceed, was identified and attributed to the very desirable reaction yield and kinetics. Finally, the photoinitiated reaction mechanism and the growth geometry of the polymer chains were investigated from the energy diagram of styrene and by the topology analysis of the crystal styrene. This study shows strong promise to produce functional polymeric materials in a highly efficient and controlled manner.

Photoinitiated Polymerization-Induced Self-Assembly (Photo-PISA): New Insights and Opportunities.

PubMed

Yeow, Jonathan; Boyer, Cyrille

2017-07-01

The polymerization-induced self-assembly (PISA) process is a useful synthetic tool for the efficient synthesis of polymeric nanoparticles of different morphologies. Recently, studies on visible light initiated PISA processes have offered a number of key research opportunities that are not readily accessible using traditional thermally initiated systems. For example, visible light mediated PISA (Photo-PISA) enables a high degree of control over the dispersion polymerization process by manipulation of the wavelength and intensity of incident light. In some cases, the final nanoparticle morphology of a single formulation can be modulated by simple manipulation of these externally controlled parameters. In addition, temporal (and in principle spatial) control over the Photo-PISA process can be achieved in most cases. Exploitation of the mild room temperature polymerizations conditions can enable the encapsulation of thermally sensitive therapeutics to occur without compromising the polymerization rate and their activities. Finally, the Photo-PISA process can enable further mechanistic insights into the morphological evolution of nanoparticle formation such as the effects of temperature on the self-assembly process. The purpose of this mini-review is therefore to examine some of these recent advances that have been made in Photo-PISA processes, particularly in light of the specific advantages that may exist in comparison with conventional thermally initiated systems.

The kinetics of polyurethane structural foam formation: Foaming and polymerization

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

Rao, Rekha R.; Mondy, Lisa A.; Long, Kevin N.

We are developing kinetic models to understand the manufacturing of polymeric foams, which evolve from low viscosity Newtonian liquids, to bubbly liquids, finally producing solid foam. Closed-form kinetics are formulated and parameterized for PMDI-10, a fast curing polyurethane, including polymerization and foaming. PMDI- 10 is chemically blown, where water and isocyanate react to form carbon dioxide. The isocyanate reacts with polyol in a competing reaction, producing polymer. Our approach is unique, though it builds on our previous work and the polymerization literature. This kinetic model follows a simplified mathematical formalism that decouples foaming and curing, including an evolving glass transitionmore » temperature to represent vitrification. This approach is based on IR, DSC, and volume evolution data, where we observed that the isocyanate is always in excess and does not affect the kinetics. Finally, the kinetics are suitable for implementation into a computational fluid dynamics framework, which will be explored in subsequent papers.« less

The kinetics of polyurethane structural foam formation: Foaming and polymerization

DOE PAGES

Rao, Rekha R.; Mondy, Lisa A.; Long, Kevin N.; ...

2017-02-15

We are developing kinetic models to understand the manufacturing of polymeric foams, which evolve from low viscosity Newtonian liquids, to bubbly liquids, finally producing solid foam. Closed-form kinetics are formulated and parameterized for PMDI-10, a fast curing polyurethane, including polymerization and foaming. PMDI- 10 is chemically blown, where water and isocyanate react to form carbon dioxide. The isocyanate reacts with polyol in a competing reaction, producing polymer. Our approach is unique, though it builds on our previous work and the polymerization literature. This kinetic model follows a simplified mathematical formalism that decouples foaming and curing, including an evolving glass transitionmore » temperature to represent vitrification. This approach is based on IR, DSC, and volume evolution data, where we observed that the isocyanate is always in excess and does not affect the kinetics. Finally, the kinetics are suitable for implementation into a computational fluid dynamics framework, which will be explored in subsequent papers.« less

Guanine- Formation During the Thermal Polymerization of Amino Acids

NASA Technical Reports Server (NTRS)

Mc Caw, B. K.; Munoz, E. F.; Ponnamperuma, C.; Young, R. S.

1964-01-01

The action of heat on a mixture of amino acids was studied as a possible abiological pathway for the synthesis of purines and pyrimidines. Guanine was detected. This result is significant in the context of chemical evolution.

Crystal structure and solution species of Ce(III) and Ce(IV) formates: from mononuclear to hexanuclear complexes.

PubMed

Hennig, Christoph; Ikeda-Ohno, Atsushi; Kraus, Werner; Weiss, Stephan; Pattison, Philip; Emerich, Hermann; Abdala, Paula M; Scheinost, Andreas C

2013-10-21

Cerium(III) and cerium(IV) both form formate complexes. However, their species in aqueous solution and the solid-state structures are surprisingly different. The species in aqueous solutions were investigated with Ce K-edge EXAFS spectroscopy. Ce(III) formate shows only mononuclear complexes, which is in agreement with the predicted mononuclear species of Ce(HCOO)(2+) and Ce(HCOO)2(+). In contrast, Ce(IV) formate forms in aqueous solution a stable hexanuclear complex of [Ce6(μ3-O)4(μ3-OH)4(HCOO)x(NO3)y](12-x-y). The structural differences reflect the different influence of hydrolysis, which is weak for Ce(III) and strong for Ce(IV). Hydrolysis of Ce(IV) ions causes initial polymerization while complexation through HCOO(-) results in 12 chelate rings stabilizing the hexanuclear Ce(IV) complex. Crystals were grown from the above-mentioned solutions. Two crystal structures of Ce(IV) formate were determined. Both form a hexanuclear complex with a [Ce6(μ3-O)4(μ3-OH)4](12+) core in aqueous HNO3/HCOOH solution. The pH titration with NaOH resulted in a structure with the composition [Ce6(μ3-O)4(μ3-OH)4(HCOO)10(NO3)2(H2O)3]·(H2O)9.5, while the pH adjustment with NH3 resulted in [Ce6(μ3-O)4(μ3-OH)4(HCOO)10(NO3)4]·(NO3)3(NH4)5(H2O)5. Furthermore, the crystal structure of Ce(III) formate, Ce(HCOO)3, was determined. The coordination polyhedron is a tricapped trigonal prism which is formed exclusively by nine HCOO(-) ligands. The hexanuclear Ce(IV) formate species from aqueous solution is widely preserved in the crystal structure, whereas the mononuclear solution species of Ce(III) formate undergoes a polymerization during the crystallization process.

Origin of the RNA world: The fate of nucleobases in warm little ponds

PubMed Central

Pudritz, Ralph E.; Semenov, Dmitry A.; Henning, Thomas K.

2017-01-01

Before the origin of simple cellular life, the building blocks of RNA (nucleotides) had to form and polymerize in favorable environments on early Earth. At this time, meteorites and interplanetary dust particles delivered organics such as nucleobases (the characteristic molecules of nucleotides) to warm little ponds whose wet–dry cycles promoted rapid polymerization. We build a comprehensive numerical model for the evolution of nucleobases in warm little ponds leading to the emergence of the first nucleotides and RNA. We couple Earth’s early evolution with complex prebiotic chemistry in these environments. We find that RNA polymers must have emerged very quickly after the deposition of meteorites (less than a few years). Their constituent nucleobases were primarily meteoritic in origin and not from interplanetary dust particles. Ponds appeared as continents rose out of the early global ocean, but this increasing availability of “targets” for meteorites was offset by declining meteorite bombardment rates. Moreover, the rapid losses of nucleobases to pond seepage during wet periods, and to UV photodissociation during dry periods, mean that the synthesis of nucleotides and their polymerization into RNA occurred in just one to a few wet–dry cycles. Under these conditions, RNA polymers likely appeared before 4.17 billion years ago. PMID:28973920

Spectroscopic studies of non-volatile residue formed by photochemistry of solid C4N2: A model of condensed aerosol formation on Titan

NASA Astrophysics Data System (ADS)

Couturier-Tamburelli, Isabelle; Gudipati, Murthy S.; Lignell, Antti; Jacovi, Ronen; Piétri, Nathalie

2014-05-01

Following our recent communication (Gudipati, M.S. et al. [2013]. Nat. Commun. 4, 1648. http://dx.doi.org/10.1038/ncomms2649) on the discovery of condensed-phase non-volatile polymeric material with similar spectral features as tholins, we present here a comprehensive spectroscopic study of photochemical formation of polymeric material from condensed dicyanoacetylene (C4N2) ice films. C4N2 is chosen as starting material for the laboratory simulations because of the detection of this and similar molecules (nitriles and cyanoacetylenes) in Titan’s atmosphere. UV-Vis and infrared spectra obtained during long-wavelength (>300 nm) photon irradiation and subsequent warming of the ice films are used to analyze changes in C4N2 ice, evolution of tholins, and derive photopolymerization mechanisms. Our data analysis revealed that many processes occur during the photolysis of condensed Titan’s aerosol analogs, including isomerization and polymerization leading to the formation of long-chain as well as aromatic cyclic polymer molecules. In the light of tremendous new data from the Cassini mission on the seasonal variations in Titan’s atmosphere, our laboratory study and its results provide fresh insight into the formation and evolution of aerosols and haze in Titan’s atmosphere.

Origin of the RNA world: The fate of nucleobases in warm little ponds.

PubMed

Pearce, Ben K D; Pudritz, Ralph E; Semenov, Dmitry A; Henning, Thomas K

2017-10-24

Before the origin of simple cellular life, the building blocks of RNA (nucleotides) had to form and polymerize in favorable environments on early Earth. At this time, meteorites and interplanetary dust particles delivered organics such as nucleobases (the characteristic molecules of nucleotides) to warm little ponds whose wet-dry cycles promoted rapid polymerization. We build a comprehensive numerical model for the evolution of nucleobases in warm little ponds leading to the emergence of the first nucleotides and RNA. We couple Earth's early evolution with complex prebiotic chemistry in these environments. We find that RNA polymers must have emerged very quickly after the deposition of meteorites (less than a few years). Their constituent nucleobases were primarily meteoritic in origin and not from interplanetary dust particles. Ponds appeared as continents rose out of the early global ocean, but this increasing availability of "targets" for meteorites was offset by declining meteorite bombardment rates. Moreover, the rapid losses of nucleobases to pond seepage during wet periods, and to UV photodissociation during dry periods, mean that the synthesis of nucleotides and their polymerization into RNA occurred in just one to a few wet-dry cycles. Under these conditions, RNA polymers likely appeared before 4.17 billion years ago.

Experimental conditions affecting the kinetics of aqueous HCN polymerization as revealed by UV-vis spectroscopy.

PubMed

Marín-Yaseli, Margarita R; Moreno, Miguel; de la Fuente, José L; Briones, Carlos; Ruiz-Bermejo, Marta

2018-02-15

HCN polymerization is one of the most important and fascinating reactions in prebiotic chemistry, and interest in HCN polymers in the field of materials science is growing. However, little is known about the kinetics of the HCN polymerization process. In the present study, a first approach to the kinetics of two sets of aqueous HCN polymerizations, from NH 4 CN and NaCN, at middle temperatures between 4 and 38°C, has been carried out. For each series, the presence of air and salts in the reaction medium has been systematically explored. A previous kinetic analysis was conducted during the conversion of the insoluble black HCN polymers obtained as gel fractions in these precipitation polymerizations for a reaction of one month, where a limit conversion was achieved at the highest polymerization temperature. The kinetic description of the gravimetric data for this complex system shows a clear change in the linear dependence with the polymerization temperature for the reaction from NH 4 CN, besides a relevant catalytic effect of ammonium, in comparison with those data obtained from the NaCN series. These results also demonstrated the notable influence of air, oxygen, and the saline medium in HCN polymer formation. Similar conclusions were reached when the sol fractions were monitored by UV-vis spectroscopy, and a Hill type correlation was used to describe the polymerization profiles obtained. This technique was chosen because it provides an easy, prompt and fast method to follow the evolution of the liquid or continuous phase of the process under study. Copyright © 2017 Elsevier B.V. All rights reserved.

Experimental conditions affecting the kinetics of aqueous HCN polymerization as revealed by UV-vis spectroscopy

NASA Astrophysics Data System (ADS)

Marín-Yaseli, Margarita R.; Moreno, Miguel; de la Fuente, José L.; Briones, Carlos; Ruiz-Bermejo, Marta

2018-02-01

HCN polymerization is one of the most important and fascinating reactions in prebiotic chemistry, and interest in HCN polymers in the field of materials science is growing. However, little is known about the kinetics of the HCN polymerization process. In the present study, a first approach to the kinetics of two sets of aqueous HCN polymerizations, from NH4CN and NaCN, at middle temperatures between 4 and 38 °C, has been carried out. For each series, the presence of air and salts in the reaction medium has been systematically explored. A previous kinetic analysis was conducted during the conversion of the insoluble black HCN polymers obtained as gel fractions in these precipitation polymerizations for a reaction of one month, where a limit conversion was achieved at the highest polymerization temperature. The kinetic description of the gravimetric data for this complex system shows a clear change in the linear dependence with the polymerization temperature for the reaction from NH4CN, besides a relevant catalytic effect of ammonium, in comparison with those data obtained from the NaCN series. These results also demonstrated the notable influence of air, oxygen, and the saline medium in HCN polymer formation. Similar conclusions were reached when the sol fractions were monitored by UV-vis spectroscopy, and a Hill type correlation was used to describe the polymerization profiles obtained. This technique was chosen because it provides an easy, prompt and fast method to follow the evolution of the liquid or continuous phase of the process under study.

Polymeric Optical Sensors for Selective and Sensitive Nitrite Detection Using Cobalt(III) Corrole and Rh(III) Porphyrin as Ionophores

PubMed Central

Yang, Si; Wo, Yaqi; Meyerhoff, Mark E.

2014-01-01

Cobalt(III) 5, 10, 15-tris(4-tert-butylphenyl) corrole with a triphenylphosphine axial ligand and rhodium(III) 5,10,15,20-tetra(p-tert-butylphenyl)porphyrin are incorporated into plasticized poly(vinyl chloride) films to fabricate nitrite-selective bulk optodes via absorbance measurements. The resulting films yield sensitive, fast and fully reversible response toward nitrite with significantly enhanced nitrite selectivity over other anions including lipophilic anions such as thiocyanate and perchlorate. The selectivity patterns differ greatly from the Hofmeister series based on anion lipophilicity and are consistent with selectivity obtained with potentiometric sensors based on the same ionophores. The optical nitrite sensors are shown to be useful for detecting rates of emission of nitric oxide (NO) from NO releasing polymers containing S-nitroso-N-acetyl-penicillamine. PMID:25150700

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

Guan, Jiwen; Song, Yang, E-mail: yang.song@uwo.ca; Department of Chemistry, University of Western Ontario, London, Ontario N6A 5B7

The polymerization process of condensed styrene to produce polystyrene as an industrially important polymeric material was investigated using a novel approach by combining external compression with ultraviolet radiation. The reaction evolution was monitored as a function of time and the reaction products were characterized by in situ Fourier transform infrared spectroscopy. By optimizing the loading pressures, we observed highly efficient and selective production of polystyrene of different tacticities. Specifically, at relatively low loading pressures, infrared spectra suggest that styrene monomers transform to amorphous atactic polystyrene (APS) with minor crystalline isotactic polystyrene. In contrast, APS was found to be the solemore » product when polymerization occurs at relatively higher loading pressures. The time-dependent reaction profiles allow the examination of the polymerization kinetics by analyzing the rate constant and activation volume as a function of pressure. As a result, an optimized pressure condition, which allows a barrierless reaction to proceed, was identified and attributed to the very desirable reaction yield and kinetics. Finally, the photoinitiated reaction mechanism and the growth geometry of the polymer chains were investigated from the energy diagram of styrene and by the topology analysis of the crystal styrene. This study shows strong promise to produce functional polymeric materials in a highly efficient and controlled manner.« less

Effect of Monomer Solubility on the Evolution of Copolymer Morphology during Polymerization-Induced Self-Assembly in Aqueous Solution

PubMed Central

2017-01-01

Polymerization-induced self-assembly (PISA) has become a widely used technique for the rational design of diblock copolymer nano-objects in concentrated aqueous solution. Depending on the specific PISA formulation, reversible addition–fragmentation chain transfer (RAFT) aqueous dispersion polymerization typically provides straightforward access to either spheres, worms, or vesicles. In contrast, RAFT aqueous emulsion polymerization formulations often lead to just kinetically-trapped spheres. This limitation is currently not understood, and only a few empirical exceptions have been reported in the literature. In the present work, the effect of monomer solubility on copolymer morphology is explored for an aqueous PISA formulation. Using 2-hydroxybutyl methacrylate (aqueous solubility = 20 g dm–3 at 70 °C) instead of benzyl methacrylate (0.40 g dm–3 at 70 °C) for the core-forming block allows access to an unusual “monkey nut” copolymer morphology over a relatively narrow range of target degrees of polymerization when using a poly(methacrylic acid) RAFT agent at pH 5. These new anisotropic nanoparticles have been characterized by transmission electron microscopy, dynamic light scattering, aqueous electrophoresis, shear-induced polarized light imaging (SIPLI), and small-angle X-ray scattering. PMID:28216792

SYNTHESIS OF A POLYMERIC HYBRID ION EXCHANGER WITH RECOVERED IRON(III) TOWARDS THE REMOVAL OF ARSENIC

EPA Science Inventory

Every year, millions of tons of ferric hydroxide loaded water treatment residuals are disposed of under current EPA regulations into landfills and other waste sites. Meanwhile, half way around the world, millions of people are drinking arsenic contaminated water on a daily bas...

Electrochemical Sensor Based on Rh(III) Ion-Imprinted Polymer as a New Modifying Agent for Rhodium Determination.

PubMed

Bai, Huiping; Xiong, Caiyun; Wang, Chunqiong; Liu, Peng; Dong, Su; Cao, Qiue

2018-05-01

A rhodium (III) ion carbon paste electrode (CPE) based on an ion imprinted polymer (IIP) as a new modifying agent has been prepared and studied. Rh(III) ion imprinted polymer was synthesized by copolymerization of acrylamide-Rh(III) complex and ethylene glycol dimethacrylate according to the precipitation polymerization. Acrylamide acted as both functional monomer and complexing agent to create selective coordination sites in a cross-linked polymer. The ion imprinted carbon paste electrode (IIP-CPE) was prepared by mixing rhodium IIP-nanoparticles and graphite powder in n-eicosane as an adhesive and then embedding them in a Teflon tube. Amperometric i-t curve method was applied as the determination technique. Several parameters, including the functional monomer, molar ratio of template, monomer and cross-linking agent, the amounts of IIP, the applied potential, the buffer solution and pH have been studied. According to the results, IIP-CPE showed a considerably higher response in comparison with the electrode embedded with non-imprinted polymer (NIP), indicating the formation of suitable recognition sites in the IIP structure during the polymerization stage. The introduced electrode showed a linear range of 1.00×10-8~3.0×10-5 mol·L-1 and detection limit of 6.0 nmol L-1 (S/N = 3). The IIP-CPE was successfully applied for the trace rhodium determination in catalyst and plant samples with RSD of less than 3.3% (n = 5) and recoveries in the range of 95.5~102.5%.

Cytosolic Extract Induces Tir Translocation and Pedestals in EPEC-Infected Red Blood Cells

PubMed Central

Swimm, Alyson I; Kalman, Daniel

2008-01-01

Enteropathogenic Escherichia coli (EPEC) are deadly contaminants in water and food, and induce protrusion of actin-filled membranous pedestals beneath themselves upon attachment to intestinal epithelia. Pedestal formation requires clustering of Tir and subsequent recruitment of cellular tyrosine kinases including Abl, Arg, and Etk as well as signaling molecules Nck, N-WASP, and Arp2/3 complex. We have developed a cytosolic extract-based cellular system that recapitulates actin pedestal formation in permeabilized red blood cells (RBC) infected with EPEC. RBC support attachment of EPEC and translocation of virulence factors, but not pedestal formation. We show here that extract induces a rapid Ca++-dependent release of Tir from the EPEC Type III secretion system, and that cytoplasmic factor(s) present in the extract facilitate translocation of Tir into the RBC plasma membrane. We show that Abl and related kinases in the extract phosphorylate Tir and that actin polymerization can be reconstituted in infected RBC following addition of cytosolic extract. Reconstitution requires the bacterial virulence factors Tir and intimin, and phosphorylation of Tir on tyrosine residue 474 results in the recruitment of Nck, N-WASP, and Arp2/3 complex beneath attached bacteria at sites of actin polymerization. Together these data describe a biochemical system for dissection of host components that mediate Type III secretion and the mechanisms by which complexes of proteins are recruited to discrete sites within the plasma membrane to initiate localized actin polymerization and morphological changes. PMID:18208322

Lignin-solubilizing ability of actinomycetes isolated from termite (Termitidae) gut.

PubMed Central

Pasti, M B; Pometto, A L; Nuti, M P; Crawford, D L

1990-01-01

The lignocellulose-degrading abilities of 11 novel actinomycete strains isolated from termite gut were determined and compared with that of the well-characterized actinomycete, Streptomyces viridosporus T7A. Lignocellulose bioconversion was followed by (i) monitoring the degradation of [14C]lignin- and [14C]cellulose-labeled phloem of Abies concolor to 14CO2 and 14C-labeled water-soluble products, (ii) determining lignocellulose, lignin, and carbohydrate losses resulting from growth on a lignocellulose substrate prepared from corn stalks (Zea mays), and (iii) quantifying production of a water-soluble lignin degradation intermediate (acid-precipitable polymeric lignin). The actinomycetes were all Streptomyces strains and could be placed into three groups, including a group of five strains that appear superior to S. viridosporus T7A in lignocellulose-degrading ability, three strains of approximately equal ability, and three strains of lesser ability. Strain A2 was clearly the superior and most effective lignocellulose decomposer of those tested. Of the assays used, total lignocellulose weight loss was most useful in determining overall bioconversion ability but not in identifying the best lignin-solubilizing strains. A screening procedure based on 14CO2 evolution from [14C-lignin]lignocellulose combined with measurement of acid-precipitable polymeric lignin yield was the most effective in identifying lignin-solubilizing strains. For the termite gut strains, the pH of the medium showed no increase after 3 weeks of growth on lignocellulose. This is markedly different from the pattern observed with S. viridosporus T7A, which raises the medium pH considerably. Production of extracellular peroxidases by the 11 strains and S. viridosporus T7A was followed for 5 days in liquid cultures.(ABSTRACT TRUNCATED AT 250 WORDS) PMID:2167628

A review of processable high temperature resistant addition-type laminating resins

NASA Technical Reports Server (NTRS)

Serafini, T. T.; Delvigs, P.

1973-01-01

An important finding that resulted from research that was conducted to develop improved ablative resins was the discovery of a novel approach to synthesize processable high temperature resistant polymers. Low molecular weight polyimide prepolymers end-capped with norbornene groups were polymerized into thermo-oxidatively stable modified polyimides without the evolution of void producing volatile materials. This paper reviews basic studies that were performed using model compounds to elucidate the polymerization mechanism of the so-called addition-type polyimides. The fabrication and properties of polyimide/graphite fiber composites using A-type polyimide prepolymer as the matrix are described. An alternate method for preparing processable A-type polyimides by means of in situ polymerization of monomeric reactants on the fiber reinforcement is also described. Polyimide/graphite fiber composite performance at elevated temperatures is presented for A-type polyimides.

Comparison of Different Encapsulating Adhesives to Enhance the Efficiencies and Lifetimes of Polymeric Solar Cells

NASA Astrophysics Data System (ADS)

Chung, Ming-Hua; Chen, Chen-Ming; Hsieh, Tsung-Eong; Tang, Rong-Ming; Tsai, Yu Sheng; Chu, Wei-Ping; Liu, Mark O.; Juang, Fuh-Shyang

2009-04-01

Polymeric solar cells (PSCs) with a derivative of C60 [[6,6]-phenyl C61-butyric acid methyl ester (PCBM)], and 3-hexylthiophene (P3HT) as active layers have been fabricated. The PSC devices were also packaged with glass and novel UV glues to improve their lifetimes and power conversion efficiencies (PCEs). After encapsulation with UV glue I, II, and III, the PCEs of PSCs reached 4, 4.82, and 6%, respectively, and their half-lifetimes increased to 16-18, 26-28, and 90 h, respectively, while the PCEs and half-lifetimes of PSCs without encapsulation were 3.76% and 2.5 h, respectively.

Preparation and Characterization of InP/Poly(methyl methacrylate) Nanocomposite Films.

PubMed

Kwon, Younghoon; Kim, Jongsung

2017-04-01

Quantum dots (QDs) are nanocrystalline semiconductors with many unusual optical properties. They exhibit very high fluorescence intensities and possess exceptional stability against photo-bleaching. In this study, we report the preparation of InP QDs-poly(methyl methacrylate) (PMMA) hybrids by fabricating QDs via a thermal decomposition reaction, followed by radical polymerization. The InP QDs were synthesized using indium(III) chloride and tris(dimethylamino)phosphine. Flexible composite films were obtained by radical polymerization using methyl methacrylate (MMA) as the monomer and 2,2′-azobis(2-methylpropionitrile) (AIBN) as a radical initiator. The PL intensity of the QDs was lowered upon composite formation with PMMA. However, the composites exhibited higher thermal stability than pure PMMA.

Versatile Methodology to Encapsulate Gold Nanoparticles in PLGA Nanoparticles Obtained by Nano-Emulsion Templating.

PubMed

Fornaguera, Cristina; Feiner-Gracia, Natàlia; Dols-Perez, Aurora; García-Celma, Maria José; Solans, Conxita

2017-05-01

Gold nanoparticles have been proved useful for many biomedical applications, specifically, for their use as advanced imaging systems. However, they usually present problems related with stability and toxicity. In the present work, gold-nanoparticles have been encapsulated in polymeric nanoparticles using a novel methodology based on nano-emulsion templating. Firstly, gold nanoparticles have been transferred from water to ethyl acetate, a solvent classified as class III by the NIH guidelines (low toxic potential). Next, the formation of nano-emulsions loaded with gold nanoparticles has been performed using a low-energy, the phase inversion composition (PIC) emulsification method, followed by solvent evaporation giving rise to polymeric nanoparticles. Using this methodology, high concentrations of gold nanoparticles (>100 pM) have been encapsulated. Increasing gold nanoparticle concentration, nano-emulsion and nanoparticle sizes increase, resulting in a decrease on the stability. It is noteworthy that the designed nanoparticles did not produce cytotoxicity neither hemolysis at the required concentration. Therefore, it can be concluded that a novel and very versatile methodology has been developed for the production of polymeric nanoparticles loaded with gold nanoparticles. Graphical Abstract Schematic representation of AuNP-loaded polymeric nanoparticles preparation from nano-emulsion templating.

Bis(1,3-di-tert-butylimidazolin-2-iminato) titanium complexes as effective catalysts for the monodisperse polymerization of propylene.

PubMed

Sharma, Manab; Yameen, Haneen Simaan; Tumanskii, Boris; Filimon, Sabina-Alexandra; Tamm, Matthias; Eisen, Moris S

2012-10-17

The use of bis(1,3-di-tert-butylimidazolin-2-iminato) titanium dichloride (1) and dimethyl (2) complexes in the polymerization of propylene is presented. The complexes were activated using different amounts of methylalumoxane (MAO), giving in each case a very active catalytic mixture and producing polymers with a narrow molecular weight distribution (polydispersity = 1.10). The use of the cocatalyst triphenylcarbenium (trityl) tetra(pentafluorophenyl)borate totally inhibits the reaction, producing the corresponding bis(1,3-di-tert-butylimidazolin-2-iminato) titanium(III) methyl complex, the trityl radical ((•)CPh(3)), the anionic MeB(C(6)F(5))(4)(-), B(C(6)F(5))(3), and the bis(1,3-di-tert-butylimidazolin-2-iminato) titanium(IV) dimethyl·B(C(6)F(5))(3) complex. The use of a combination of physical methods such as NMR, ESR-C(60), and MALDI-TOF analyses enabled us to propose a plausible mechanism for the polymerization of propylene, presenting that the polymerization is mainly carried out in a living fashion. In addition, we present a slow equilibrium toward a small amount of a dormant species responsible for 2,1-misinsertions and chain transfer processes.

Theoretical prediction and experimental determination of the effect of mold characteristics on temperature and monomer conversion fraction profiles during polymerization of a PMMA-based bone cement.

PubMed

Vallo, Claudia I

2002-01-01

The present work is concerned with applications of a kinetic model for free-radical polymerization of a polymethylmethacrylate-based bone cement. Autocatalytic behavior at the first part of the reaction as well as a diffusion control phenomenon near vitrification are described by the model. Comparison of theoretical computations with experimental measurements for the temperature evolution during batch casting demonstrated the capacity of the proposed model to represent the kinetic behavior of the polymerization reaction. Temperature evolution and monomer conversion were simulated for the cure of the cement in molds made of different materials. The maximum monomer conversion fraction was markedly influenced by the physical properties of the mold material. The unreacted monomer acts as a plasticizer that influences the mechanical behavior of the cement. Hence, the same cement formulation cured in molds of different materials may result in different mechanical response because of the differences in the amounts of residual monomer. Standardization of the mold type to prepare specimens for the mechanical characterization of bone cements is recommended. Theoretical prediction of temperature evolution during hip replacement indicated that for cement thickness lower than 6 mm the peak temperature at the bone-cement interface was below the limit stated for thermal injury (50 degrees C for more than 1 min). The use of thin cement layers is recommended to diminish the risk of thermal injury; however, it is accompanied by an increase in the amount of unreacted monomer present in the cured material. Copyright 2002 Wiley Periodicals, Inc. J Biomed Mater Res (Appl Biomater) 63: 627-642, 2002

Molecular evolution and diversification of snake toxin genes, revealed by analysis of intron sequences.

PubMed

Fujimi, T J; Nakajyo, T; Nishimura, E; Ogura, E; Tsuchiya, T; Tamiya, T

2003-08-14

The genes encoding erabutoxin (short chain neurotoxin) isoforms (Ea, Eb, and Ec), LsIII (long chain neurotoxin) and a novel long chain neurotoxin pseudogene were cloned from a Laticauda semifasciata genomic library. Short and long chain neurotoxin genes were also cloned from the genome of Laticauda laticaudata, a closely related species of L. semifasciata, by PCR. A putative matrix attached region (MAR) sequence was found in the intron I of the LsIII gene. Comparative analysis of 11 structurally relevant snake toxin genes (three-finger-structure toxins) revealed the molecular evolution of these toxins. Three-finger-structure toxin genes diverged from a common ancestor through two types of evolutionary pathways (long and short types), early in the course of evolution. At a later stage of evolution in each gene, the accumulation of mutations in the exons, especially exon II, by accelerated evolution may have caused the increased diversification in their functions. It was also revealed that the putative MAR sequence found in the LsIII gene was integrated into the gene after the species-level divergence.

Structure and membrane remodeling activity of ESCRT-III helical polymers

PubMed Central

McCullough, John; Clippinger, Amy K.; Talledge, Nathaniel; Skowyra, Michael L.; Saunders, Marissa G.; Naismith, Teresa V.; Colf, Leremy A.; Afonine, Pavel; Arthur, Christopher; Sundquist, Wesley I.; Hanson, Phyllis I.; Frost, Adam

2015-01-01

The Endosomal Sorting Complexes Required for Transport (ESCRT) proteins mediate fundamental membrane remodeling events that require stabilizing negative membrane curvature. These include endosomal intralumenal vesicle formation, HIV budding, nuclear envelope closure and cytokinetic abscission. ESCRT-III subunits perform key roles in these processes by changing conformation and polymerizing into membrane-remodeling filaments. Here, we report the 4 Å resolution cryo-EM reconstruction of a one-start, double-stranded helical copolymer composed of two different human ESCRT-III subunits, CHMP1B and IST1. The inner strand comprises “open” CHMP1B subunits that interlock in an elaborate domain-swapped architecture, and is encircled by an outer strand of “closed” IST1 subunits. Unlike other ESCRT-III proteins, CHMP1B and IST1 polymers form external coats on positively-curved membranes in vitro and in vivo. Our analysis suggests how common ESCRT-III filament architectures could stabilize different degrees and directions of membrane curvature. PMID:26634441

Highly Luminescent, Water-Soluble Lanthanide Fluorobenzoates: Syntheses, Structures and Photophysics, Part I: Lanthanide Pentafluorobenzoates.

PubMed

Kalyakina, Alena S; Utochnikova, Valentina V; Bushmarinov, Ivan S; Ananyev, Ivan V; Eremenko, Igor L; Volz, Daniel; Rönicke, Franziska; Schepers, Ute; Van Deun, Rik; Trigub, Alexander L; Zubavichus, Yan V; Kuzmina, Natalia P; Bräse, Stefan

2015-12-01

Highly luminescent, photostable, and soluble lanthanide pentafluorobenzoates have been synthesized and thoroughly characterized, with a focus on Eu(III) and Tb(III) complexes as visible emitters and Nd(III) , Er(III) , and Yb(III) complexes as infrared emitters. Investigation of the crystal structures of the complexes in powder form and as single crystals by using X-ray diffraction revealed five different structural types, including monomeric, dimeric, and polymeric. The local structure in different solutions was studied by using X-ray absorption spectroscopy. The photoluminescence quantum yields (PLQYs) of terbium and europium complexes were 39 and 15 %, respectively; the latter value was increased almost twice by using the heterometallic complex [Tb0.5 Eu0.5 (pfb)3 (H2 O)] (Hpfb=pentafluorobenzoic acid). Due to the effectively utilized sensitization strategy (pfb)(-) →Tb→Eu, a pure europium luminescence with a PLQY of 29 % was achieved. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Mussel-Inspired Protein Nanoparticles Containing Iron(III)-DOPA Complexes for pH-Responsive Drug Delivery.

PubMed

Kim, Bum Jin; Cheong, Hogyun; Hwang, Byeong Hee; Cha, Hyung Joon

2015-06-15

A novel bioinspired strategy for protein nanoparticle (NP) synthesis to achieve pH-responsive drug release exploits the pH-dependent changes in the coordination stoichiometry of iron(III)-3,4-dihydroxyphenylalanine (DOPA) complexes, which play a major cross-linking role in mussel byssal threads. Doxorubicin-loaded polymeric NPs that are based on Fe(III)-DOPA complexation were thus synthesized with a DOPA-modified recombinant mussel adhesive protein through a co-electrospraying process. The release of doxorubicin was found to be predominantly governed by a change in the structure of the Fe(III)-DOPA complexes induced by an acidic pH value. It was also demonstrated that the fabricated NPs exhibited effective cytotoxicity towards cancer cells through efficient cellular uptake and cytosolic release. Therefore, it is anticipated that Fe(III)-DOPA complexation can be successfully utilized as a new design principle for pH-responsive NPs for diverse controlled drug-delivery applications. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Monitoring of Diisopropyl Fluorophosphate Hydrolysis by Fluoride-Selective Polymeric Films Using Absorbance Spectroscopy

PubMed Central

Ramanathan, Madhumati; Wang, Lin; Wild, James R.; Meyeroff, Mark E.; Simonian, Aleksandr L.

2012-01-01

In this study, a novel system for the detection and quantification of organofluorophosphonates (OFP) has been developed by using an optical sensing polymeric membrane to detect the fluoride ions produced upon OFP hydrolysis. Diisopropyl fluorophosphate (DFP), a structural analogue of Type G Chemical Warfare Agents such as Sarin (GB) and Soman (GD), is used as the surrogate target analyte. An optical sensing fluoride-ion-selective polymeric film was formulated from plasticized PVC containing aluminum(III) octaethylporphyrin and ETH 7075 chromoionophore (Al[OEP]-ETH 7075). Selected formulations were used to detect the fluoride ions produced by the catalytic hydrolysis of DFP by the enzyme organophosphate hydrolase (OPH, EC 3.1.8.1). The changes in absorbance that corresponded to the deprotonated state of chromoionophore within the film results from simultaneous co-extraction of fluoride and protons as DFP hydrolysis takes place in the solution phase in contact with the film. The developed sensing system demonstrates excellent sensitivity for concentrations as low as 0.1 µM DFP. PMID:20441875

Effect of alkaline precipitation on Cr species of Cr(III)-bearing complexes typically used in the tannery industry.

PubMed

Wang, Dandan; Ye, Yuxuan; Liu, Hui; Ma, Hongrui; Zhang, Weiming

2018-02-01

Various organic compounds extensively used in the leather industry could influence the performance of alkaline precipitation with Cr(III). This study focused on two typical Cr(III)-bearing complexes (Cr(III)-collagen and Cr(III)-citrate) ubiquitous in tannery effluent yet with distinct treatment efficiencies, as Cr(III) was much more difficult to remove in the Cr(III)-citrate solution. Comprehensive analytical methods were employed to explore the intrinsic mechanism. It was found that a lower removal efficiency towards Cr(III) was significantly associated with higher oligomers. The molecular size of the Cr(III)-citrate complex continued to increase with rising pH, making it larger overall than Cr(III)-collagen species. The growing oligomer moiety of dissolved Cr(III)-complex species could persist in the stronger basic pH range, leading to the large amount of residual Cr(III) in the Cr(III)-citrate system. Combining this result with potentiometric titration and X-ray photoelectron spectroscopy data, it was believed that the polymeric species other than monomers facilitated resisting the attack from hydroxide ions, and the postulated Cr(III)-citrate species towards higher oligomers were discovered. Beyond that, both charge neutralization and sweeping effects were presented among the gradually emerging flocs in the Cr(III)-collagen system together with the electric double layer compression effect derived from salinity, thus resulting in a larger floc size and higher Cr(III) removal efficiency in saline solutions. Copyright © 2017 Elsevier Ltd. All rights reserved.

Nanoscale Origin of the Dichotimous Viscosity-Pressure Behavior in Silicate Melts

NASA Astrophysics Data System (ADS)

Wang, Y.; Sakamaki, T.; Skiner, L.; Jing, Z.; Yu, T.; Kono, Y.; Park, C.; Shen, G.; Rivers, M. L.; Sutton, S. R.

2013-12-01

A defining characteristic of silicate melts is the degree of polymerization (tetrahedral connectivity), which dictates physical properties such as viscosity and density. While viscosity of depolymerized silicate melts increases with pressure consistent with free volume theory, isothermal viscosity of polymerized melts decreases with pressure up to ~3 - 5 GPa, above which it turns over to normal (positive) pressure dependence. We conducted high-pressure melt structure studies along the jadeite (Jd) - diopside (Di) join, using a Paris-Edinburgh Press at the HPCAT beamline 16-BM-B and measured Jd melt density using a DIA type apparatus based on x-ray absorption at GSECARS beamline 13-BM-D. Structures of polymerized (Jd and Jd50Di50) and depolymerized (Di) melts show distinct responses to pressure. For Jd melt, T-O, T-T bond lengths (where T denotes tetrahedrally coordinated Al and Si) and T-O-T angle all exhibit rapid, sometimes non-linear decrease with increasing pressure to ~3 GPa. For Di melt, these parameters vary linearly with pressure and change very little. Molecular dynamics calculations, constrained by the x-ray structural data, were employed to examine details of structural evolution in polymerized and depolymerized liquids. A structural model is developed to link structural evolution to changes in melt properties, such as density and viscosity, with pressure. We show that the pressure of the viscosity turnover corresponds to the tetrahedral packing limit, below which the structure is compressed through tightening of the inter-tetrahedral bond angle, resulting in continual breakup of tetrahedral connectivity and viscosity decrease. Above the turnover pressure, Si and Al coordination increases to allow further packing, with increasing viscosity. This structural response prescribes the distribution of melt viscosity and density with depth, and may be the main controlling factor for magma transport rates in terrestrial planetary interiors.

405 nm diode laser, halogen lamp and LED device comparison in dental composites cure: an "in vitro" experimental trial.

PubMed

Fornaini, C; Lagori, G; Merigo, E; Rocca, J-P; Chiusano, M; Cucinotta, A

2015-12-30

A 405 nm diode laser is indicated for composite materials polymerizing, thanks to the recent evolution in their compositions, absorbing in blue part of the spectrum. The purpose of this research was to evaluate its performance on two different kinds of composite resins. Two different composites were polymerized with a traditional halogen lamp, a LED device and a 405 nm diode laser. The depth of the cure, the volumetric shrinkage, and the degree of the conversion (DC%) of the double bond during the curing process were measured. One-way ANOVA test, Kruskal-Wallis tests, and Dunn comparison tests were used for statistic analysis. Regarding the depth of polymerization, the laser had the worst performance on one composite while on the other, no significant difference with the other devices was observed. The volumetric shrinkage showed that laser produced the lowest change in both of the composites. The DC% measure confirmed these findings. Based on the results of this preliminary study, it is not possible to recommend the 405 nm diode laser for the polymerization of dental composites.

Stress reduction in phase-separated, cross-linked networks: influence of phase structure and kinetics of reaction

PubMed Central

Szczepanski, Caroline R.; Stansbury, Jeffrey W.

2014-01-01

A mechanism for polymerization shrinkage and stress reduction was developed for heterogeneous networks formed via ambient, photo-initiated polymerization-induced phase separation (PIPS). The material system used consists of a bulk homopolymer matrix of triethylene glycol dimethacrylate (TEGDMA) modified with one of three non-reactive, linear prepolymers (poly-methyl, ethyl and butyl methacrylate). At higher prepolymer loading levels (10–20 wt%) an enhanced reduction in both shrinkage and polymerization stress is observed. The onset of gelation in these materials is delayed to a higher degree of methacrylate conversion (~15–25%), providing more time for phase structure evolution by thermodynamically driven monomer diffusion between immiscible phases prior to network macro-gelation. The resulting phase structure was probed by introducing a fluorescently tagged prepolymer into the matrix. The phase structure evolves from a dispersion of prepolymer at low loading levels to a fully co-continuous heterogeneous network at higher loadings. The bulk modulus in phase separated networks is equivalent or greater than that of poly(TEGDMA), despite a reduced polymerization rate and cross-link density in the prepolymer-rich domains. PMID:25418999

A Review on Surface Stress-Based Miniaturized Piezoresistive SU-8 Polymeric Cantilever Sensors

NASA Astrophysics Data System (ADS)

Mathew, Ribu; Ravi Sankar, A.

2018-06-01

In the last decade, microelectromechanical systems (MEMS) SU-8 polymeric cantilevers with piezoresistive readout combined with the advances in molecular recognition techniques have found versatile applications, especially in the field of chemical and biological sensing. Compared to conventional solid-state semiconductor-based piezoresistive cantilever sensors, SU-8 polymeric cantilevers have advantages in terms of better sensitivity along with reduced material and fabrication cost. In recent times, numerous researchers have investigated their potential as a sensing platform due to high performance-to-cost ratio of SU-8 polymer-based cantilever sensors. In this article, we critically review the design, fabrication, and performance aspects of surface stress-based piezoresistive SU-8 polymeric cantilever sensors. The evolution of surface stress-based piezoresistive cantilever sensors from solid-state semiconductor materials to polymers, especially SU-8 polymer, is discussed in detail. Theoretical principles of surface stress generation and their application in cantilever sensing technology are also devised. Variants of SU-8 polymeric cantilevers with different composition of materials in cantilever stacks are explained. Furthermore, the interdependence of the material selection, geometrical design parameters, and fabrication process of piezoresistive SU-8 polymeric cantilever sensors and their cumulative impact on the sensor response are also explained in detail. In addition to the design-, fabrication-, and performance-related factors, this article also describes various challenges in engineering SU-8 polymeric cantilevers as a universal sensing platform such as temperature and moisture vulnerability. This review article would serve as a guideline for researchers to understand specifics and functionality of surface stress-based piezoresistive SU-8 cantilever sensors.[Figure not available: see fulltext.

Recruitment dynamics of ESCRT-III and Vps4 to endosomes and implications for reverse membrane budding

PubMed Central

Bykov, Yury S; Sprenger, Simon; Pakdel, Mehrshad; Vogel, Georg F; Jih, Gloria; Skillern, Wesley; Behrouzi, Reza; Babst, Markus; Schmidt, Oliver; Hess, Michael W; Briggs, John AG

2017-01-01

The ESCRT machinery mediates reverse membrane scission. By quantitative fluorescence lattice light-sheet microscopy, we have shown that ESCRT-III subunits polymerize rapidly on yeast endosomes, together with the recruitment of at least two Vps4 hexamers. During their 3–45 s lifetimes, the ESCRT-III assemblies accumulated 75–200 Snf7 and 15–50 Vps24 molecules. Productive budding events required at least two additional Vps4 hexamers. Membrane budding was associated with continuous, stochastic exchange of Vps4 and ESCRT-III components, rather than steady growth of fixed assemblies, and depended on Vps4 ATPase activity. An all-or-none step led to final release of ESCRT-III and Vps4. Tomographic electron microscopy demonstrated that acute disruption of Vps4 recruitment stalled membrane budding. We propose a model in which multiple Vps4 hexamers (four or more) draw together several ESCRT-III filaments. This process induces cargo crowding and inward membrane buckling, followed by constriction of the nascent bud neck and ultimately ILV generation by vesicle fission. PMID:29019322

Optical fluoride sensor based on monomer-dimer equilibrium of scandium(III)-octaethylporphyrin in a plasticized polymeric film.

PubMed

Kang, Youngjea; Kampf, Jeff W; Meyerhoff, Mark E

2007-08-29

A fluoride-selective optical sensor based on scandium(III)-octaethylporphyrin (Sc(III)OEP) as an ionophore within a plasticized PVC film is described. The presence of fluoride ion in the aqueous sample phase increases the formation of a difluoro-bridged Sc(III)OEP dimer species in the polymer film. The ability of the Sc(III) porphyrin to form the dimeric structure in the presence of fluoride is confirmed by UV-vis spectroscopy and X-ray crystallography. For more practical sensing applications, a pH chromoionophore (ETH 7075) is added to the plasticized PVC film along with Sc(III)OEP and the observed optical response is based on coextraction of protons with sample phase fluoride to create the dimeric porphyrin and a protonated chromoionophore species. The selectivity pattern observed is F- > ClO4(-), SCN-, NO3(-) > Br-, Cl-. Only organic salicylate is a significant interferent. Fast and reversible fluoride response is observed over the range of 10(-4) to 10(-2) M fluoride, allowing use of the sensing film in a waveguide configuration for flow-injection measurements.

Optical Fluoride Sensor Based on Monomer-Dimer Equilibrium of Scandium(III)-Octaethylporphyrin in a Plasticized Polymeric Film

PubMed Central

Kang, Youngjea; Kampf, Jeff W.; Meyerhoff, Mark E.

2007-01-01

A fluoride-selective optical sensor based on scandium(III) octaethylporphyrin (Sc(III)OEP) as an ionophore within a plasticized PVC film is described. The presence of fluoride ion in the aqueous sample phase increases the formation of a difluoro-bridged Sc(III)OEP dimer species in the polymer film. The ability of the Sc(III) porphyrin to form the dimeric structure in the presence of fluoride is confirmed by UV-Vis spectroscopy and X-ray crystallography. For more practical sensing applications, a pH chromoionophore (ETH 7075) is added to the plasticized PVC film along with Sc(III)OEP and the observed optical response is based on co-extraction of protons with sample phase fluoride to create the dimeric porphyrin and a protonated chromoionophore species. The selectivity pattern observed is F-≫ClO4-, SCN-, NO3->Br-, Cl-. Only organic salicylate is a significant interferent. Fast and reversible fluoride response is observed over the range of 10-4 ~10-2 M fluoride, allowing use of the sensing film in a waveguide configuration for flow-injection measurements. PMID:17719905

Coordination Polymer: Synthesis, Spectral Characterization and Thermal Behaviour of Starch-Urea Based Biodegradable Polymer and Its Polymer Metal Complexes

PubMed Central

Malik, Ashraf; Parveen, Shadma; Ahamad, Tansir; Alshehri, Saad M.; Singh, Prabal Kumar; Nishat, Nahid

2010-01-01

A starch-urea-based biodegradable coordination polymer modified by transition metal Mn(II), Co(II), Ni(II), Cu(II), and Zn(II) was prepared by polycondensation of starch and urea. All the synthesized polymeric compounds were characterized by Fourier transform-infrared spectroscopy (FT-IR), 1H-NMR spectroscopy, 13C-NMR spectroscopy, UV-visible spectra, magnetic moment measurements, differential scanning calorimeter (DSC), and thermogravimetric analysis (TGA). The results of electronic spectra and magnetic moment measurements indicate that Mn(II), Co(II), and Ni(II) complexes show octahedral geometry, while Cu(II) and Zn(II) complexes show square planar and tetrahedral geometry, respectively. The thermogravimetric analysis revealed that all the polymeric metal complexes are more thermally stable than the parental ligand. In addition, biodegradable studies of all the polymeric compounds were also carried out through ASTM standards of biodegradable polymers by CO2 evolution method. PMID:20414461

Real-Time UV-Visible Spectroscopy Analysis of Purple Membrane-Polyacrylamide Film Formation Taking into Account Fano Line Shapes and Scattering

PubMed Central

Gomariz, María; Blaya, Salvador; Acebal, Pablo; Carretero, Luis

2014-01-01

We theoretically and experimentally analyze the formation of thick Purple Membrane (PM) polyacrylamide (PA) films by means of optical spectroscopy by considering the absorption of bacteriorhodopsin and scattering. We have applied semiclassical quantum mechanical techniques for the calculation of absorption spectra by taking into account the Fano effects on the ground state of bacteriorhodopsin. A model of the formation of PM-polyacrylamide films has been proposed based on the growth of polymeric chains around purple membrane. Experimentally, the temporal evolution of the polymerization process of acrylamide has been studied as function of the pH solution, obtaining a good correspondence to the proposed model. Thus, due to the formation of intermediate bacteriorhodopsin-doped nanogel, by controlling the polymerization process, an alternative methodology for the synthesis of bacteriorhodopsin-doped nanogels can be provided. PMID:25329473

Real-time UV-visible spectroscopy analysis of purple membrane-polyacrylamide film formation taking into account Fano line shapes and scattering.

PubMed

Gomariz, María; Blaya, Salvador; Acebal, Pablo; Carretero, Luis

2014-01-01

We theoretically and experimentally analyze the formation of thick Purple Membrane (PM) polyacrylamide (PA) films by means of optical spectroscopy by considering the absorption of bacteriorhodopsin and scattering. We have applied semiclassical quantum mechanical techniques for the calculation of absorption spectra by taking into account the Fano effects on the ground state of bacteriorhodopsin. A model of the formation of PM-polyacrylamide films has been proposed based on the growth of polymeric chains around purple membrane. Experimentally, the temporal evolution of the polymerization process of acrylamide has been studied as function of the pH solution, obtaining a good correspondence to the proposed model. Thus, due to the formation of intermediate bacteriorhodopsin-doped nanogel, by controlling the polymerization process, an alternative methodology for the synthesis of bacteriorhodopsin-doped nanogels can be provided.

Meiotic Clade AAA ATPases: Protein Polymer Disassembly Machines.

PubMed

Monroe, Nicole; Hill, Christopher P

2016-05-08

Meiotic clade AAA ATPases (ATPases associated with diverse cellular activities), which were initially grouped on the basis of phylogenetic classification of their AAA ATPase cassette, include four relatively well characterized family members, Vps4, spastin, katanin and fidgetin. These enzymes all function to disassemble specific polymeric protein structures, with Vps4 disassembling the ESCRT-III polymers that are central to the many membrane-remodeling activities of the ESCRT (endosomal sorting complexes required for transport) pathway and spastin, katanin p60 and fidgetin affecting multiple aspects of cellular dynamics by severing microtubules. They share a common domain architecture that features an N-terminal MIT (microtubule interacting and trafficking) domain followed by a single AAA ATPase cassette. Meiotic clade AAA ATPases function as hexamers that can cycle between the active assembly and inactive monomers/dimers in a regulated process, and they appear to disassemble their polymeric substrates by translocating subunits through the central pore of their hexameric ring. Recent studies with Vps4 have shown that nucleotide-induced asymmetry is a requirement for substrate binding to the pore loops and that recruitment to the protein lattice via MIT domains also relieves autoinhibition and primes the AAA ATPase cassettes for substrate binding. The most striking, unifying feature of meiotic clade AAA ATPases may be their MIT domain, which is a module that is found in a wide variety of proteins that localize to ESCRT-III polymers. Spastin also displays an adjacent microtubule binding sequence, and the presence of both ESCRT-III and microtubule binding elements may underlie the recent findings that the ESCRT-III disassembly function of Vps4 and the microtubule-severing function of spastin, as well as potentially katanin and fidgetin, are highly coordinated. Copyright © 2015 Elsevier Ltd. All rights reserved.

Novel polymer anchored Cr(III) Schiff base complexes: Synthesis, characterization and antimicrobial properties

NASA Astrophysics Data System (ADS)

Selvi, Canan; Nartop, Dilek

2012-09-01

New polymer-bound Schiff bases and Cr(III) complexes have been synthesized by the reaction of 4-benzyloxybenzaldehyde, polymer-bound with 2-aminophenol, 2-amino-4-chlorophenol and 2-amino-4-methylphenol. The structure of polymeric-Schiff bases and their Cr(III) complexes have been characterized by elemental analyses, magnetic measurements, IR, UV-Vis, TG-DTA and 1H-NMR. All these compounds have also been investigated for antibacterial activity by the well-diffusion method against Staphylococcus aureus (RSKK-07035), Shigella dysenteria type 10 (RSKK 1036), Listeria monocytogenes 4b(ATCC 19115, Escherichia coli (ATCC 1230), Salmonella typhi H (NCTC 901.8394), Staphylococcus epidermis (ATCC 12228), Brucella abortus (RSKK-03026), Micrococcs luteus (ATCC 93419, Bacillus cereus sp., Pseudomonas putida sp. and for antifungal activity against Candida albicans (Y-1200-NIH).

Terrestrial evolution of polymerization of amino acids - Heat to ATP

NASA Technical Reports Server (NTRS)

Fox, S. W.; Nakashima, T.

1981-01-01

Sets of amino acids containing sufficient trifunctional monomer are thermally polymerized at temperatures such as 65 deg; the amino acids order themselves. Various polymers have diverse catalytic activities. The polymers aggregate, in aqueous solution, to cell-like structures having those activities plus emergent properties, e.g. proliferatability. Polyamino acids containing sufficient lysine catalyze conversion of free amino acids, by ATP, to small peptides and a high molecular weight fraction. The lysine-rich proteinoid is active in solution, within suspensions of cell-like particles, or in other particles composed of lysine-rich proteinoid and homopolyribonucleotide. Selectivities are observed. An archaic polyamino acid prelude to coded protein synthesis is indicated.

Assessing the relative contributions of EspA and CsgA in cellular adherence and biofilm formation of enterohemorrhagic Escherichia coli O157:H7

USDA-ARS?s Scientific Manuscript database

In enterohemorrhagic Escherichia coli O157:H7 (O157), the locus of enterocyte effacement (LEE) encodes a type III secretion system with an extracellular filamentous structure consisting of the polymerized translocator protein EspA. The EspA filaments provide transient interactions between bacterial ...

Evolution of Dengue Virus Type 3 Genotype III in Venezuela: Diversification, Rates and Population Dynamics

PubMed Central

2010-01-01

Background Dengue virus (DENV) is a member of the genus Flavivirus of the family Flaviviridae. DENV are comprised of four distinct serotypes (DENV-1 through DENV-4) and each serotype can be divided in different genotypes. Currently, there is a dramatic emergence of DENV-3 genotype III in Latin America. Nevertheless, we still have an incomplete understanding of the evolutionary forces underlying the evolution of this genotype in this region of the world. In order to gain insight into the degree of genetic variability, rates and patterns of evolution of this genotype in Venezuela and the South American region, phylogenetic analysis, based on a large number (n = 119) of envelope gene sequences from DENV-3 genotype III strains isolated in Venezuela from 2001 to 2008, were performed. Results Phylogenetic analysis revealed an in situ evolution of DENV-3 genotype III following its introduction in the Latin American region, where three different genetic clusters (A to C) can be observed among the DENV-3 genotype III strains circulating in this region. Bayesian coalescent inference analyses revealed an evolutionary rate of 8.48 × 10-4 substitutions/site/year (s/s/y) for strains of cluster A, composed entirely of strains isolated in Venezuela. Amino acid substitution at position 329 of domain III of the E protein (A→V) was found in almost all E proteins from Cluster A strains. Conclusions A significant evolutionary change between DENV-3 genotype III strains that circulated in the initial years of the introduction in the continent and strains isolated in the Latin American region in recent years was observed. The presence of DENV-3 genotype III strains belonging to different clusters was observed in Venezuela, revealing several introduction events into this country. The evolutionary rate found for Cluster A strains circulating in Venezuela is similar to the others previously established for this genotype in other regions of the world. This suggests a lack of correlation among DENV genotype III substitution rate and ecological pattern of virus spread. PMID:21087501

Effect of polysoap on physical and tribology properties of soybean oil-based grease

USDA-ARS?s Scientific Manuscript database

The overall objective of this work was to evaluate the evolution of soybean oil based grease containing polysoaps made from polymeric epoxdized soybean oil. With this aim, lubricating greases were prepared from a mixed soap comprising lithium soap and triethanol ammonium polysoap synthesized from so...

Effects of toxic metals and chemicals on biofilm and biocorrosion.

PubMed

Fang, Herbert H P; Xu, Li-Chong; Chan, Kwong-Yu

2002-11-01

Microbes in marine biofilms aggregated into clusters and increased the production of extracellular polymeric substances (EPS), by over 100% in some cases, when the seawater media containing toxic metals and chemicals, such as Cd(II), Cu(II), Pb(II), Zn(II), AI(III), Cr(III), glutaraldehyde, and phenol. The formation of microbial cluster and the increased production of EPS, which contained 84-92% proteins and 8-16% polysaccharides, accelerated the corrosion of the mild steel. However, there was no quantitative relationship between the degree of increased corrosion and the toxicity of metals/chemicals towards sulfate-reducing bacteria, or the increased EPS production.

A Simple Qualitative Analysis Scheme for Several Environmentally Important Elements

ERIC Educational Resources Information Center

Lambert, Jack L.; Meloan, Clifton E.

1977-01-01

Describes a scheme that uses precipitation, gas evolution, complex ion formation, and flame tests to analyze for the following ions: Hg(I), Hg(II), Sb(III), Cr(III), Pb(II), Sr(II), Cu(II), Cd(II), As(III), chloride, nitrate, and sulfate. (MLH)

Correlating Oxygen Evolution Catalysts Activity and Electronic Structure by a High-Throughput Investigation of Ni1-y-zFeyCrzOx

PubMed Central

Schwanke, Christoph; Stein, Helge Sören; Xi, Lifei; Sliozberg, Kirill; Schuhmann, Wolfgang; Ludwig, Alfred; Lange, Kathrin M.

2017-01-01

High-throughput characterization by soft X-ray absorption spectroscopy (XAS) and electrochemical characterization is used to establish a correlation between electronic structure and catalytic activity of oxygen evolution reaction (OER) catalysts. As a model system a quasi-ternary materials library of Ni1-y-zFeyCrzOx was synthesized by combinatorial reactive magnetron sputtering, characterized by XAS, and an automated scanning droplet cell. The presence of Cr was found to increase the OER activity in the investigated compositional range. The electronic structure of NiII and CrIII remains unchanged over the investigated composition spread. At the Fe L-edge a linear combination of two spectra was observed. These spectra were assigned to FeIII in Oh symmetry and FeIII in Td symmetry. The ratio of FeIII Oh to FeIII Td increases with the amount of Cr and a correlation between the presence of the FeIII Oh and a high OER activity is found. PMID:28287134

Correlating Oxygen Evolution Catalysts Activity and Electronic Structure by a High-Throughput Investigation of Ni1-y-zFeyCrzOx

NASA Astrophysics Data System (ADS)

Schwanke, Christoph; Stein, Helge Sören; Xi, Lifei; Sliozberg, Kirill; Schuhmann, Wolfgang; Ludwig, Alfred; Lange, Kathrin M.

2017-03-01

High-throughput characterization by soft X-ray absorption spectroscopy (XAS) and electrochemical characterization is used to establish a correlation between electronic structure and catalytic activity of oxygen evolution reaction (OER) catalysts. As a model system a quasi-ternary materials library of Ni1-y-zFeyCrzOx was synthesized by combinatorial reactive magnetron sputtering, characterized by XAS, and an automated scanning droplet cell. The presence of Cr was found to increase the OER activity in the investigated compositional range. The electronic structure of NiII and CrIII remains unchanged over the investigated composition spread. At the Fe L-edge a linear combination of two spectra was observed. These spectra were assigned to FeIII in Oh symmetry and FeIII in Td symmetry. The ratio of FeIII Oh to FeIII Td increases with the amount of Cr and a correlation between the presence of the FeIII Oh and a high OER activity is found.

A model for shrinkage strain in photo polymerization of dental composites.

PubMed

Petrovic, Ljubomir M; Atanackovic, Teodor M

2008-04-01

We formulate a new model for the shrinkage strain developed during photo polymerization in dental composites. The model is based on the diffusion type fractional order equation, since it has been proved that polymerization reaction is diffusion controlled (Atai M, Watts DC. A new kinetic model for the photo polymerization shrinkage-strain of dental composites and resin-monomers. Dent Mater 2006;22:785-91). Our model strongly confirms the observation by Atai and Watts (see reference details above) and their experimental results. The shrinkage strain is modeled by a nonlinear differential equation in (see reference details above) and that equation must be solved numerically. In our approach, we use the linear fractional order differential equation to describe the strain rate due to photo polymerization. This equation is solved exactly. As shrinkage is a consequence of the polymerization reaction and polymerization reaction is diffusion controlled, we postulate that shrinkage strain rate is described by a diffusion type equation. We find explicit form of solution to this equation and determine the strain in the resin monomers. Also by using equations of linear viscoelasticity, we determine stresses in the polymer due to the shrinkage. The time evolution of stresses implies that the maximal stresses are developed at the very beginning of the polymerization process. The stress in a dental composite that is light treated has the largest value short time after the treatment starts. The strain settles at the constant value in the time of about 100s (for the cases treated in Atai and Watts). From the model developed here, the shrinkage strain of dental composites and resin monomers is analytically determined. The maximal value of stresses is important, since this value must be smaller than the adhesive bond strength at cavo-restoration interface. The maximum stress determined here depends on the diffusivity coefficient. Since diffusivity coefficient increases as polymerization proceeds, it follows that the periods of light treatments should be shorter at the beginning of the treatment and longer at the end of the treatment, with dark interval between the initial low intensity and following high intensity curing. This is because at the end of polymerization the stress relaxation cannot take place.

Low concentrations of Al(III) accelerate the formation of biofilm: Multiple effects of hormesis and flocculation.

PubMed

Cui, Xiaochun; Huo, Mingxin; Chen, Congli; Yu, Zhisen; Zhou, Chen; Li, Anran; Qiao, Bingqian; Zhou, Dandan; Crittenden, John C

2018-09-01

Residual Al(III) (at low concentration) is common in water treatment plants (WTPs) and is associated with bacteria. We hypothesize that Al(III) accelerate biofouling due to its hydrolysis and hormesis characteristics, as compared with other cations. To verify this, we elaborated the roles of Al(III) at low concentrations on the biofilm formation. Al(III) hormesis (<2.0mg/L) stimulated bacteria growth increased by ~3.7 times, and extracellular polymeric substances production also enhanced. Al(III) flocculation resulted in the suspended cells precipitation instantly, for Al(III) dosages of 0.6 and 2.0mg/L and the concentration of Al(III) decreased by 0.07 and 0.14mg/L, respectively. Al(III) poisoned the bridged bacterial cells and decreased their ATP by 22.36% and 55.91%, respectively. Al(III) formed polymer presented strong affinity with bacterial outer membrane, and this damaged the bacterial outer membrane. This caused proteins to leak at the combined point. Al-polymer bound to NH 2 and/or NH on the leaked protein, contributed to biofilm formation. Biofilm maturity was aided by polysaccharides, which shielded Al(III) toxicity for the formed biofilm. Thus, the biofilm exhibited a distinguished double-layer microstructure, principally with proteins and inactivated cells at the bottom, polysaccharides and activated cells at the top. Thus, hormesis and flocculation caused by low concentration Al(III) mutually promoted each other, and together accelerated biofilm formation. Copyright © 2018 Elsevier B.V. All rights reserved.

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

Palmieri, M.D.; Fritz, J.S.

Metal ions are determined by adding N-methylfurohydroxamic acid to an aqueous sample and then separating the metal chelates by direct injection onto a liquid chromatographic column. Separations on a C/sub 8/ silica column and a polystyrene-divinylbenzene column are compared, with better separations seen on the polymeric column. The complexes formed at low pH values are cationic and are separated by an ion pairing mechanism. Retention times and selectivity of the metal complexes can be varied by changing the pH. Several metal ions can be separated and quantified; separation conditions, linear calibration curve ranges, and detection limits are presented for Zr(IV),more » Hf(IV), Fe(III), Nb(V), Al(III), and Sb(III). Interferences due to the presence of other ions in solution are investigated. Finally, an antiperspirant sample is analyzed for zirconium by high-performance liquid chromatography.« less

Universal Sequence Replication, Reversible Polymerization and Early Functional Biopolymers: A Model for the Initiation of Prebiotic Sequence Evolution

PubMed Central

Walker, Sara Imari; Grover, Martha A.; Hud, Nicholas V.

2012-01-01

Many models for the origin of life have focused on understanding how evolution can drive the refinement of a preexisting enzyme, such as the evolution of efficient replicase activity. Here we present a model for what was, arguably, an even earlier stage of chemical evolution, when polymer sequence diversity was generated and sustained before, and during, the onset of functional selection. The model includes regular environmental cycles (e.g. hydration-dehydration cycles) that drive polymers between times of replication and functional activity, which coincide with times of different monomer and polymer diffusivity. Template-directed replication of informational polymers, which takes place during the dehydration stage of each cycle, is considered to be sequence-independent. New sequences are generated by spontaneous polymer formation, and all sequences compete for a finite monomer resource that is recycled via reversible polymerization. Kinetic Monte Carlo simulations demonstrate that this proposed prebiotic scenario provides a robust mechanism for the exploration of sequence space. Introduction of a polymer sequence with monomer synthetase activity illustrates that functional sequences can become established in a preexisting pool of otherwise non-functional sequences. Functional selection does not dominate system dynamics and sequence diversity remains high, permitting the emergence and spread of more than one functional sequence. It is also observed that polymers spontaneously form clusters in simulations where polymers diffuse more slowly than monomers, a feature that is reminiscent of a previous proposal that the earliest stages of life could have been defined by the collective evolution of a system-wide cooperation of polymer aggregates. Overall, the results presented demonstrate the merits of considering plausible prebiotic polymer chemistries and environments that would have allowed for the rapid turnover of monomer resources and for regularly varying monomer/polymer diffusivities. PMID:22493682

Schiff Base as Additive for Preventing Gas Evolution in Li4Ti5O12-Based Lithium-Ion Battery.

PubMed

Daigle, Jean-Christophe; Asakawa, Yuichiro; Hovington, Pierre; Zaghib, Karim

2017-11-29

Lithium titanium oxide (Li 4 Ti 5 O 12 )-based electrodes are very promising for long-life cycle batteries. However, the surface reactivity of Li 4 Ti 5 O 12 in organic electrolytes leading to gas evolution is still a problem that may cause expansion of pouch cells. In this study, we report the use of Schiff base (1,8-diazabicyclo[5.4.0]undec-7-ene) as an additive that prevents gas evolution during cell aging by a new mechanism involving the solid electrolyte interface on the anode surface. The in situ ring opening polymerization of cyclic carbonates occurs during the first cycles to decrease gas evolution by 9.7 vol % without increasing the internal resistance of the battery.

Polymerization of Building Blocks of Life on Europa and Other Icy Moons.

PubMed

Kimura, Jun; Kitadai, Norio

2015-06-01

The outer Solar System may provide a potential habitat for extraterrestrial life. Remote sensing data from the Galileo spacecraft suggest that the jovian icy moons--Europa, Ganymede, and possibly Callisto--may harbor liquid water oceans underneath their icy crusts. Although compositional information required for the discussion of habitability is limited because of significantly restricted observation data, organic molecules are ubiquitous in the Universe. Recently, in situ spacecraft measurements and experiments suggest that amino acids can be formed abiotically on interstellar ices and comets. These amino acids could be continuously delivered by meteorite or comet impacts to icy moons. Here, we show that polymerization of organic monomers, in particular amino acids and nucleotides, could proceed spontaneously in the cold environment of icy moons, in particular the jovian icy moon Europa as a typical example, based on thermodynamic calculations, though kinetics of formation are not addressed. Observed surface temperature on Europa is 120 and 80 K in the equatorial region and polar region, respectively. At such low temperatures, Gibbs energies of polymerization become negative, and the estimated thermal structure of the icy crust should contain a shallow region (i.e., at a depth of only a few kilometers) favorable for polymerization. Investigation of the possibility of organic monomer polymerization on icy moons could provide good constraints on the origin and early evolution of extraterrestrial life.

Structure and membrane remodeling activity of ESCRT-III helical polymers

DOE PAGES

McCullough, John; Clippinger, Amy K.; Talledge, Nathaniel; ...

2015-12-18

The endosomal sorting complexes required for transport (ESCRT) proteins mediate fundamental membrane remodeling events that require stabilizing negative membrane curvature. These include endosomal intralumenal vesicle formation, HIV budding, nuclear envelope closure, and cytokinetic abscission. ESCRT-III subunits perform key roles in these processes by changing conformation and polymerizing into membrane-remodeling filaments. Here, we report the 4 angstrom resolution cryogenic electron microscopy reconstruction of a one-start, double-stranded helical copolymer composed of two different human ESCRT-III subunits, charged multivesicular body protein 1B (CHMP1B) and increased sodium tolerance 1 (IST1). The inner strand comprises “open” CHMP1B subunits that interlock in an elaborate domain-swapped architecturemore » and is encircled by an outer strand of “closed” IST1 subunits. Unlike other ESCRT-III proteins, CHMP1B and IST1 polymers form external coats on positively curved membranes in vitro and in vivo. In conclusion, our analysis suggests how common ESCRT-III filament architectures could stabilize different degrees and directions of membrane curvature.« less

Cobalt-Bridged Ionic Liquid Polymer on a Carbon Nanotube for Enhanced Oxygen Evolution Reaction Activity.

PubMed

Ding, Yuxiao; Klyushin, Alexander; Huang, Xing; Jones, Travis; Teschner, Detre; Girgsdies, Frank; Rodenas, Tania; Schlögl, Robert; Heumann, Saskia

2018-03-19

By taking inspiration from the catalytic properties of single-site catalysts and the enhancement of performance through ionic liquids on metal catalysts, we exploited a scalable way to place single cobalt ions on a carbon-nanotube surface bridged by polymerized ionic liquid. Single dispersed cobalt ions coordinated by ionic liquid are used as heterogeneous catalysts for the oxygen evolution reaction (OER). Performance data reveals high activity and stable operation without chemical instability. © 2017 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.

Strength Enhancement and Application Development of Carbon Foam for Thermal Protection Systems

DTIC Science & Technology

2004-09-01

to implementation was the inherent weakness and friability of the carbon foams. Under a MDA funded SBIR program, Ceramic Composites Inc . has...there are two approaches under consideration for utilizing carbon foams. Allcomp Inc.iii, Materials and Electrochemical Researchiv, Touchstonev...Ceramic Composites Inc . (CCI) elected to take an alternative approach to enhancing the strength of carbon foam. For our evaluation, two polymeric pre

Contributions of EspA filaments and curli fimbriae in cellular adherence and biofilm formation of enterohemorrhagic Escherichia coli O157:H7

USDA-ARS?s Scientific Manuscript database

In Escherichia coli O157:H7 (O157), the filamentous structure of the type III secretion system is produced from the polymerization of the EspA protein. EspA filaments are essential for O157 adherence to epithelial cells. In previous studies, we demonstrated that O157 hha deletion mutants showed incr...

Immobilization of Polyoxometalates on Tailored Polymeric Surfaces.

PubMed

Aguado-Ureta, Saioa; Rodríguez-Hernández, Juan; Del Campo, Adolfo; Perez-Álvarez, Leyre; Ruiz-Rubio, Leire; Vilas, José Luis; Artetxe, Beñat; Reinoso, Santiago; Gutiérrez-Zorrilla, Juan M

2018-03-02

Herein we describe the preparation of hybrid polymer-inorganic interfaces by the immobilization of polyoxometalate nanoclusters on functionalized polymer surfaces. The polymeric surfaces were made of polystyrene- b -poly(acrylic acid)/polystyrene (PS- b -PAA/PS) blends by spin coating on a silicon wafer. The functionalization of the polymer film was obtained by interfacial migration of the amphiphilic block copolymer toward the interface upon water vapor annealing. The carboxylic acid functional groups contained in the PAA block were then employed to anchor the [Ln III (α-SiW 11 O 39 )] 5- polyoxometalates (Ln: Ce, Er). This purpose was achieved by immersing the films in aqueous solutions of the in situ-formed inorganic nanoclusters. X-ray photoelectron and confocal Raman spectroscopies, together with atomic force microscopy, confirmed the immobilization of the inorganic species at the interface.

Chemistry through cocrystals: pressure-induced polymerization of C 2H 2·C 6H 6 to an extended crystalline hydrocarbon

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

Ward, Matthew D.; Huang, Haw-Tyng; Zhu, Li

The 1:1 acetylene–benzene cocrystal, C 2H 2·C 6H 6, was synthesized under pressure in a diamond anvil cell (DAC) and its evolution under pressure was studied with single-crystal X-ray diffraction and Raman spectroscopy.

Chemistry through cocrystals: pressure-induced polymerization of C 2H 2·C 6H 6 to an extended crystalline hydrocarbon

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

Ward, Matthew D.; Huang, Haw-Tyng; Zhu, Li

The 1 : 1 acetylene–benzene cocrystal, C 2H 2·C 6H 6, was synthesized under pressure in a diamond anvil cell (DAC) and its evolution under pressure was studied with single-crystal X-ray diffraction and Raman spectroscopy.

CHEMICAL ENRICHMENT OF DAMPED Ly{alpha} SYSTEMS AS A DIRECT CONSTRAINT ON POPULATION III STAR FORMATION

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

Kulkarni, Girish; Hennawi, Joseph F.; Rollinde, Emmanuel

2013-08-01

Observations of damped Ly{alpha} absorbers (DLAs) can be used to measure gas-phase metallicities at large cosmological look-back times with high precision. Furthermore, relative abundances can still be measured accurately deep into the reionization epoch (z > 6) using transitions redward of Ly{alpha}, even though Gunn-Peterson absorption precludes measurement of neutral hydrogen. In this paper, we study the chemical evolution of DLAs using a model for the coupled evolution of galaxies and the intergalactic medium (IGM), which is constrained by a variety of observations. Our goal is to explore the influence of Population III stars on the abundance patterns of DLAsmore » to determine the degree to which abundance measurements can discriminate between different Population III stellar initial mass functions (IMFs). We include effects, such as inflows onto galaxies due to cosmological accretion and outflows from galaxies due to supernova feedback. A distinct feature of our model is that it self-consistently calculates the effect of Population III star formation on the reionization of an inhomogeneous IGM, thus allowing us to calculate the thermal evolution of the IGM and implement photoionization feedback on low-mass galaxy formation. We find that if the critical metallicity of Population III to II/I transition is {approx}< 10{sup -4} Z{sub Sun }, then the cosmic Population III star formation rate drops to zero for z < 8. Nevertheless, at high redshift (z {approx} 6), chemical signatures of Population III stars remain in low-mass galaxies (halo mass {approx}< 10{sup 9} M{sub Sun }). This is because photoionization feedback suppresses star formation in these galaxies until relatively low redshift (z {approx} 10), and the chemical record of their initial generation of Population III stars is retained. We model DLAs as these low-mass galaxies, and assign to them a mass-dependent H I absorption cross-section in order to predict the expected distribution of DLA abundance ratios. We find that these distributions are anchored toward abundance ratios set by Population II supernova yields, but they exhibit a tail which depends significantly on the Population III IMF for z > 5. Thus, a sample of DLA metallicity and relative abundance measurements at high redshift holds the promise to constrain Population III enrichment and the Population III IMF. We find that a sample of just 10 DLAs with relative abundances measured to an accuracy of 0.1 dex is sufficient to constrain the Population III IMF at 4{sigma}. These constraints may prove stronger than other probes of Population III enrichment, such as metal-poor stars and individual metal-poor DLAs. Our results provide a global picture of the thermal, ionization, and chemical evolution of the universe, and have the potential to rule out certain Population III scenarios.« less

Efficient Formation of Light-Absorbing Polymeric Nanoparticles from the Reaction of Soluble Fe(III) with C4 and C6 Dicarboxylic Acids.

PubMed

Tran, Ashley; Williams, Geoffrey; Younus, Shagufta; Ali, Nujhat N; Blair, Sandra L; Nizkorodov, Sergey A; Al-Abadleh, Hind A

2017-09-05

The role of transition metals in the formation and aging of secondary organic aerosol (SOA) from aliphatic and aromatic precursors in heterogeneous/multiphase reactions is not well understood. The reactivity of soluble Fe(III) toward known benzene photooxidation products that include fumaric (trans-butenedioic) and muconic (trans,trans-2,4-hexadienedioic) acids was investigated. Efficient formation of brightly colored nanoparticles was observed that are mostly rod- or irregular-shaped depending on the structure of the organic precursor. The particles were characterized for their optical properties, growth rate, elemental composition, iron content, and oxidation state. Results indicate that these particles have mass absorption coefficients on the same order as black carbon and larger than that of biomass burning aerosols. The particles are also amorphous in nature and consist of polymeric chains of Fe centers complexed to carboxylate groups. The oxidation state of Fe was found to be in between Fe(III) and Fe(II) in standard compounds. The organic reactant to iron molar ratio and pH were found to affect the particle growth rate. Control experiments using maleic acid (cis-butenedioic acid) and succinic acid (butanedioic acid) produced no particles. The formation of particles reported herein could account for new pathways that lead to SOA and brown carbon formation mediated by transition metals. In addition, the multiple chemically active components in these particles (iron, organics, and acidic groups) may have an effect on their chemical reactivity (enhanced uptake of trace gases, catalysis, and production of reactive oxygen species) and their likely poor cloud/ice nucleation properties.

Simultaneous acoustic and dielectric real time curing monitoring of epoxy systems

NASA Astrophysics Data System (ADS)

Gkikas, G.; Saganas, Ch.; Grammatikos, S. A.; Aggelis, D. G.; Paipetis, A. S.

2012-04-01

The attainment of structural integrity of the reinforcing matrix in composite materials is of primary importance for the final properties of the composite structure. The detailed monitoring of the curing process on the other hand is paramount (i) in defining the optimal conditions for the impregnation of the reinforcement by the matrix (ii) in limiting the effects of the exotherm produced by the polymerization reaction which create unwanted thermal stresses and (iii) in securing optimal behavior in matrix controlled properties, such as off axis or shear properties and in general the durability of the composite. Dielectric curing monitoring is a well known technique for distinguishing between the different stages of the polymerization of a typical epoxy system. The technique successfully predicts the gelation and the vitrification of the epoxy and has been extended for the monitoring of prepregs. Recent work has shown that distinct changes in the properties of the propagated sound in the epoxy which undergoes polymerization is as well directly related to the gelation and vitrification of the resin, as well as to the attainment of the final properties of the resin system. In this work, a typical epoxy is simultaneously monitored using acoustic and dielectric methods. The system is isothermally cured in an oven to avoid effects from the polymerization exotherm. Typical broadband sensors are employed for the acoustic monitoring, while flat interdigital sensors are employed for the dielectric scans. All stages of the polymerization process were successfully monitored and the validity of both methods was cross checked and verified.

Advanced clay nanocomposites based on in situ photopolymerization utilizing novel polymerizable organoclays

NASA Astrophysics Data System (ADS)

Kim, Soon Ki

Polymer nanocomposite technology has had significant impact on material design. With the environmental advantages of photopolymerization, a research has recently focused on producing nanocomposites utilizing inexpensive clay particles based on in situ photopolymerization. In this research, novel polymerizable organoclays and thiol-ene photopolymerization have been utilized to develop advanced photopolymer clay nanocomposites and to overcome several limitations in conventional free radical photopolymers. To this end, factors important in nanocomposite processes such as monomer composition, clay dispersion, and photopolymerization behavior in combination with the evolution of ultimate nanocomposite properties have been investigated. For monomer-organoclay compositions, higher chemical compatibility of components induces enhanced clay exfoliation, resulting in photopolymerization rate increases due to an amplified clay template effect. Additionally, by affecting the stoichiometric ratio between thiol and acrylate double bond in the clay gallery, thiolated organoclays enhance thiol-ene copolymerization with increased final thiol conversion while acrylated organoclays encourage acrylate homopolymerization. In accordance with the reaction behavior, incorporation of thiolated organoclays makes polymer chains more flexible with decreased glass transition temperature due to higher formation of thio-ether linkages while adding acrylated organoclays significantly increases the modulus. Photopolymer nanocomposites also help overcome two major drawbacks in conventional free radical photopolymerization, namely severe polymerization shrinkage and oxygen inhibition during polymerization. With addition of a low level of thiol monomers, the oxygen inhibition in various acrylate systems can be overcome by addition of only 5wt% thiolated organoclay. The same amount of polymerizable organoclay also induces up to 90% decreases in the shrinkage stress for acrylate or thiol-acrylate systems. However, nonreactive clays do not reduce the stress substantially and even decreases the polymerization rate in air. Additionally, the clay morphology and polymerization behavior are closely related with evolution of ultimate nanocomposite performance. Use of polymerizable organoclay significantly improves overall toughness of nanocomposites by increasing either modulus or elongation at break based on the type of polymerizable organoclay, which demonstrates the promise of this technology as a modulation and/or optimization tool for nanocomposite properties.

Secondary mineral formation associated with respiration of nontronite, NAu-1 by iron reducing bacteria

PubMed Central

O'Reilly, S Erin; Watkins, Janet; Furukawa, Yoko

2005-01-01

Experimental batch and miscible-flow cultures were studied in order to determine the mechanistic pathways of microbial Fe(III) respiration in ferruginous smectite clay, NAu-1. The primary purpose was to resolve if alteration of smectite and release of Fe precedes microbial respiration. Alteration of NAu-1, represented by the morphological and mineralogical changes, occurred regardless of the extent of microbial Fe(III) reduction in all of our experimental systems, including those that contained heat-killed bacteria and those in which O2, rather than Fe(III), was the primary terminal electron acceptor. The solid alteration products observed under transmission electron microscopy included poorly crystalline smectite with diffuse electron diffraction signals, discrete grains of Fe-free amorphous aluminosilicate with increased Al/Si ratio, Fe-rich grains, and amorphous Si globules in the immediate vicinity of bacterial cells and extracellular polymeric substances. In reducing systems, Fe was also found as siderite. The small amount of Fe partitioned to the aqueous phase was primarily in the form of dissolved Fe(III) species even in the systems in which Fe(III) was the primary terminal electron acceptor for microbial respiration. From these observations, we conclude that microbial respiration of Fe(III) in our laboratory systems proceeded through the following: (1) alteration of NAu-1 and concurrent release of Fe(III) from the octahedral sheets of NAu-1; and (2) subsequent microbial respiration of Fe(III).

Research in Energetic Compounds

DTIC Science & Technology

1983-01-01

with hypochlorous acid gave a chlorohydrocarbon, but reaction of the dioxime with chlorine gave 2,6-dichloro-2.6-dinitrosobicyclo[3.3.1)- non&ne. This...Catalyst Concentration on Yield . .3 III. Effect of Monomer Concentration on Yield... 4 IV. Boron Trifluoride and I.q-Butanedzol Catalysis. o V...from 3-azidooxetane with catalysis by boron trifluoride •4 etherate. A problem with this polymerization was that yields were generally in the 50

Sulfonated poly(ether ether ketone)/poly(vinyl alcohol) sensitizing system for solution photogeneration of small Ag, Au, and Cu crystallites.

PubMed

Korchev, A S; Shulyak, T S; Slaten, B L; Gale, W F; Mills, G

2005-04-28

Illumination of air-free aqueous solutions containing sulfonated poly(ether ether ketone) and poly(vinyl alcohol) with 350 nm light results in benzophenone ketyl radicals of the polyketone. The polymer radicals form with a quantum yield 0.02 and decay with a second-order rate constant 6 orders of magnitude lower than that of typical alpha-hydroxy radicals. Evidence is presented that the polymeric benzophenone ketyl radicals reduce Ag+, Cu2+, and AuCl4- to metal particles of nanometer dimensions. Decreases in the reduction rates with increasing Ag(I), Cu(II), and Au(III) concentrations are explained using a kinetic model in which the metal ions quench the excited state of the polymeric benzophenone groups, which forms the macromolecular radicals. Quenching is fastest for Ag+, whereas Cu2+ and AuCl4- exhibit similar rate constants. Particle formation becomes more complex as the number of equivalents needed to reduce the metal ions increases; the Au(III) system is an extreme case where the radical reactions operate in parallel with secondary light-initiated and thermal reduction channels. For each metal ion, the polymer-initiated photoreactions produce crystallites possessing distinct properties, such as a very strong plasmon in the Ag case or the narrow size distribution exhibited by Au particles.

Formulation and Immunogenicity studies of Type III Secretion System needle antigens as Vaccine Candidates

PubMed Central

Barrett, Brooke S.; Markham, Aaron P.; Esfandiary, Reza; Picking, Wendy L.; Picking, William D.; Joshi, Sangeeta B.; Middaugh, C. Russell

2013-01-01

Bacterial infections caused by Shigella flexneri, Salmonella typhimurium and Burkholderia pseudomallei are currently difficult to prevent due to the lack of a licensed vaccine. Here we present formulation and immunogenicity studies for the three type III secretion system (TTSS) needle proteins MxiHΔ5, PrgIΔ5 and BsaLΔ5 (each truncated by five residues at its C terminus) as potential candidates for vaccine development. These antigens are found to be thermally stabilized by the presence of carbohydrates and polyols. Additionally, all adsorb readily to aluminum hydroxide apparently through a combination of hydrogen bonds and/or Van der Waals forces. The interaction of these proteins with the aluminum-based adjuvant changes with time to resulting in varying degrees of irreversible binding. Peptide maps of desorbed protein, however, suggest that chemical changes are not responsible for this irreversible association. The ability of MxiHΔ5 and PrgIΔ5 to elicit strong humoral immune responses was tested in a murine model. When administered intramuscularly as monomers, the needle components exhibited dose dependent immunogenic behavior. The polymerized version of MxiH was exceptionally immunogenic even at low doses. The responses of both monomeric and polymerized forms were boosted by adsorption to an aluminum salt adjuvant. PMID:20845448

Comparative genomics of a cannabis pathogen reveals insight into the evolution of pathogenicity in Xanthomonas

PubMed Central

Jacobs, Jonathan M.; Pesce, Céline; Lefeuvre, Pierre; Koebnik, Ralf

2015-01-01

Pathogenic bacteria in the genus Xanthomonas cause diseases on over 350 plant species, including cannabis (Cannabis sativa L.). Because of regulatory limitations, the biology of the Xanthomonas-cannabis pathosystem remains largely unexplored. To gain insight into the evolution of Xanthomonas strains pathogenic to cannabis, we sequenced the genomes of two geographically distinct Xanthomonas strains, NCPPB 3753 and NCPPB 2877, which were previously isolated from symptomatic plant tissue in Japan and Romania. Comparative multilocus sequence analysis of housekeeping genes revealed that they belong to Group 2, which comprises most of the described species of Xanthomonas. Interestingly, both strains lack the Hrp Type III secretion system and do not contain any of the known Type III effectors. Yet their genomes notably encode two key Hrp pathogenicity regulators HrpG and HrpX, and hrpG and hrpX are in the same genetic organization as in the other Group 2 xanthomonads. Promoter prediction of HrpX-regulated genes suggests the induction of an aminopeptidase, a lipase and two polygalacturonases upon plant colonization, similar to other plant-pathogenic xanthomonads. Genome analysis of the distantly related Xanthomonas maliensis strain 97M, which was isolated from a rice leaf in Mali, similarly demonstrated the presence of HrpG, HrpX, and a HrpX-regulated polygalacturonase, and the absence of the Hrp Type III secretion system and known Type III effectors. Given the observation that some Xanthomonas strains across distinct taxa do not contain hrpG and hrpX, we speculate a stepwise evolution of pathogenicity, which involves (i) acquisition of key regulatory genes and cell wall-degrading enzymes, followed by (ii) acquisition of the Hrp Type III secretion system, which is ultimately accompanied by (iii) successive acquisition of Type III effectors. PMID:26136759

Polymerase ribozyme efficiency increased by G/T-rich DNA oligonucleotides

PubMed Central

Yao, Chengguo; Müller, Ulrich F.

2011-01-01

The RNA world hypothesis states that the early evolution of life went through a stage where RNA served as genome and as catalyst. The replication of RNA world organisms would have been facilitated by ribozymes that catalyze RNA polymerization. To recapitulate an RNA world in the laboratory, a series of RNA polymerase ribozymes was developed previously. However, these ribozymes have a polymerization efficiency that is too low for self-replication, and the most efficient ribozymes prefer one specific template sequence. The limiting factor for polymerization efficiency is the weak sequence-independent binding to its primer/template substrate. Most of the known polymerase ribozymes bind an RNA heptanucleotide to form the P2 duplex on the ribozyme. By modifying this heptanucleotide, we were able to significantly increase polymerization efficiency. Truncations at the 3′-terminus of this heptanucleotide increased full-length primer extension by 10-fold, on a specific template sequence. In contrast, polymerization on several different template sequences was improved dramatically by replacing the RNA heptanucleotide with DNA oligomers containing randomized sequences of 15 nt. The presence of G and T in the random sequences was sufficient for this effect, with an optimal composition of 60% G and 40% T. Our results indicate that these DNA sequences function by establishing many weak and nonspecific base-pairing interactions to the single-stranded portion of the template. Such low-specificity interactions could have had important functions in an RNA world. PMID:21622900

Polymerization of Building Blocks of Life on Europa and Other Icy Moons

PubMed Central

Kitadai, Norio

2015-01-01

Abstract The outer Solar System may provide a potential habitat for extraterrestrial life. Remote sensing data from the Galileo spacecraft suggest that the jovian icy moons—Europa, Ganymede, and possibly Callisto—may harbor liquid water oceans underneath their icy crusts. Although compositional information required for the discussion of habitability is limited because of significantly restricted observation data, organic molecules are ubiquitous in the Universe. Recently, in situ spacecraft measurements and experiments suggest that amino acids can be formed abiotically on interstellar ices and comets. These amino acids could be continuously delivered by meteorite or comet impacts to icy moons. Here, we show that polymerization of organic monomers, in particular amino acids and nucleotides, could proceed spontaneously in the cold environment of icy moons, in particular the jovian icy moon Europa as a typical example, based on thermodynamic calculations, though kinetics of formation are not addressed. Observed surface temperature on Europa is 120 and 80 K in the equatorial region and polar region, respectively. At such low temperatures, Gibbs energies of polymerization become negative, and the estimated thermal structure of the icy crust should contain a shallow region (i.e., at a depth of only a few kilometers) favorable for polymerization. Investigation of the possibility of organic monomer polymerization on icy moons could provide good constraints on the origin and early evolution of extraterrestrial life. Key Words: Planetary science—Europa—Planetary habitability and biosignatures—Extraterrestrial life—Extraterrestrial organic compounds. Astrobiology 15, 430–441. PMID:26060981

Immobilization of Polyoxometalates on Tailored Polymeric Surfaces

PubMed Central

Aguado-Ureta, Saioa; Rodríguez-Hernández, Juan; del Campo, Adolfo; Perez-Álvarez, Leyre

2018-01-01

Herein we describe the preparation of hybrid polymer–inorganic interfaces by the immobilization of polyoxometalate nanoclusters on functionalized polymer surfaces. The polymeric surfaces were made of polystyrene-b-poly(acrylic acid)/polystyrene (PS-b-PAA/PS) blends by spin coating on a silicon wafer. The functionalization of the polymer film was obtained by interfacial migration of the amphiphilic block copolymer toward the interface upon water vapor annealing. The carboxylic acid functional groups contained in the PAA block were then employed to anchor the [LnIII(α-SiW11O39)]5− polyoxometalates (Ln: Ce, Er). This purpose was achieved by immersing the films in aqueous solutions of the in situ-formed inorganic nanoclusters. X-ray photoelectron and confocal Raman spectroscopies, together with atomic force microscopy, confirmed the immobilization of the inorganic species at the interface. PMID:29498656

Origins of the protein synthesis cycle

NASA Technical Reports Server (NTRS)

Fox, S. W.

1981-01-01

Largely derived from experiments in molecular evolution, a theory of protein synthesis cycles has been constructed. The sequence begins with ordered thermal proteins resulting from the self-sequencing of mixed amino acids. Ordered thermal proteins then aggregate to cell-like structures. When they contained proteinoids sufficiently rich in lysine, the structures were able to synthesize offspring peptides. Since lysine-rich proteinoid (LRP) also catalyzes the polymerization of nucleoside triphosphate to polynucleotides, the same microspheres containing LRP could have synthesized both original cellular proteins and cellular nucleic acids. The LRP within protocells would have provided proximity advantageous for the origin and evolution of the genetic code.

Antibiotics and evolution: food for thought.

PubMed

Strachan, C R; Davies, J

2016-03-01

The role of secondary metabolites in effecting and modulating reactions during early biochemical evolution has been largely unappreciated. It is possible that low molecular weight effectors were gradually replaced by polypeptides as polymerizing reactions became more complex, but retained some ability to interact with original receptor sites. Indeed, by reviewing the era of antibiotics in this light we can begin to reconcile the ancient and contemporary activities of these molecules. The corollary being that secondary metabolites participate in a vast array of interactions in nature and investigating their intended receptors will be revealing in both pharmacological and evolutionary terms.

Unusual Electronic Structures of CO2 at Deep Mantle Pressures

NASA Astrophysics Data System (ADS)

Shieh, S. R.; Jarrige, I.; Hiraoka, N.; Wu, M.; Tse, J.; MI, Z.; Kaci, L.; Cai, Y.

2011-12-01

Carbon dioxide (CO2) is an important planetary gas phase found in the Venus, Earth and Mars. The high-pressure behavior of CO2 will have important implications for understanding the evolution and dynamics of planetary interiors. CO2 shows six solid phases and one amorphous phase at various pressure and temperature conditions. However, knowledge of its electronic structure remains unclear and may provide clues for the stability fields. Here we report the electronic structures of CO2 at high pressure and room temperature. The high-pressure inelastic x-ray scattering measurements of CO2 were conducted at beamline BL12XU, SPring-8. A monochromatic beam with incident energy about 10 KeV was focused to a size of 20 by 30 um2. The inelastic x-ray scattering photons were collected at about 35 degrees and a solid state Si detector with resolution of about 1.4 eV was used. Each spectrum was collected for 8-20 hours. Our oxygen K-edge results show that a strong pi resonance peak and some weak sigma peaks were observed in CO2-I. For the carbon K-edge of CO2-I, only a single strong pi resonance peak and a weak broad sigma peak at 313 eV was observed. This unique feature of carbon K-edge spectrum differs from those of graphite and diamond. Furthermore, we found that feature of oxygen K-edge spectra showed change at above 7.4 GPa, indicating the phase transition to CO2-III at pressure lower than those of x-ray diffraction reports. Moreover, at about 50 GPa, both oxygen and carbon K-edge of CO2 exhibit dramatic feature change and could be attributed to polymerization phenomena. It is found that only theoretical calculations including excitonic effects reproduced the experimental trend and indicate polymerization has occurred at 50 GPa and 300 K.

Photoinitiated Polymerization‐Induced Self‐Assembly (Photo‐PISA): New Insights and Opportunities

PubMed Central

Yeow, Jonathan

2017-01-01

The polymerization‐induced self‐assembly (PISA) process is a useful synthetic tool for the efficient synthesis of polymeric nanoparticles of different morphologies. Recently, studies on visible light initiated PISA processes have offered a number of key research opportunities that are not readily accessible using traditional thermally initiated systems. For example, visible light mediated PISA (Photo‐PISA) enables a high degree of control over the dispersion polymerization process by manipulation of the wavelength and intensity of incident light. In some cases, the final nanoparticle morphology of a single formulation can be modulated by simple manipulation of these externally controlled parameters. In addition, temporal (and in principle spatial) control over the Photo‐PISA process can be achieved in most cases. Exploitation of the mild room temperature polymerizations conditions can enable the encapsulation of thermally sensitive therapeutics to occur without compromising the polymerization rate and their activities. Finally, the Photo‐PISA process can enable further mechanistic insights into the morphological evolution of nanoparticle formation such as the effects of temperature on the self‐assembly process. The purpose of this mini‐review is therefore to examine some of these recent advances that have been made in Photo‐PISA processes, particularly in light of the specific advantages that may exist in comparison with conventional thermally initiated systems. PMID:28725534

Dissolved Divalent Metal and pH Effects on Amino Acid Polymerization: A Thermodynamic Evaluation.

PubMed

Kitadai, Norio

2017-03-01

Polymerization of amino acids is a fundamentally important step for the chemical evolution of life. Nevertheless, its response to changing environmental conditions has not yet been well understood because of the lack of reliable quantitative information. For thermodynamics, detailed prediction over diverse combinations of temperature and pH has been made only for a few amino acid-peptide systems. This study used recently reported thermodynamic dataset for the polymerization of the simplest amino acid "glycine (Gly)" to its short peptides (di-glycine and tri-glycine) to examine chemical and structural characteristics of amino acids and peptides that control the temperature and pH dependence of polymerization. Results showed that the dependency is strongly controlled by the intramolecular distance between the amino and carboxyl groups in an amino acid structure, although the side-chain group role is minor. The polymerization behavior of Gly reported earlier in the literature is therefore expected to be a typical feature for those of α-amino acids. Equilibrium calculations were conducted to examine effects of dissolved metals as a function of pH on the monomer-polymer equilibria of Gly. Results showed that metals shift the equilibria toward the monomer side, particularly at neutral and alkaline pH. Metals that form weak interaction with Gly (e.g., Mg 2+ ) have no noticeable influence on the polymerization, although strong interaction engenders significant decrease of the equilibrium concentrations of Gly peptides. Considering chemical and structural characteristics of Gly and Gly peptides that control their interactions with metals, it can be expected that similar responses to the addition of metals are applicable in the polymerization of neutral α-amino acids. Neutral and alkaline aqueous environments with dissolved metals having high affinity with neutral α-amino acids (e.g., Cu 2+ ) are therefore not beneficial places for peptide bond formation on the primitive Earth.

Effect of wet oxidation on the fingerprints of polymeric substances from an activated sludge.

PubMed

Urrea, José Luis; Collado, Sergio; Oulego, Paula; Díaz, Mario

2016-11-15

Thermal pre-treatments of activated sludge involve the release of a high amount of polymeric substances into the bulk medium. The molecular size of these polymers will largely define the subsequent biological treatment of the liquid effluent generated. In this work, the effects of wet oxidation treatment (WO) on the fingerprints of the polymeric substances which compose the activated sludge, were analysed. For a better understanding of these transformations, the sludge was separated into its main fractions: soluble microbial products (SMP), loosely bound extracellular polymeric substances (LB-EPS), tightly bound extracellular polymeric substances (TB-EPS) and naked cells, and then each one was subjected to WO separately (190 °C and 65 bar), determining the fingerprints evolution by size exclusion technique. Results revealed a fast degradation of larger molecules (over 500 kDa) during the first minutes of treatment (40 min). WO also increases the absorptive properties of proteins (especially for 30 kDa), which is possibly due to the hydroxylation of phenylalanine amino acids in their structure. WO of naked cells involved the formation of molecules between 23 and 190 kDa, which are related to the release of cytoplasmic polymers, and more hydrophobic polymers, probably from the cell membrane. The results allowed to establish a relationship between the location of polymeric material and its facility to become oxidised; thus, the more internal the polymeric material in the cell, the easier its oxidation. When working directly with the raw sludge, hydrolysis mechanisms played a key role during the starting period. Once a high degree of solubilisation was reached, the molecules were rapidly oxidised into other compounds with refractory characteristics. The final effluent after WO showed almost 90% of low molecular weight solubilised substances (0-35 kDa). Copyright © 2016 Elsevier Ltd. All rights reserved.

Studies on silicon NMR characterization and kinetic modeling of the structural evolution of siloxane-based materials and their applications in drug delivery and adsorption

NASA Astrophysics Data System (ADS)

Ambati, Jyothirmai

This dissertation presents studies of the synthetic processes and applications of siloxane-based materials. Kinetic investigations of bridged organoalkoxysilanes that are precursors to organic-inorganic hybrid polysilsesquioxanes are a primary focus. Quick gelation despite extensive cyclization is found during the polymerization of bridged silane precursors except for silanes with certain short bridges. This work is an attempt to characterize and understand some of the distinct features of bridged silanes using experimental characterization, kinetic modeling and simulation. In addition to this, the dissertation shows how the properties of siloxane-materials can be engineered for drug delivery and adsorption. The phase behavior of polymerizing mixtures is first investigated to identify the solutions that favor kinetic characterization. Microphase separation is found to cause gradual loss of NMR signal for certain initial compositions. Distortionless Enhancement by Polarization Transfer 29Si NMR is employed to identify the products of polymerization of some short-bridged silanes under no signal loss conditions. This technique requires knowing indirect 29Si-1H scalar coupling constants which sometimes cannot be measured due to second-order effects. However, the B3LYP density functional method with 6-31G basis set is found to predict accurate 29Si- 1H coupling constants of organoalkoxysilanes and siloxanes. The scalar coupling constants thus estimated are employed to resolve non-trivial coupled NMR spectra and quantitative kinetic modeling is performed using the DEPT Si NMR transients. In order to investigate the role of the organic bridging group, the structural evolution of bridged and non-bridged silanes are compared using Monte Carlo simulations. Kinetic and simulation models suggest that cyclization plays a key role right from the onset of polymerization for bridged silanes even more than in non-bridged silanes. The simulations indicate that the carbosiloxane rings formed from short-bridged precursors slow down but do not prevent gelation. The tuning of siloxane-based materials for adsorption technologies are also discussed here. In the first example, antioxidant enzyme loading is investigated as a means to reduce oxidative stress generated by silica nanoparticle drug carriers. Materials are engineered for promising enzyme loading and protection from proteolysis. Second, the potential of copper sulfate impregnation to enhance adsorption of ammonia by silica is explored by molecular simulation. KEYWORDS: Sol-gel Polymerization, Kinetic Investigation, Si NMR, Bridged Silanes, DFT Calculations.

Galapagos III World Evolution Summit: why evolution matters

PubMed Central

Paz-y-Miño-C, Guillermo; Espinosa, Avelina

2016-01-01

There is no place on Earth like the Galapagos Islands and no better destination to discuss the reality of evolution. Under the theme ‘Why Does Evolution Matter’, the University San Francisco of Quito (USFQ), Ecuador, and its Galapagos Institute for the Arts and Sciences (GAIAS), organized the III World Evolution Summit in San Cristóbal Island. The 200-attendee meeting took place on 1 to 5 June 2013; it included 12 keynote speakers, 20 oral presentations by international scholars, and 31 posters by faculty, postdocs, and graduate and undergraduate students. The Summit encompassed five sessions: evolution and society, pre-cellular evolution and the RNA world, behavior and environment, genome, and microbes and diseases. USFQ and GAIAS launched officially the Lynn Margulis Center for Evolutionary Biology and showcased the Galapagos Science Center, in San Cristóbal, an impressive research facility conceptualized in partnership with the University of North Carolina at Chapel Hill, USA. USFQ and GAIAS excelled at managing the conference with exceptional vision and at highlighting the relevance of Galapagos in the history of modern evolutionary thinking; Charles Darwin’s visit to this volcanic archipelago in 1835 unfolded unprecedented scientific interest in what today is a matchless World Heritage. PMID:26925190

Bacterial flagella and Type III secretion: case studies in the evolution of complexity.

PubMed

Pallen, M J; Gophna, U

2007-01-01

Bacterial flagella at first sight appear uniquely sophisticated in structure, so much so that they have even been considered 'irreducibly complex' by the intelligent design movement. However, a more detailed analysis reveals that these remarkable pieces of molecular machinery are the product of processes that are fully compatible with Darwinian evolution. In this chapter we present evidence for such processes, based on a review of experimental studies, molecular phylogeny and microbial genomics. Several processes have played important roles in flagellar evolution: self-assembly of simple repeating subunits, gene duplication with subsequent divergence, recruitment of elements from other systems ('molecular bricolage'), and recombination. We also discuss additional tentative new assignments of homology (FliG with MgtE, FliO with YscJ). In conclusion, rather than providing evidence of intelligent design, flagellar and non-flagellar Type III secretion systems instead provide excellent case studies in the evolution of complex systems from simpler components.

Heparin-mimicking multilayer coating on polymeric membrane via LbL assembly of cyclodextrin-based supramolecules.

PubMed

Deng, Jie; Liu, Xinyue; Ma, Lang; Cheng, Chong; Shi, Wenbin; Nie, Chuanxiong; Zhao, Changsheng

2014-12-10

In this study, multifunctional and heparin-mimicking star-shaped supramolecules-deposited 3D porous multilayer films with improved biocompatibility were fabricated via a layer-by-layer (LbL) self-assembly method on polymeric membrane substrates. Star-shaped heparin-mimicking polyanions (including poly(styrenesulfonate-co-sodium acrylate; Star-PSS-AANa) and poly(styrenesulfonate-co-poly(ethylene glycol)methyl ether methacrylate; Star-PSS-EGMA)) and polycations (poly(methyl chloride-quaternized 2-(dimethylamino)ethyl methacrylate; Star-PMeDMA) were first synthesized by atom transfer radical polymerization (ATRP) from β-cyclodextrin (β-CD) based cores. Then assembly of 3D porous multilayers onto polymeric membrane surfaces was carried out by alternating deposition of the polyanions and polycations via electrostatic interaction. The surface morphology and composition, water contact angle, blood activation, and thrombotic potential as well as cell viability for the coated heparin-mimicking films were systematically investigated. The results of surface ATR-FTIR spectra and XPS spectra verified successful deposition of the star-shaped supramolecules onto the biomedical membrane surfaces; scanning electron microscopy (SEM) and atomic force microscopy (AFM) observations revealed that the modified substrate had 3D porous surface morphology, which might have a great biological influence on the biointerface. Furthermore, systematic in vitro investigation of protein adsorption, platelet adhesion, human platelet factor 4 (PF4, indicates platelet activation), activate partial thromboplastin time (APTT), thrombin time (TT), coagulation activation (thrombin-antithrombin III complex (TAT, indicates blood coagulant)), and blood-related complement activation (C3a and C5a, indicates inflammation potential) confirmed that the heparin-mimicking multilayer coated membranes exhibited ultralow blood component activations and excellent hemocompatibility. Meanwhile, after surface coating, endothelial cell viability was also promoted, which indicated that the heparin-mimicking multilayer coating might extend the application fields of polymeric membranes in biomedical fields.

Feedback Interactions of Polymerized Actin with the Cell Membrane: Waves, Pulses, and Oscillations

NASA Astrophysics Data System (ADS)

Carlsson, Anders

Polymerized filaments of the protein actin have crucial functions in cell migration, and in bending the cell membrane to drive endocytosis or the formation of protrusions. The nucleation and polymerization of actin filaments are controlled by upstream agents in the cell membrane, including nucleation-promoting factors (NPFs) that activate the Arp2/3 complex to form new branches on pre-existing filaments. But polymerized actin (F-actin) also feeds back on the assembly of NPFs. We explore the effects of the resulting feedback loop of F-actin and NPFs on two phenomena: actin pulses that drive endocytosis in yeast, and actin waves traveling along the membrane of several cell types. In our model of endocytosis in yeast, the actin network is grown explicitly in three dimensions, exerts a negative feedback interaction on localized patch of NPFs in the membrane, and bends the membrane by exerting a distribution of forces. This model explains observed actin and NPF pulse dynamics, and the effects of several interventions including i) NPF mutations, ii) inhibition of actin polymerization, and iii) deletion of a protein that allows F-actin to bend the cell membrane. The model predicts that mutation of the active region of an NPF will enhance the accumulation of that NPF, and we confirm this prediction by quantitative fluorescence microscopy. For actin waves, we treat a similar model, with NPFs distributed over a larger region of the cell membrane. This model naturally generates actin waves, and predicts a transition from wave behavior to spatially localized oscillations when NPFs are confined to a small region. We also predict a transition from waves to static polarization as the negative-feedback coupling between F-actin and the NPFs is reduced. Supported by NIGMS Grant R01 GM107667.

Responsive polymer-based colloids for drug delivery and bioconversion

NASA Astrophysics Data System (ADS)

Kudina, Olena

Responsive polymer-based colloids (RPBC) are the colloidal structures containing responsive polymeric component which is able to adapt its physico-chemical properties to the environment by undergoing chemical and/or conformational changes. The goal of the dissertation is to develop and characterize several groups of RPBC with different morphological complexity and explore their potential in drug delivery and bioconversion. The role of RPBC morphology for these specific applications is discussed in details. Three groups of RPBC were fabricated: i. polymeric micelles; ii. mixed polymeric micelles; iii. hybrid polymer-inorganic particles. All fabricated RPBCs contain polymeric component in their structure. The dissertation investigates how the changes of the responsive polymeric component properties are reflected in morphologies of RPBC. The first group of RPBC, polymeric micelles, was formed by the self-assembly of amphiphilic invertible polymers (AIPs) synthesized in our group. AIPs self-assemble into invertible micellar assemblies (IMAs) in solvents of different polarity. In this work, IMAs ability to invert the structure as a response to the change in solvent polarity was demonstrated using 1H NMR spectroscopy and SANS. It was shown that the IMAs incorporate hydrophobic cargo either in the core or in the shell, depending on the chemical structure of cargo molecules. Following in vitro study demonstrates that loaded with drug (curcumin) IMAs are cytotoxic to osteosarcoma cells. Mixed polymeric micelles represent another, more complex, RPBC morphologies studied in the dissertation. Mixed micelles were fabricated from AIPs and amphiphilic oligomers synthesized from pyromellitic dianhydride, polyethylene glycol methyl ethers, and alkanols/cholesterol. The combination of selected AIP and oligomers based on cholesterol results in mixed micelles with an increased drug-loading capacity (from 10% w/w loaded curcumin in single component IMAs to 26%w/w in mixed micelles). Even more complex colloids are hybrid polymer-inorganic particles, the third RPBC group studied in dissertation. Material was designed as core--shell particles with superparamagnetic core engulfed by grafted polymer brushes. These particles were loaded with enzymes (cellulases), thus, are turned into enzymogels for cellulose bioconversion. The study demonstrates that such RPBCs can be used multiple times during hydrolysis and provide an about four-fold increase in glucose production in comparison to free enzymes.

Forensic engineering of advanced polymeric materials. Part III - Biodegradation of thermoformed rigid PLA packaging under industrial composting conditions.

PubMed

Musioł, Marta; Sikorska, Wanda; Adamus, Grazyna; Janeczek, Henryk; Richert, Jozef; Malinowski, Rafal; Jiang, Guozhan; Kowalczuk, Marek

2016-06-01

This paper presents a forensic engineering study on the biodegradation behaviour of prototype packaging thermoformed from PLA-extruded film and plain PLA film under industrial composting conditions. Hydrolytic degradation in water was conducted for reference. The effects of composting duration on changes in molar mass, glass transition temperature and degree of crystallinity of the polymeric material were monitored using gel permeation chromatography (GPC) and differential scanning calorimetry (DSC). The chemical structure of water soluble degradation products of the polymeric material was determined using nuclear magnetic resonance (NMR) and electrospray ionization mass spectrometry (ESI-MS). The results show that the biodegradation process is less dependent on the thermoforming process of PLA and more dependent on the composting/degradation conditions that are applied. The increase in the dispersity index, leading to the bimodal molar mass distribution profile, suggests an autocatalytic hydrolysis effect at the early stage of the composting process, during which the bulk hydrolysis mechanism dominantly operates. Both the prototype PLA-packaging and PLA rigid film samples were shown to have a gradual increase in opacity due to an increase in the degree of crystallinity. Copyright © 2016 Elsevier Ltd. All rights reserved.

Electrochemical ion transfer mediated by a lipophilic Os(ii)/Os(iii) dinonyl bipyridyl probe incorporated in thin film membranes.

PubMed

Jansod, Sutida; Wang, Lu; Cuartero, Maria; Bakker, Eric

2017-09-28

A new lipophilic dinonyl bipyridyl Os(ii)/Os(iii) complex successfully mediates ion transfer processes across voltammetric thin membranes. An added lipophilic cation-exchanger may impose voltammetric anion or cation transfer waves of Gaussian shape that are reversible and repeatable. The peak potential is found to shift with the ion concentration in agreement with the Nernst equation. The addition of tridodecylmethylammonium nitrate to the polymeric film dramatically reduces the peak separation from 240 mV to 65 mV, and the peak width to a near-theoretical value of 85 mV, which agrees with a surface confined process. It is suggested that the cationic additive serves as a phase transfer catalyst.

Photonics of a conjugated organometallic Pt-Ir polymer and its model compounds exhibiting hybrid CT excited states.

PubMed

Soliman, Ahmed M; Fortin, Daniel; Zysman-Colman, Eli; Harvey, Pierre D

2012-04-13

Trans- dichlorobis(tri-n-butylphosphine)platinum(II) reacts with bis(2- phenylpyridinato)-(5,5'-diethynyl-2,2'-bipyridine)iridium(III) hexafluorophosphate to form the luminescent conjugated polymer poly[trans-[(5,5'-ethynyl-2,2'-bipyridine)bis(2- phenylpyridinato)-iridium(III)]bis(tri-n-butylphosphine)platinum(II)] hexafluorophosphate ([Pt]-[Ir])n. Gel permeation chromatography indicates a degree of polymerization of 9 inferring the presence of an oligomer. Comparison of the absorption and emission band positions and their temperature dependence, emission quantum yields, and lifetimes with those for models containing only the [Pt] or the [Ir] units indicates hybrid excited states including features from both chromophores. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Syntheses, crystal structures, and properties of six new lanthanide(III) transition metal tellurium(IV) oxyhalides with three types of structures.

PubMed

Shen, Yue-Ling; Mao, Jiang-Gao

2005-07-25

Solid-state reactions of lanthanide(III) oxide (and lanthanide(III) oxyhalide), transition metal halide (and transition metal oxide), and TeO(2) at high temperature lead to six new lanthanide transition metal tellurium(IV) oxyhalides with three different types of structures, namely, DyCuTe(2)O(6)Cl, ErCuTe(2)O(6)Cl, ErCuTe(2)O(6)Br, Sm(2)Mn(Te(5)O(13))Cl(2), Dy(2)Cu(Te(5)O(13))Br(2), and Nd(4)Cu(TeO(3))(5)Cl(3). Compounds DyCuTe(2)O(6)Cl, ErCuTe(2)O(6)Cl, and ErCuTe(2)O(6)Br are isostructural. The lanthanide(III) ion is eight-coordinated by eight oxygen atoms, and the copper(II) ion is five-coordinated by four oxygens and a halide anion in a distorted square pyramidal geometry. The interconnection of Ln(III) and Cu(II) ions by bridging tellurite anions results in a three-dimensional (3D) network with tunnels along the a-axis; the halide anion and the lone-pair electrons of the tellurium(IV) ions are oriented toward the cavities of the tunnels. Compounds Sm(2)Mn(Te(5)O(13))Cl(2) and Dy(2)Cu(Te(5)O(13))Br(2) are isostructural. The lanthanide(III) ions are eight-coordinated by eight oxygens, and the divalent transition metal ion is octahedrally coordinated by six oxygens. Two types of polymeric tellurium(IV) oxide anions are formed: Te(3)O(8)(4)(-) and Te(4)O(10)(4)(-). The interconnection of the lanthanide(III) and divalent transition metal ions by the above two types of polymeric tellurium(IV) oxide anions leads to a 3D network with long, narrow-shaped tunnels along the b-axis. The halide anions remain isolated and are located at the above tunnels. Nd(4)Cu(TeO(3))(5)Cl(3) features a different structure. All five of the Nd(III) ions are eight-coordinated (NdO(8) for Nd(1), Nd(2), Nd(4), and Nd(5) and NdO(7)Cl for Nd(3)), and the copper(I) ion is tetrahedrally coordinated by four chloride anions. The interconnection of Nd(III) ions by bridging tellurite anions resulted in a 3D network with large tunnels along the b-axis. The CuCl(4) tetrahedra are interconnected into a 1D two-unit repeating (zweier) chain via corner-sharing. These 1D copper(I) chloride chains are inserted into the tunnels of the neodymium(III) tellurite via Nd-Cl-Cu bridges. Luminescent studies show that ErCuTe(2)O(6)Cl and Nd(4)Cu(TeO(3))(5)Cl(3) exhibit strong luminescence in the near-IR region. Magnetic measurements indicate the antiferromagnetic interactions between magnetic centers in these compounds.

Extraction, evolution, and sensory impact of phenolic compounds during red wine maceration.

PubMed

Casassa, L Federico; Harbertson, James F

2014-01-01

We review the extraction into wine and evolution of major phenolic classes of sensory relevance. We present a historical background to highlight that previously established aspects of phenolic extraction and retention into red wine are still subjects of much research. We argue that management of the maceration length is one of the most determining factors in defining the proportion and chemical fate of phenolic compounds in wine. The extraction of anthocyanins, flavonols, flavan-3-ols, and oligomeric and polymeric proanthocyanidins (PAs) is discussed in the context of their individual extraction patterns but also with regard to their interaction with other wine components. The same approach is followed to present the sensory implications of phenolic and phenolic-derived compounds in wine. Overall, we conclude that the chemical diversity of phenolic compounds in grapes is further enhanced as soon as vacuolar and pulp components are released upon crushing, adding a variety of new sensory dimensions to the already present chemical diversity. Polymeric pigments formed by the covalent reaction of anthocyanin and PAs are good candidates to explain some of the observed sensory changes in the color, taste, and mouthfeel attributes of red wines during maceration and aging.

Dimethacrylate network formation and polymer property evolution as determined by the selection of monomers and curing conditions

PubMed Central

Stansbury, Jeffrey W.

2011-01-01

Objectives This overview is intended to highlight connections between monomer structure and the development of highly crosslinked photopolymer networks including the conversion dependent properties of shrinkage, modulus and stress. Methods A review is provided that combines the polymer science and dental materials literature along with examples of relevant experimental results, which include measurements of reaction kinetics, photorheology as well as polymerization shrinkage and stress. Results While new monomers are continually under development for dental materials applications, mixtures of dimethacrylate monomers persist as the most common form of dental resins used on composite restorative materials. Monomer viscosity and reaction potential is derived from molecular structure and by employing real-time near-infrared spectroscopic techniques, the development of macromolecular networks is linked to the evolution of polymerization shrinkage (measured by linometer), modulus (measured by photorheometer), and stress (measured by tensometer). Relationships between the respective polymer properties are examined. Significance Through a better understanding of the polymer network formation and property development processes using conventional dimethacrylate monomer formulations, the rational design of improved materials is facilitated with the ultimate goal of achieving dental polymers that deliver enhanced clinical outcomes. PMID:22192248

Crystal structures of three lead(II) acetate-bridged di-amino-benzene coordination polymers.

PubMed

Geiger, David K; Parsons, Dylan E; Zick, Patricia L

2014-12-01

Poly[tris-(acetato-κ(2) O,O')(μ2-acetato-κ(3) O,O':O)tetra-kis-(μ3-acetato-κ(4) O,O':O:O')bis-(benzene-1,2-di-amine-κN)tetra-lead(II)], [Pb4(CH3COO)8(C6H8N2)2] n , (I), poly[(acetato-κ(2) O,O')(μ3-acetato-κ(4) O,O':O:O')(4-chloro-benzene-1,2-diamine-κN)lead(II)], [Pb(CH3COO)2(C6H7ClN2)] n , (II), and poly[(κ(2) O,O')(μ3-acetato-κ(4) O,O':O:O')(3,4-di-amino-benzo-nitrile-κN)lead(II)], [Pb(CH3COO)2(C7H7N3)] n , (III), have polymeric structures in which monomeric units are joined by bridging acetate ligands. All of the Pb(II) ions exhibit hemidirected coordination. The repeating unit in (I) is composed of four Pb(II) ions having O6, O6N, O7 and O6N coordination spheres, respectively, where N represents a monodentate benzene-1,2-di-amine ligand and O acetate O atoms. Chains along [010] are joined by bridging acetate ligands to form planes parallel to (10-1). (II) and (III) are isotypic and have one Pb(II) ion in the asymmetric unit that has an O6N coordination sphere. Pb2O2 units result from a symmetry-imposed inversion center. Polymeric chains parallel to [100] exhibit hydrogen bonding between the amine and acetate ligands. In (III), additional hydrogen bonds between cyano groups and non-coordinating amines join the chains by forming R 2 (2)(14) rings.

Constraining the Statistics of Population III Binaries

NASA Technical Reports Server (NTRS)

Stacy, Athena; Bromm, Volker

2012-01-01

We perform a cosmological simulation in order to model the growth and evolution of Population III (Pop III) stellar systems in a range of host minihalo environments. A Pop III multiple system forms in each of the ten minihaloes, and the overall mass function is top-heavy compared to the currently observed initial mass function in the Milky Way. Using a sink particle to represent each growing protostar, we examine the binary characteristics of the multiple systems, resolving orbits on scales as small as 20 AU. We find a binary fraction of approx. 36, with semi-major axes as large as 3000 AU. The distribution of orbital periods is slightly peaked at approx. < 900 yr, while the distribution of mass ratios is relatively flat. Of all sink particles formed within the ten minihaloes, approx. 50 are lost to mergers with larger sinks, and 50 of the remaining sinks are ejected from their star-forming disks. The large binary fraction may have important implications for Pop III evolution and nucleosynthesis, as well as the final fate of the first stars.

Lanthanide-based coordination polymers assembled by a flexible multidentate linker: design, structure, photophysical properties, and dynamic solid-state behavior.

PubMed

Marchal, Claire; Filinchuk, Yaroslav; Chen, Xiao-Yan; Imbert, Daniel; Mazzanti, Marinella

2009-01-01

Four picolinate building blocks were implemented into the multidentate linker N,N',N'-tetrakis[(6-carboxypyridin-2-yl)methyl]butylenediamine (H(4)tpabn) with a linear flexible spacer to promote the assembly of lanthanide-based 1D coordination polymers. The role of the linker in directing the geometry of the final assembly is evidenced by the different results obtained in the presence of Htpabn(3-) and tpabn(4-) ions. The tpabn(4-) ion leads to the desired 1D polymer {[Nd(tpabn)]H(3)O x 6 H(2)O}(infinity) (12). The Htpabn(3-) ion leads to the assembly of Tb(III) and Er(III) ions into 1D zigzag chains of the general formula {[M(Htpabn)] x xH(2)O}(infinity) (M = Tb, x = 14 (1); M = Tb, x = 8 (11); M = Er, x = 14 (2); M = Er, x = 5.5 (4)), a 2D network is formed by the Eu(III) ion (i.e., {[Eu(Htpabn)] x 10 H(2)O}(infinity) (7)), and both supramolecular isomers (1D and 2D) are obtained by the Tb(III) ion. The high flexibility of the polymeric chains results in a dynamic behavior with a solvent-induced reversible structural transition. The Tb(III)- and Eu(III)-containing polymers display high-luminescence quantum yields (38 and 18%, respectively). A sizeable near-IR luminescence emission is observed for the Er(III)- and Nd(III)-containing polymers when lattice water molecules are removed.

Equilibrium polymerization of cyclic carbonate oligomers. III. Chain branching and the gel transition

NASA Astrophysics Data System (ADS)

Ballone, P.; Jones, R. O.

2002-10-01

Ring-opening polymerization of cyclic polycarbonate oligomers, where monofunctional active sites act on difunctional monomers to produce an equilibrium distribution of rings and chains, leads to a "living polymer." Monte Carlo simulations [two-dimensional (2D) and three-dimensional (3D)] of the effects of single [J. Chem. Phys. 115, 3895 (2001)] and multiple active sites [J. Chem. Phys. 116, 7724 (2002)] are extended here to trifunctional active sites that lead to branching. Low concentrations of trifunctional particles c3 reduce the degree of polymerization significantly in 2D, and higher concentrations (up to 32%) lead to further large changes in the phase diagram. Gel formation is observed at high total density and sizable c3 as a continuous transition similar to percolation. Polymer and gel are much more stable in 3D than in 2D, and both the total density and the value of c3 required to produce high molecular weight aggregates are reduced significantly. The degree of polymerization in high-density 3D systems is increased by the addition of trifunctional monomers and reduced slightly at low densities and low c3. The presence of branching makes equilibrium states more sensitive (in 2D and 3D) to changes in temperature T. The stabilities of polymer and gel are enhanced by increasing T, and—for sufficiently high values of c3—there is a reversible polymer-gel transformation at a density-dependent floor temperature.

Recent advances in preparation and application of hybrid organic-silica monolithic capillary columns.

PubMed

Ou, Junjie; Lin, Hui; Zhang, Zhenbin; Huang, Guang; Dong, Jing; Zou, Hanfa

2013-01-01

Hybrid organic-silica monolithic columns, regarded as a second generation of silica-based monoliths, have received much interest due to their unique properties over the pure silica-based monoliths. This review mainly focuses on development in the fields of preparation of hybrid monolithic columns in a capillary and their application for CEC and capillary liquid chromatography separation, as well as for sample pretreatment of solid-phase microextraction and immobilized enzyme reactor since July 2010. The preparation approaches are comprehensively summarized with three routes: (i) general sol-gel process using trialkoxysilanes and tetraalkoxysilanes as coprecursors; (ii) "one-pot" process of alkoxysilanes and organic monomers concomitantly proceeding sol-gel chemistry and free radical polymerization; and (iii) other polymerization approaches of organic monomers containing silanes. The modification of hybrid monoliths containing reactive groups to acquire the desired surface functionality is also described. © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Antimicrobial Polymer

DOEpatents

McDonald, William F.; Wright, Stacy C.; Taylor, Andrew C.

2004-09-28

A polymeric composition having antimicrobial properties and a process for rendering the surface of a substrate antimicrobial are disclosed. The polymeric composition comprises a crosslinked chemical combination of (i) a polymer having amino group-containing side chains along a backbone forming the polymer, (ii) an antimicrobial agent selected from metals, metal alloys, metal salts, metal complexes and mixtures thereof, and (iii) a crosslinking agent containing functional groups capable of reacting with the amino groups. In one example embodiment, the polymer is a polyamide formed from a maleic anhydride or maleic acid ester monomer and alkylamines thereby producing a polyamide having amino substituted alkyl chains on one side of the polyamide backbone; the crosslinking agent is a phosphine having the general formula (A).sub.3 P wherein A is hydroxyalkyl; and the metallic antimicrobial agent is selected from chelated silver ions, silver metal, chelated copper ions, copper metal, chelated zinc ions, zinc metal and mixtures thereof.

Dynamic void behavior in polymerizing polymethyl methacrylate cement.

PubMed

Muller, Scott D; McCaskie, Andrew W

2006-02-01

Cement mantle voids remain controversial with respect to survival of total hip arthroplasty. Void evolution is poorly understood, and attempts at void manipulation can only be empirical. We induced voids in a cement model simulating the constraints of the proximal femur. Intravoid pressure and temperature were recorded throughout polymerization, and the initial and final void volumes were measured. Temperature-dependent peak intravoid pressures and void volume increases were observed. After solidification, subatmospheric intravoid pressures were observed. The magnitude of these observations could not be explained by the ideal gas law. Partial pressures of the void gas at peak pressures demonstrated a dominant effect of gaseous monomer, thereby suggesting that void growth is a pressure-driven phenomenon resulting from temperature-dependent evaporation of monomer into existing trapped air voids.

A parallel algorithm for step- and chain-growth polymerization in molecular dynamics.

PubMed

de Buyl, Pierre; Nies, Erik

2015-04-07

Classical Molecular Dynamics (MD) simulations provide insight into the properties of many soft-matter systems. In some situations, it is interesting to model the creation of chemical bonds, a process that is not part of the MD framework. In this context, we propose a parallel algorithm for step- and chain-growth polymerization that is based on a generic reaction scheme, works at a given intrinsic rate and produces continuous trajectories. We present an implementation in the ESPResSo++ simulation software and compare it with the corresponding feature in LAMMPS. For chain growth, our results are compared to the existing simulation literature. For step growth, a rate equation is proposed for the evolution of the crosslinker population that compares well to the simulations for low crosslinker functionality or for short times.

A parallel algorithm for step- and chain-growth polymerization in molecular dynamics

NASA Astrophysics Data System (ADS)

de Buyl, Pierre; Nies, Erik

2015-04-01

Classical Molecular Dynamics (MD) simulations provide insight into the properties of many soft-matter systems. In some situations, it is interesting to model the creation of chemical bonds, a process that is not part of the MD framework. In this context, we propose a parallel algorithm for step- and chain-growth polymerization that is based on a generic reaction scheme, works at a given intrinsic rate and produces continuous trajectories. We present an implementation in the ESPResSo++ simulation software and compare it with the corresponding feature in LAMMPS. For chain growth, our results are compared to the existing simulation literature. For step growth, a rate equation is proposed for the evolution of the crosslinker population that compares well to the simulations for low crosslinker functionality or for short times.

Method for the preparation of novel polyacetylene-type polymers

DOEpatents

Zeigler, John M.

1989-01-01

Polymerization of acetylenic monomers is achieved by using a catalyst which is the reaction product of a tungsten compound and a reducing agent effective to reduce W(VI) to W(III) and/or IV), e.g., WCl.sub.6.(organo-Li, organo-Mg or polysilane). The resultant silylated polymers are of heretofore unachievable high molecular weight and can be used as precursors to a wide variety of new acetylenic polymers by application of substitution reactions.

Chemical Evolution and the Evolutionary Definition of Life.

PubMed

Higgs, Paul G

2017-06-01

Darwinian evolution requires a mechanism for generation of diversity in a population, and selective differences between individuals that influence reproduction. In biology, diversity is generated by mutations and selective differences arise because of the encoded functions of the sequences (e.g., ribozymes or proteins). Here, I draw attention to a process that I will call chemical evolution, in which the diversity is generated by random chemical synthesis instead of (or in addition to) mutation, and selection acts on physicochemical properties, such as hydrolysis, photolysis, solubility, or surface binding. Chemical evolution applies to short oligonucleotides that can be generated by random polymerization, as well as by template-directed replication, and which may be too short to encode a specific function. Chemical evolution is an important stage on the pathway to life, between the stage of "just chemistry" and the stage of full biological evolution. A mathematical model is presented here that illustrates the differences between these three stages. Chemical evolution leads to much larger differences in molecular concentrations than can be achieved by selection without replication. However, chemical evolution is not open-ended, unlike biological evolution. The ability to undergo Darwinian evolution is often considered to be a defining feature of life. Here, I argue that chemical evolution, although Darwinian, does not quite constitute life, and that a good place to put the conceptual boundary between non-life and life is between chemical and biological evolution.

A mixed group II/group III twintron in the Euglena gracilis chloroplast ribosomal protein S3 gene: evidence for intron insertion during gene evolution.

PubMed Central

Copertino, D W; Christopher, D A; Hallick, R B

1991-01-01

The splicing of a 409 nucleotide intron from the Euglena gracilis chloroplast ribosomal protein S3 gene (rps3) was examined by cDNA cloning and sequencing, and northern hybridization. Based on the characterization of a partially spliced pre-mRNA, the intron was characterized as a 'mixed' twintron, composed of a 311 nucleotide group II intron internal to a 98 nucleotide group III intron. Twintron excision is via a 2-step sequential splicing pathway, with removal of the internal group II intron preceding excision of the external group III intron. Based on secondary structural analysis of the twintron, we propose that group III introns may represent highly degenerate versions of group II introns. The existence of twintrons is interpreted as evidence that group II introns were inserted during the evolution of Euglena chloroplast genes from a common ancestor with eubacteria, archaebacteria, cyanobacteria, and other chloroplasts. Images PMID:1721702

Low-metallicity Star Formation (IAU S255)

NASA Astrophysics Data System (ADS)

Hunt, Leslie K.; Madden, Suzanne C.; Schneider, Raffaella

2009-01-01

Preface; SOC and LOC; Participants; Life at the conference; Conference photo; Session I. Population III and Metal-Free Star Formation: 1. Open questions in the study of population III star formation S. C. O. Glover, P. C. Clark, T. H. Greif, J. L. Johnson, V. Bromm, R. S. Klessen and A. Stacy; 2. Protostar formation in the early universe Naoki Yoshida; 3. Population III.1 stars: formation, feedback and evolution of the IMF Jonathan C. Tan; 4. The formation of the first galaxies and the transition to low-mass star formation T. H. Greif, D. R. G. Schleicher, J. L. Johnson, A.-K. Jappsen, R. S. Klessen, P. C. Clark, S. C. O. Glover, A. Stacy and V. Bromm; 5. Low-metallicity star formation: the characteristic mass and upper mass limit Kazuyuki Omukai; 6. Dark stars: dark matter in the first stars leads to a new phase of stellar evolution Katherine Freese, Douglas Spolyar, Anthony Aguirre, Peter Bodenheimer, Paolo Gondolo, J. A. Sellwood and Naoki Yoshida; 7. Effects of dark matter annihilation on the first stars F. Iocco, A. Bressan, E. Ripamonti, R. Schneider, A. Ferrara and P. Marigo; 8. Searching for Pop III stars and galaxies at high redshift Daniel Schaerer; 9. The search for population III stars Sperello di Serego Alighieri, Jaron Kurk, Benedetta Ciardi, Andrea Cimatti, Emanuele Daddi and Andrea Ferrara; 10. Observational search for population III stars in high-redshift galaxies Tohru Nagao; Session II. Metal Enrichment, Chemical Evolution, and Feedback: 11. Cosmic metal enrichment Andrea Ferrara; 12. Insights into the origin of the galaxy mass-metallicity relation Henry Lee, Eric F. Bell and Rachel S. Somerville; 13. LSD and AMAZE: the mass-metallicity relation at z > 3 F. Mannucci and R. Maiolino; 14. Three modes of metal-enriched star formation at high redshift Britton D. Smith, Matthew J. Turk, Steinn Sigurdsson, Brian W. O'Shea and Michael L. Norman; 15. Primordial supernovae and the assembly of the first galaxies Daniel Whalen, Bob Van Veelen, Brian W. O'Shea and Michael L. Norman; 16. Damped Lyα systems as probes of chemical evolution over cosmological timescales Miroslava Dessauges-Zavadsky; 17. Connecting high-redshift galaxy populations through observations of local damped Lyman alpha dwarf galaxies Regina E. Schulte-Ladbeck; 18. Chemical enrichment and feedback in low metallicity environments: constraints on galaxy formation Francesca Matteucci; 19. Effects of reionization on dwarf galaxy formation Massimo Ricotti; 20. The importance of following the evolution of the dust in galaxies on their SEDs A. Schurer, F. Calura, L. Silva, A. Pipino, G. L. Granato, F. Matteucci and R. Maiolino; 21. About the chemical evolution of dSphs (and the peculiar globular cluster ωCen) Andrea Marcolini and Annibale D'Ercole; 22. Young star clusters in the small Magellanic cloud: impact of local and global conditions on star formation Elena Sabbi, Linda J. Smith, Lynn R. Carlson, Antonella Nota, Monca Tosi, Michele Cignoni, Jay S. Gallagher III, Marco Sirianni and Margaret Meixner; 23. Modeling the ISM properties of metal-poor galaxies and gamma-ray burst hosts Emily M. Levesque, Lisa J. Kewley, Kirsten Larson and Leonie Snijders; 24. Dwarf galaxies and the magnetisation of the IGM Uli Klein; Session III. Explosive Events in Low-Metallicity Environments: 25. Supernovae and their evolution in a low metallicity ISM Roger A. Chevalier; 26. First stars - type Ib supernovae connection Ken'ichi Nomoto, Masaomi Tanaka, Yasuomi Kamiya, Nozomu Tominaga and Keiichi Maeda; 27. Supernova nucleosynthesis in the early universe Nozomu Tominaga, Hideyuki Umeda, Keiichi Maeda, Ken'ichi Nomoto and Nobuyuki Iwamoto; 28. Powerful explosions at Z = 0? Sylvia Ekström, Georges Meynet, Raphael Hirschi and André Maeder; 29. Wind anisotropy and stellar evolution Cyril Georgy, Georges Meynet and André Maeder; 30. Low-mass and metal-poor gamma-ray burst

Low-Metallicity Star Formation: From the First Stars to Dwarf Galaxies

NASA Astrophysics Data System (ADS)

Hunt, Leslie K.; Madden, Suzanne C.; Schneider, Raffaella

2008-12-01

Preface; SOC and LOC; Participants; Life at the conference; Conference photo; Session I. Population III and Metal-Free Star Formation: 1. Open questions in the study of population III star formation S. C. O. Glover, P. C. Clark, T. H. Greif, J. L. Johnson, V. Bromm, R. S. Klessen and A. Stacy; 2. Protostar formation in the early universe Naoki Yoshida; 3. Population III.1 stars: formation, feedback and evolution of the IMF Jonathan C. Tan; 4. The formation of the first galaxies and the transition to low-mass star formation T. H. Greif, D. R. G. Schleicher, J. L. Johnson, A.-K. Jappsen, R. S. Klessen, P. C. Clark, S. C. O. Glover, A. Stacy and V. Bromm; 5. Low-metallicity star formation: the characteristic mass and upper mass limit Kazuyuki Omukai; 6. Dark stars: dark matter in the first stars leads to a new phase of stellar evolution Katherine Freese, Douglas Spolyar, Anthony Aguirre, Peter Bodenheimer, Paolo Gondolo, J. A. Sellwood and Naoki Yoshida; 7. Effects of dark matter annihilation on the first stars F. Iocco, A. Bressan, E. Ripamonti, R. Schneider, A. Ferrara and P. Marigo; 8. Searching for Pop III stars and galaxies at high redshift Daniel Schaerer; 9. The search for population III stars Sperello di Serego Alighieri, Jaron Kurk, Benedetta Ciardi, Andrea Cimatti, Emanuele Daddi and Andrea Ferrara; 10. Observational search for population III stars in high-redshift galaxies Tohru Nagao; Session II. Metal Enrichment, Chemical Evolution, and Feedback: 11. Cosmic metal enrichment Andrea Ferrara; 12. Insights into the origin of the galaxy mass-metallicity relation Henry Lee, Eric F. Bell and Rachel S. Somerville; 13. LSD and AMAZE: the mass-metallicity relation at z > 3 F. Mannucci and R. Maiolino; 14. Three modes of metal-enriched star formation at high redshift Britton D. Smith, Matthew J. Turk, Steinn Sigurdsson, Brian W. O'Shea and Michael L. Norman; 15. Primordial supernovae and the assembly of the first galaxies Daniel Whalen, Bob Van Veelen, Brian W. O'Shea and Michael L. Norman; 16. Damped Lyα systems as probes of chemical evolution over cosmological timescales Miroslava Dessauges-Zavadsky; 17. Connecting high-redshift galaxy populations through observations of local damped Lyman alpha dwarf galaxies Regina E. Schulte-Ladbeck; 18. Chemical enrichment and feedback in low metallicity environments: constraints on galaxy formation Francesca Matteucci; 19. Effects of reionization on dwarf galaxy formation Massimo Ricotti; 20. The importance of following the evolution of the dust in galaxies on their SEDs A. Schurer, F. Calura, L. Silva, A. Pipino, G. L. Granato, F. Matteucci and R. Maiolino; 21. About the chemical evolution of dSphs (and the peculiar globular cluster ωCen) Andrea Marcolini and Annibale D'Ercole; 22. Young star clusters in the small Magellanic cloud: impact of local and global conditions on star formation Elena Sabbi, Linda J. Smith, Lynn R. Carlson, Antonella Nota, Monca Tosi, Michele Cignoni, Jay S. Gallagher III, Marco Sirianni and Margaret Meixner; 23. Modeling the ISM properties of metal-poor galaxies and gamma-ray burst hosts Emily M. Levesque, Lisa J. Kewley, Kirsten Larson and Leonie Snijders; 24. Dwarf galaxies and the magnetisation of the IGM Uli Klein; Session III. Explosive Events in Low-Metallicity Environments: 25. Supernovae and their evolution in a low metallicity ISM Roger A. Chevalier; 26. First stars - type Ib supernovae connection Ken'ichi Nomoto, Masaomi Tanaka, Yasuomi Kamiya, Nozomu Tominaga and Keiichi Maeda; 27. Supernova nucleosynthesis in the early universe Nozomu Tominaga, Hideyuki Umeda, Keiichi Maeda, Ken'ichi Nomoto and Nobuyuki Iwamoto; 28. Powerful explosions at Z = 0? Sylvia Ekström, Georges Meynet, Raphael Hirschi and André Maeder; 29. Wind anisotropy and stellar evolution Cyril Georgy, Georges Meynet and André Maeder; 30. Low-mass and metal-poor gamma-ray burst

Decreased solubilization of Pu(IV) polymers by humic acids under anoxic conditions

NASA Astrophysics Data System (ADS)

Xie, Jinchuan; Lin, Jianfeng; Liang, Wei; Li, Mei; Zhou, Xiaohua

2016-11-01

Pu(IV) polymer has a very low solubility (log[Pu(IV)aq]total = -10.4 at pH 7.2 and I = 0). However, some aspects of their environmental fate remain unclear. Humic acids are able to complex with Pu4+ ions and their dissolved species (<10 kD) in the groundwater (neutral to alkaline pH) may cause solubilization of the polymers. Also, humic acids have the native reducing capacity and potentially reduce the polymeric Pu(IV) to Pu(III)aq (log[Pu(III)aq]total = -5.3 at pH 7.2 and I = 0). Solubilization and reduction of the polymers can enhance their mobility in subsurface environments. Nevertheless, humic acids readily coat the surfaces of metal oxides via electrostatic interaction and ligand exchange mechanisms. The humic coatings are expected to prevent both solubilization and reduction of the polymers. Experiments were conducted under anoxic and slightly alkaline (pH 7.2) conditions in order to study whether humic acids have effects on stability of the polymers. The results show that the polymeric Pu(IV) was almost completely transformed into aqueous Pu(IV) in the presence of EDTA ligands. In contrast, the dissolved humic acids did not solubilize the polymers but in fact decreased their solubility by one order of magnitude. The humic coatings were responsible for the decreased solubilization. Such coatings limited the contact between the polymers and EDTA ligands, especially at the relatively high concentrations of humic acids (>0.57 mg/L). Solubilization of the humic-coated polymers was thus inhibited to a significant extent although EDTA, having the great complexation ability, was present in the humic solutions. Reduction of Pu(IV) polymers by the humic acids was also not observed in the absence of EDTA. In the presence of EDTA, the polymers were partially reduced to Pu(III)aq by the humic acids of 0.57 mg/L and the percentage of Pu(III)aq accounted for 51.7% of the total aqueous Pu. This demonstrates that the humic acids were able to reduce the aqueous Pu(IV), instead of the polymeric Pu(IV). Such a demonstration is supported by the very positive redox potential of aqueous Pu(IV)-EDTA complex: Eho ‧ (PuL24-/PuL25-) = 154.3 mV >>Eh (PuO2 (am) /Pu3+) = -182.7 mV calculated at 10-10 mol/L Pu3+ and pH 7.2. At the higher humic concentrations (>0.57 mg/L), the polymers were reduced to a lesser extent because the much denser humic coatings resulted in lower concentrations of the aqueous Pu(IV). Consequently, humic acids make Pu(IV) polymers pretty stable unless the artificial ligands such as EDTA are present in the groundwater.

Sensor calibration of polymeric Hopkinson bars for dynamic testing of soft materials

NASA Astrophysics Data System (ADS)

Martarelli, Milena; Mancini, Edoardo; Lonzi, Barbara; Sasso, Marco

2018-02-01

Split Hopkinson pressure bar (SHPB) testing is one of the most common techniques for the estimation of the constitutive behaviour of metallic materials. In this paper, the characterisation of soft rubber-like materials has been addressed by means of polymeric bars thanks to their reduced mechanical impedance. Due to their visco-elastic nature, polymeric bars are more sensitive to temperature changes than metallic bars, and due to their low conductance, the strain gauges used to measure the propagating wave in an SHPB may be exposed to significant heating. Consequently, a calibration procedure has been proposed to estimate quantitatively the temperature influence on strain gauge output. Furthermore, the calibration is used to determine the elastic modulus of the polymeric bars, which is an important parameter for the synchronisation of the propagation waves measured in the input and output bar strain gate stations, and for the correct determination of stress and strain evolution within the specimen. An example of the application has been reported in order to demonstrate the effectiveness of the technique. Different tests at different strain rates have been carried out on samples made of nytrile butadyene rubber (NBR) from the same injection moulding batch. Thanks to the correct synchronisation of the measured propagation waves measured by the strain gauges and applying the calibrated coefficients, the mechanical behaviour of the NBR material is obtained in terms of strain-rate-strain and stress-strain engineering curves.

Monte Carlo simulations of radioactive waste encapsulated by bisphenol-A polycarbonate and effect of bismuth-III oxide filler material

NASA Astrophysics Data System (ADS)

Özdemir, Tonguç

2017-06-01

Radioactive waste generated from the nuclear industry and non-power applications should carefully be treated, conditioned and disposed according to the regulations set by the competent authority(ies). Bisphenol-a polycarbonate (BPA-PC), a very widely used polymer, might be considered as a potential candidate material for low level radioactive waste encapsulation. In this work, the dose rate distribution in the radioactive waste drum (containing radioactive waste and the BPA-PC polymer matrix) was determined using Monte Carlo simulations. Moreover, the change of mechanical properties of BPA-PC was estimated and their variation within the waste drum was determined for the periods of 15, 30 and 300 years after disposal to the final disposal site. The change of the dose rate within the waste drum with different contents of bismuth-III oxide were also simulated. It was concluded that addition of bismuth-III oxide filler decreases the dose delivered to the polymeric matrix due to photoelectric effect.

In situ immobilization on the silica gel surface and adsorption capacity of polymer-based azobenzene on toxic metal ions

NASA Astrophysics Data System (ADS)

Savchenko, Irina; Yanovska, Elina; Sternik, Dariusz; Kychkyruk, Olga; Ol'khovik, Lidiya; Polonska, Yana

2018-03-01

In situ immobilization of poly[(4-methacryloyloxy-(4'-carboxy)azobenzene] on silica gel surface has been performed by radical polymerization of monomer. The fact of polymer immobilization is confirmed by IR spectroscopy. TG and DSC-MS analysis showed that the mass of the immobilized polymer was 10.61%. The SEM-microphotograph-synthesized composite analysis showed that the immobilized polymer on the silica gel surface is placed in the form of fibers. It has been found that the synthesized composite exhibits the sorption ability in terms of microquantities of Cu(II), Cd(II), Pb(II), Mn(II) and Fe(III) ions in a neutral aqueous medium. The quantitative sorption of microquantities of Pb(II) and Fe(III) ions has been recorded. It has been found that immobilization of the silica gel surface leads to an increase in its sorption capacitance for Fe(III), Cu(II) and Pb(II) ions by half.

The effect of iron to manganese substitution on microperoxidase 8 catalysed peroxidase and cytochrome P450 type of catalysis.

PubMed

Primus, J L; Boersma, M G; Mandon, D; Boeren, S; Veeger, C; Weiss, R; Rietjens, I M

1999-06-01

This study describes the catalytic properties of manganese microperoxidase 8 [Mn(III)MP8] compared to iron microperoxidase 8 [Fe(III)MP8]. The mini-enzymes were tested for pH-dependent activity and operational stability in peroxidase-type conversions, using 2-methoxyphenol and 3,3'-dimethoxybenzidine, and in a cytochrome P450-like oxygen transfer reaction converting aniline to para-aminophenol. For the peroxidase type of conversions the Fe to Mn replacement resulted in a less than 10-fold decrease in the activity at optimal pH, whereas the aniline para-hydroxylation is reduced at least 30-fold. In addition it was observed that the peroxidase type of conversions are all fully blocked by ascorbate and that aniline para-hydroxylation by Fe(III)MP8 is increased by ascorbate whereas aniline para-hydroxylation by Mn(III)MP8 is inhibited by ascorbate. Altogether these results indicate that different types of reactive metal oxygen intermediates are involved in the various conversions. Compound I/II, scavenged by ascorbate, may be the reactive species responsible for the peroxidase reactions, the polymerization of aniline and (part of) the oxygen transfer to aniline in the absence of ascorbate. The para-hydroxylation of aniline by Fe(III)MP8, in the presence of ascorbate, must be mediated by another reactive iron-oxo species which could be the electrophilic metal(III) hydroperoxide anion of microperoxidase 8 [M(III)OOH MP8]. The lower oxidative potential of Mn, compared to Fe, may affect the reactivity of both compound I/II and the metal(III) hydroperoxide anion intermediate, explaining the differential effect of the Fe to Mn substitution on the pH-dependent behavior, the rate of catalysis and the operational stability of MP8.

Polymerization Experiment Of Amino Acids Under High Pressure And Temperature Conditions Simulating The Deep Lithosphere

NASA Astrophysics Data System (ADS)

Ohara, S.; Kakegawa, T.; Nakazawa, H.

2005-12-01

Chemical evolution in deep sea or deep lithosphere is one of the popular hypotheses for the origin of life on the early Earth. In such hypothesis, effects of pressure and temperature on polymerization (and/or stability) of amino acids needed to be evaluated. In this study, high temperature and pressure experiments were performed using of a test-tube-type autoclave for polymerization of amino acids. Approximately 100 mg of Glycine powder were placed into sterilized gold capsule. Multiple experiments were done at 150 degrees for 1 to 8 days at variable pressures (25MPa, 50MPa, 75MPa and 100MPa). Glycine peptides were identified and quantified by high performance liquid chromatography (HPLC). Each capsule was opened carefully and 1 ml of mobile phase was added to release the amino acids and oligopeptide from the solid phase. Liquid phases were separated by the cetrifugal method. Peptides were identified by retention times of authentic reference substances. The reaction yields were determined as percentage of the reactant converted to the reaction product. Pligopeptides more than hexamer were additionally identified by the detection of the molecular ion by liquid chromatography mass spectrometry (LC / MS). A HPLC chromatogram of the products indicated at least seven oligomers: diketopiperazine (cyc(Gly)2), di-glycine (Gly2), tri-glycine (Gly3), tetra-glycine (Gly4), penta-glycine (Gly5) and hexa-glycine (Gly6). We also identified hepta-glycine (Gly7), octa-glycine (Gly8) and nona-glycine (Gly9) with LC/MS. This is the first report that up to nona-glycine was synthesized under high temperature and pressure conditions. In addition, our experiments indicate that polymerization occurs wide range of pressure from 25 to 100 MPa. On the other hand, yields of total amounts of peptide did not change with pressure, suggesting that an unknown process in the autoclave is limiting the yield. We speculate the activity of water vapor, generated by peptide formation reaction, controlled the yield in the autoclave. The results from this study support the theory that chemical evolution could happen in deep Earth environments, such as inside of lithosphere.

Bayesian phylogeny of sucrose transporters: ancient origins, differential expansion and convergent evolution in monocots and dicots

PubMed Central

Peng, Duo; Gu, Xi; Xue, Liang-Jiao; Leebens-Mack, James H.; Tsai, Chung-Jui

2014-01-01

Sucrose transporters (SUTs) are essential for the export and efficient movement of sucrose from source leaves to sink organs in plants. The angiosperm SUT family was previously classified into three or four distinct groups, Types I, II (subgroup IIB), and III, with dicot-specific Type I and monocot-specific Type IIB functioning in phloem loading. To shed light on the underlying drivers of SUT evolution, Bayesian phylogenetic inference was undertaken using 41 sequenced plant genomes, including seven basal lineages at key evolutionary junctures. Our analysis supports four phylogenetically and structurally distinct SUT subfamilies, originating from two ancient groups (AG1 and AG2) that diverged early during terrestrial colonization. In both AG1 and AG2, multiple intron acquisition events in the progenitor vascular plant established the gene structures of modern SUTs. Tonoplastic Type III and plasmalemmal Type II represent evolutionarily conserved descendants of AG1 and AG2, respectively. Type I and Type IIB were previously thought to evolve after the dicot-monocot split. We show, however, that divergence of Type I from Type III SUT predated basal angiosperms, likely associated with evolution of vascular cambium and phloem transport. Type I SUT was subsequently lost in monocots along with vascular cambium, and independent evolution of Type IIB coincided with modified monocot vasculature. Both Type I and Type IIB underwent lineage-specific expansion. In multiple unrelated taxa, the newly-derived SUTs exhibit biased expression in reproductive tissues, suggesting a functional link between phloem loading and reproductive fitness. Convergent evolution of Type I and Type IIB for SUT function in phloem loading and reproductive organs supports the idea that differential vascular development in dicots and monocots is a strong driver for SUT family evolution in angiosperms. PMID:25429293

Different arsenate and phosphate incorporation effects on the nucleation and growth of iron(III) (Hydr)oxides on quartz.

PubMed

Neil, Chelsea W; Lee, Byeongdu; Jun, Young-Shin

2014-10-21

Iron(III) (hydr)oxides play an important role in the geochemical cycling of contaminants in natural and engineered aquatic systems. The ability of iron(III) (hydr)oxides to immobilize contaminants can be related to whether the precipitates form heterogeneously (e.g., at mineral surfaces) or homogeneously in solution. Utilizing grazing incidence small-angle X-ray scattering (GISAXS), we studied heterogeneous iron(III) (hydr)oxide nucleation and growth on quartz substrates for systems containing arsenate and phosphate anions. For the iron(III) only system, the radius of gyration (Rg) of heterogeneously formed precipitates grew from 1.5 to 2.5 (± 1.0) nm within 1 h. For the system containing 10(-5) M arsenate, Rg grew from 3.6 to 6.1 (± 0.5) nm, and for the system containing 10(-5) M phosphate, Rg grew from 2.0 to 4.0 (± 0.2) nm. While the systems containing these oxyanions had more growth, the system containing only iron(III) had the most nucleation events on substrates. Ex situ analyses of homogeneously and heterogeneously formed precipitates indicated that precipitates in the arsenate system had the highest water content and that oxyanions may bridge iron(III) hydroxide polymeric embryos to form a structure similar to ferric arsenate or ferric phosphate. These new findings are important because differences in nucleation and growth rates and particle sizes will impact the number of available reactive sites and the reactivity of newly formed particles toward aqueous contaminants.

Soluble silylated polyacetylene derivatives and their use as percursors to novel polyacetylene-type polymers

DOEpatents

Zeigler, John M.

1989-01-01

Polymerization of acetylenic monomers is achieved by using a catalyst which is the reaction product of a tungsten compound and a reducing agent effective to reduce W(VI) to W(III and/or IV), e.g., WCl.sub.6.(organo-Li, organo-Mg or polysilane). The resultant silylated polymers are of heretofore unachievable high molecular weight and can be used as precursors to a wide variety of new acetylenic polymers by application of substitution reactions.

Method for the preparation of novel polyacetylene-type polymers

DOEpatents

Zeigler, J.M.

1987-11-09

Polymerization of acetylenic monomers is achieved by using a catalyst which is the reaction product of a tungsten compound and a reducing agent effective to reduce W(VI) to W(III and/or IV), e.g., WCl/sub 6//center dot/(organo-Li, organo-Mg or polysilane). The resultant silylated polymers are of heretofore unachievable high molecular weight and can be used as precursors to a wide variety of new acetylenic polymers by application of substitution reactions. 1 tab.

Influence of prefermentary clarification on the composition of apple musts.

PubMed

Hubert, Bertrand; Baron, Alain; Le Quere, Jean-Michel; Renard, Catherine M G C

2007-06-27

The polyphenol contents and colors of cider apple juices were compared before (NCM, not clarified must) and after five clarification treatments: enzymatic depectinization by pectinases followed by (i) sedimentation (depectinized and decanted juice), (ii) tangential microfiltration (microfiltered juice) or (iii) fining using gelatin (gelatin-treated juice); (iv) enzymatic gelification of pectin by pectin methylesterase followed by natural keeving by a cider manufacturer (producer keeved juice), or (v) flotation (floated with nitrogen gas juice). The pressing of the apples led to the highly selective extraction of the flavan-3-ols with the lowest molecular weights: In the apples, the number average degree of polymerization of the flavanols was 14.7, and it dropped to 2.2 in the NCM. Keeving had the highest impact on the reduction of both flavanol content and number average degree of polymerization. The flavanol concentrations were decreased in the permeate by fining (30%) much more than by depectinization. The clarification step led to a further decrease of the number average degree of polymerization. Hydroxycinnamic acids were less affected by the extraction process (with extraction yields >50%) and not affected by clarification. The color evolved with all treatments: L*, a*, b*, and chromaticity distance index measures indicated a reduction of orange-yellow saturation except after sedimentation.

High throughput atmospheric pressure plasma-induced graft polymerization for identifying protein-resistant surfaces.

PubMed

Gu, Minghao; Kilduff, James E; Belfort, Georges

2012-02-01

Three critical aspects of searching for and understanding how to find highly resistant surfaces to protein adhesion are addressed here with specific application to synthetic membrane filtration. They include the (i) discovery of a series of previously unreported monomers from a large library of monomers with high protein resistance and subsequent low fouling characteristics for membrane ultrafiltration of protein-containing fluids, (ii) development of a new approach to investigate protein-resistant mechanisms from structure-property relationships, and (iii) adaptation of a new surface modification method, called atmospheric pressure plasma-induced graft polymerization (APP), together with a high throughput platform (HTP), for low cost vacuum-free synthesis of anti-fouling membranes. Several new high-performing chemistries comprising two polyethylene glycol (PEG), two amines and one zwitterionic monomers were identified from a library (44 commercial monomers) of five different classes of monomers as strong protein-resistant monomers. Combining our analysis here, using the Hansen solubility parameters (HSP) approach, and data from the literature, we conclude that strong interactions with water (hydrogen bonding) and surface flexibility are necessary for producing the highest protein resistance. Superior protein-resistant surfaces and subsequent anti-fouling performance was obtained with the HTP-APP as compared with our earlier HTP-photo graft-induced polymerization (PGP). Copyright © 2011 Elsevier Ltd. All rights reserved.

Size exclusion chromatography with evaporative light scattering detection as a method for speciation analysis of polydimethylsiloxanes. III. Identification and determination of dimeticone and simeticone in pharmaceutical formulations.

PubMed

Mojsiewicz-Pieńkowska, Krystyna

2012-01-25

The pharmaceutical industry is one of the more important sectors for the use of polydimethylsiloxanes (PDMS), which belong to the organosilicon polymers. In drugs for internal use, they are used as an active pharmaceutical ingredient (API) called dimeticone or simeticone. Due to their specific chemical nature, PDMS can have different degrees of polymerization, which determine the molecular weight and viscosity. The Pharmacopoeial monographs for dimeticone and simeticone, only give the permitted polymerization and viscosity range. It is, however, essential to know also the degree of polymerization or the specific molecular weight of PDMS that are present in pharmaceutical formulations. In the literature there is information about the impact of particle size, and thus molecular weight, on the toxicity, absorption and migration in living organisms. This study focused on the use of a developed method - the exclusion chromatography with evaporative light scattering detector (SEC-ELSD) - for identification and determination of dimeticone and simeticone in various pharmaceutical formulations. The method had a high degree of specificity and was suitable for speciation analysis of these polymers. So far the developed method has not been used in the control of medicinal products containing dimeticone or simeticone. Copyright © 2011 Elsevier B.V. All rights reserved.

Modeling liquid crystal polymeric devices

NASA Astrophysics Data System (ADS)

Gimenez Pinto, Vianney Karina

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

A nano-disperse ferritin-core mimetic that efficiently corrects anemia without luminal iron redox activity

PubMed Central

Powell, Jonathan J.; Bruggraber, Sylvaine F.A.; Faria, Nuno; Poots, Lynsey K.; Hondow, Nicole; Pennycook, Timothy J.; Latunde-Dada, Gladys O.; Simpson, Robert J.; Brown, Andy P.; Pereira, Dora I.A.

2014-01-01

The 2-5 nm Fe(III) oxo-hydroxide core of ferritin is less ordered and readily bioavailable compared to its pure synthetic analogue, ferrihydrite. We report the facile synthesis of tartrate-modified, nano-disperse ferrihydrite of small primary particle size, but with enlarged or strained lattice structure (~ 2.7 Å for the main Bragg peak versus 2.6 Å for synthetic ferrihydrite). Analysis indicated that co-precipitation conditions can be achieved for tartrate inclusion into the developing ferrihydrite particles, retarding both growth and crystallization and favoring stabilization of the cross-linked polymeric structure. In murine models, gastrointestinal uptake was independent of luminal Fe(III) reduction to Fe(II) and, yet, absorption was equivalent to that of ferrous sulphate, efficiently correcting the induced anemia. This process may model dietary Fe(III) absorption and potentially provide a side effect-free form of cheap supplemental iron. From the Clinical Editor Small size tartrate-modified, nano-disperse ferrihydrite was used for efficient gastrointestinal delivery of soluble Fe(III) without the risk for free radical generation in murine models. This method may provide a potentially side effect-free form iron supplementation. PMID:24394211

Impact constraints on the environment for chemical evolution and the continuity of life

NASA Technical Reports Server (NTRS)

Oberbeck, Verne R.; Fogleman, Guy

1990-01-01

The moon and the earth were bombarded heavily by planetesimals and asteroids that were capable of interfering with chemical evolution and the origin of life. This paper explores the frequency of giant terrestrial impacts able to stop prebiotic chemistry in the probable regions of chemical evolution. The limited time available between impacts disruptive to prebiotic chemistry at the time of the oldest evidence of life suggests the need for a rapid process for chemical evolution of life. On the other hand, rapid chemical evolution in cloud systems and lakes or other shallow evaporating water bodies would have been possible because reactants could have been concentrated and polymerized rapidly in this environment. Thus life probably could have originated near the surface between frequent surface-sterilizing impacts. There may not have been continuity of life depending on sunlight because there is evidence that life, existing as early as 3.8 Gyr ago, may have been destroyed by giant impacts. The first such organisms on earth were probably not the ancestors of present life.

Fabrication of AlN/BN bishell hollow nanofibers by electrospinning and atomic layer deposition

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

Haider, Ali; Kayaci, Fatma; Uyar, Tamer

2014-09-01

Aluminum nitride (AlN)/boron nitride (BN) bishell hollow nanofibers (HNFs) have been fabricated by successive atomic layer deposition (ALD) of AlN and sequential chemical vapor deposition (CVD) of BN on electrospun polymeric nanofibrous template. A four-step fabrication process was utilized: (i) fabrication of polymeric (nylon 6,6) nanofibers via electrospinning, (ii) hollow cathode plasma-assisted ALD of AlN at 100 °C onto electrospun polymeric nanofibers, (iii) calcination at 500 °C for 2 h in order to remove the polymeric template, and (iv) sequential CVD growth of BN at 450 °C. AlN/BN HNFs have been characterized for their chemical composition, surface morphology, crystal structure, and internal nanostructuremore » using X-ray photoelectron spectroscopy, scanning electron microscopy, transmission electron microscopy, energy dispersive X-ray spectroscopy, and selected area electron diffraction. Measurements confirmed the presence of crystalline hexagonal BN and AlN within the three dimensional (3D) network of bishell HNFs with relatively low impurity content. In contrast to the smooth surface of the inner AlN layer, outer BN coating showed a highly rough 3D morphology in the form of BN nano-needle crystallites. It is shown that the combination of electrospinning and plasma-assisted low-temperature ALD/CVD can produce highly controlled multi-layered bishell nitride ceramic hollow nanostructures. While electrospinning enables easy fabrication of nanofibrous template, self-limiting reactions of plasma-assisted ALD and sequential CVD provide control over the wall thicknesses of AlN and BN layers with sub-nanometer accuracy.« less

Taming Prebiotic Chemistry: The Role of Heterogeneous and Interfacial Catalysis in the Emergence of a Prebiotic Catalytic/Information Polymer System

PubMed Central

Monnard, Pierre-Alain

2016-01-01

Cellular life is based on interacting polymer networks that serve as catalysts, genetic information and structural molecules. The complexity of the DNA, RNA and protein biochemistry suggests that it must have been preceded by simpler systems. The RNA world hypothesis proposes RNA as the prime candidate for such a primal system. Even though this proposition has gained currency, its investigations have highlighted several challenges with respect to bulk aqueous media: (1) the synthesis of RNA monomers is difficult; (2) efficient pathways for monomer polymerization into functional RNAs and their subsequent, sequence-specific replication remain elusive; and (3) the evolution of the RNA function towards cellular metabolism in isolation is questionable in view of the chemical mixtures expected on the early Earth. This review will address the question of the possible roles of heterogeneous media and catalysis as drivers for the emergence of RNA-based polymer networks. We will show that this approach to non-enzymatic polymerizations of RNA from monomers and RNA evolution cannot only solve some issues encountered during reactions in bulk aqueous solutions, but may also explain the co-emergence of the various polymers indispensable for life in complex mixtures and their organization into primitive networks. PMID:27827919

H2 Production Under Visible Light Irradiation from Aqueous Methanol Solution on CaTiO3:Cu Prepared by Spray Pyrolysis

NASA Astrophysics Data System (ADS)

Lim, Sung Nam; Song, Shin Ae; Jeong, Yong-Cheol; Kang, Hyun Woo; Park, Seung Bin; Kim, Ki Young

2017-10-01

Perovskite-type photocatalysts of CaCu x Ti1- x O3 (0 ≤ x ≤ 0.02) powder were prepared by spray pyrolysis of aqueous solution or aqueous solution with polymeric additive. The effects of the amount of copper ions doped in the photocatalyst and the precursor type on the photocatalytic activity under visible-light irradiation were investigated. The crystal structure, oxidation state, and light adsorption properties of the prepared photocatalysts were analyzed using x-ray diffraction, x-ray photoelectron spectroscopy, and diffuse reflectance spectroscopy, respectively. The doping of copper ions in CaTiO3 allowed visible-light absorption owing to a narrowing of the band gap energy of the host material through the formation of a new donor level for copper ions. Among the doped samples prepared from the aqueous precursor, CaTiO3 doped with 1 mol.% copper ions had the highest hydrogen evolution rate (140.7 μmol g-1 h-1). Notably, the hydrogen evolution rate of the photocatalyst doped with 1 mol.% copper ions prepared from the aqueous precursor with polymeric additive (295.0 μmol g-1 h-1) was two times greater than that prepared from the aqueous precursor, due to the morphology effect.

Oil-in-oil emulsions: a unique tool for the formation of polymer nanoparticles.

PubMed

Klapper, Markus; Nenov, Svetlin; Haschick, Robert; Müller, Kevin; Müllen, Klaus

2008-09-01

Polymer latex particles are nanofunctional materials with widespread applications including electronics, pharmaceuticals, photonics, cosmetics, and coatings. These materials are typically prepared using waterborne heterogeneous systems such as emulsion, miniemulsion, and suspension polymerization. However, all of these processes are limited to water-stable catalysts and monomers mainly polymerizable via radical polymerization. In this Account, we describe a method to overcome this limitation: nonaqueous emulsions can serve as a versatile tool for the synthesis of new types of polymer nanoparticles. To form these emulsions, we first needed to find two nonmiscible nonpolar/polar aprotic organic solvents. We used solvent mixtures of either DMF or acetonitrile in alkanes and carefully designed amphiphilic block and statistical copolymers, such as polyisoprene- b-poly(methyl methacrylate) (PI- b-PMMA), as additives to stabilize these emulsions. Unlike aqueous emulsions, these new emulsion systems allowed the use of water-sensitive monomers and catalysts. Although polyaddition and polycondensation reactions usually lead to a large number of side products and only to oligomers in the aqueous phase, these new conditions resulted in high-molecular-weight, defect-free polymers. Furthermore, conducting nanoparticles were produced by the iron(III)-induced synthesis of poly(ethylenedioxythiophene) (PEDOT) in an emulsion of acetonitrile in cyclohexane. Because metallocenes are sensitive to nitrile and carbonyl groups, the acetonitrile and DMF emulsions were not suitable for carrying out metallocene-catalyzed olefin polymerization. Instead, we developed a second system, which consists of alkanes dispersed in perfluoroalkanes. In this case, we designed a new amphipolar polymeric emulsifier with fluorous and aliphatic side chains to stabilize the emulsions. Such heterogeneous mixtures facilitated the catalytic polymerization of ethylene or propylene to give spherical nanoparticles of high molecular weight polyolefins. These nonaqueous systems also allow for the combination of different polymerization techniques to obtain complex architectures such as core-shell structures. Previously, such structures primarily used vinylic monomers, which greatly limited the number of polymer combinations. We have demonstrated how nonaqueous emulsions allow the use of a broad variety of hydrolyzable monomers and sensitive catalysts to yield polyester, polyurethane, polyamide, conducting polymers, and polyolefin latex particles in one step under ambient reaction conditions. This nonpolar emulsion strategy dramatically increases the chemical palette of polymers that can form nanoparticles via emulsion polymerization.

Prebiotic chemistry in clouds

NASA Technical Reports Server (NTRS)

Oberbeck, Verne R.; Marshall, John; Shen, Thomas

1991-01-01

The chemical evolution hypothesis of Woese (1979), according to which prebiotic reactions occurred rapidly in droplets in giant atmospheric reflux columns was criticized by Scherer (1985). This paper proposes a mechanism for prebiotic chemistry in clouds that answers Scherer's concerns and supports Woese's hypothesis. According to this mechanism, rapid prebiotic chemical evolution was facilitated on the primordial earth by cycles of condensation and evaporation of cloud drops containing clay condensation nuclei and nonvolatile monomers. For example, amino acids supplied by, or synthesized during entry of meteorites, comets, and interplanetary dust, would have been scavenged by cloud drops containing clay condensation nuclei and would be polymerized within cloud systems during cycles of condensation, freezing, melting, and evaporation of cloud drops.

Effect of Population III Multiplicity on Dark Star Formation

NASA Technical Reports Server (NTRS)

Stacy, Athena; Pawlik, Andreas H.; Bromm, Volker; Loeb, Abraham

2012-01-01

We numerically study the mutual interaction between dark matter (DM) and Population III (Pop III) stellar systems in order to explore the possibility of Pop III dark stars within this physical scenario. We perform a cosmological simulation, initialized at z approx. 100, which follows the evolution of gas and DM. We analyze the formation of the first mini halo at z approx. 20 and the subsequent collapse of the gas to densities of 10(exp 12)/cu cm. We then use this simulation to initialize a set of smaller-scale 'cut-out' simulations in which we further refine the DM to have spatial resolution similar to that of the gas. We test multiple DM density profiles, and we employ the sink particle method to represent the accreting star-forming region. We find that, for a range of DM configurations, the motion of the Pop III star-disk system serves to separate the positions of the protostars with respect to the DM density peak, such that there is insufficient DM to influence the formation and evolution of the protostars for more than approx. 5000 years. In addition, the star-disk system causes gravitational scattering of the central DM to lower densities, further decreasing the influence of DM over time. Any DM-powered phase of Pop III stars will thus be very short-lived for the typical multiple system, and DM will not serve to significantly prolong the life of Pop III stars.

Pelagic photoferrotrophy and iron cycling in a modern ferruginous basin.

PubMed

Llirós, Marc; García-Armisen, Tamara; Darchambeau, François; Morana, Cédric; Triadó-Margarit, Xavier; Inceoğlu, Özgül; Borrego, Carles M; Bouillon, Steven; Servais, Pierre; Borges, Alberto V; Descy, Jean-Pierre; Canfield, Don E; Crowe, Sean A

2015-09-08

Iron-rich (ferruginous) ocean chemistry prevailed throughout most of Earth's early history. Before the evolution and proliferation of oxygenic photosynthesis, biological production in the ferruginous oceans was likely driven by photoferrotrophic bacteria that oxidize ferrous iron {Fe(II)} to harness energy from sunlight, and fix inorganic carbon into biomass. Photoferrotrophs may thus have fuelled Earth's early biosphere providing energy to drive microbial growth and evolution over billions of years. Yet, photoferrotrophic activity has remained largely elusive on the modern Earth, leaving models for early biological production untested and imperative ecological context for the evolution of life missing. Here, we show that an active community of pelagic photoferrotrophs comprises up to 30% of the total microbial community in illuminated ferruginous waters of Kabuno Bay (KB), East Africa (DR Congo). These photoferrotrophs produce oxidized iron {Fe(III)} and biomass, and support a diverse pelagic microbial community including heterotrophic Fe(III)-reducers, sulfate reducers, fermenters and methanogens. At modest light levels, rates of photoferrotrophy in KB exceed those predicted for early Earth primary production, and are sufficient to generate Earth's largest sedimentary iron ore deposits. Fe cycling, however, is efficient, and complex microbial community interactions likely regulate Fe(III) and organic matter export from the photic zone.

Evaluation of wetting ability of five new saliva substitutes on heat-polymerized acrylic resin for retention of complete dentures in dry mouth patients: a comparative study

PubMed Central

Mohsin, Abdul Habeeb Bin; Reddy, Varalakshmi; Kumar, Praveen; Raj, Jeevan; Babu, Siva Santosh

2017-01-01

Introduction The aim of this study was to evaluate & compare the wetting ability of five saliva substitutes & distilled water on heat-polymerized acrylic resin. Contact angle of the saliva substitute on denture base can be taken as an indicator of wettability. Good wetting of heat-polymerized acrylic resin is critical for optimum retention of complete dentures. Methods Two hundred & forty samples of heat-polymerized acrylic resin were fabricated using conventional method. 240 samples divided into 6 groups with 40 samples in each group. Advancing & Receding contact angles were measured using Contact Angle Goniometer & DSA4 software analysis. Results Anova test was carried out to test the significance in difference of contact angle values in the six groups. The mean of advancing angle values & mean of receding angle values of all the six groups has shown statistically significant difference between the groups. The mean of angle of hysteresis values of all the six groups are statistically not significant between the groups. A multiple comparison using Bonferroni’s test was carried out to verify the significance of difference between the contact angles in a pair of groups. Statistically significant difference was seen when Aqwet (Group II) was compared to Distilled water (Group I), Wet Mouth (Group III), E-Saliva (Group IV), Biotene (Group V), and Moi-Stir (Group VI). Conclusion The contact angles of five saliva substitutes and distilled water were measured and compared. Group II (AQWET) has the lowest advancing and receding contact angle values and the highest angle of hysteresis on heat-polymerized acrylic resin. Based on contact angle values, Group II (AQWET) has the best wetting ability on heat-cured acrylic resins. The ability of saliva to wet the denture surface is one of the most important properties for complete denture retention in dry mouth cases. PMID:29187918

Polymer-Based Black Phosphorus (bP) Hybrid Materials by in Situ Radical Polymerization: An Effective Tool To Exfoliate bP and Stabilize bP Nanoflakes

PubMed Central

2018-01-01

Black phosphorus (bP) has been recently investigated for next generation nanoelectronic multifunctional devices. However, the intrinsic instability of exfoliated bP (the bP nanoflakes) toward both moisture and air has so far overshadowed its practical implementation. In order to contribute to fill this gap, we report here the preparation of new hybrid polymer-based materials where bP nanoflakes (bPn) exhibit a significantly improved stability. The new materials have been prepared by different synthetic paths including: (i) the mixing of conventionally liquid-phase exfoliated bP (in dimethyl sulfoxide, DMSO) with poly(methyl methacrylate) (PMMA) solution; (ii) the direct exfoliation of bP in a polymeric solution; (iii) the in situ radical polymerization after exfoliating bP in the liquid monomer (methyl methacrylate, MMA). This last methodology concerns the preparation of stable suspensions of bPn–MMA by sonication-assisted liquid-phase exfoliation (LPE) of bP in the presence of MMA followed by radical polymerization. The hybrids characteristics have been compared in order to evaluate the bP dispersion and the effectiveness of the bPn interfacial interactions with polymer chains aimed at their long-term environmental stabilization. The passivation of the bPn is particularly effective when the hybrid material is prepared by in situ polymerization. By using this synthetic methodology, the nanoflakes, even if with a gradient of dispersion (size of aggregates), preserve their chemical structure from oxidation (as proved by both Raman and 31P-solid state NMR studies) and are particularly stable to air and UV light exposure. The feasibility of this approach, capable of efficiently exfoliating bP while protecting the bPn, has been then verified by using different vinyl monomers (styrene and N-vinylpyrrolidone), thus obtaining hybrids where the nanoflakes are embedded in polymer matrices with a variety of intriguing thermal, mechanical, and solubility characteristics.

Mechanistic insights for block copolymer morphologies: how do worms form vesicles?

PubMed

Blanazs, Adam; Madsen, Jeppe; Battaglia, Giuseppe; Ryan, Anthony J; Armes, Steven P

2011-10-19

Amphiphilic diblock copolymers composed of two covalently linked, chemically distinct chains can be considered to be biological mimics of cell membrane-forming lipid molecules, but with typically more than an order of magnitude increase in molecular weight. These macromolecular amphiphiles are known to form a wide range of nanostructures (spheres, worms, vesicles, etc.) in solvents that are selective for one of the blocks. However, such self-assembly is usually limited to dilute copolymer solutions (<1%), which is a significant disadvantage for potential commercial applications such as drug delivery and coatings. In principle, this problem can be circumvented by polymerization-induced block copolymer self-assembly. Here we detail the synthesis and subsequent in situ self-assembly of amphiphilic AB diblock copolymers in a one pot concentrated aqueous dispersion polymerization formulation. We show that spherical micelles, wormlike micelles, and vesicles can be predictably and efficiently obtained (within 2 h of polymerization, >99% monomer conversion) at relatively high solids in purely aqueous solution. Furthermore, careful monitoring of the in situ polymerization by transmission electron microscopy reveals various novel intermediate structures (including branched worms, partially coalesced worms, nascent bilayers, "octopi", "jellyfish", and finally pure vesicles) that provide important mechanistic insights regarding the evolution of the particle morphology during the sphere-to-worm and worm-to-vesicle transitions. This environmentally benign approach (which involves no toxic solvents, is conducted at relatively high solids, and requires no additional processing) is readily amenable to industrial scale-up, since it is based on commercially available starting materials.

Noble-metal-free g-C3N4/Ni(dmgH)2 composite for efficient photocatalytic hydrogen evolution under visible light irradiation

NASA Astrophysics Data System (ADS)

Cao, Shao-Wen; Yuan, Yu-Peng; Barber, James; Loo, Say Chye Joachim; Xue, Can

2014-11-01

We report an economic photocatalytic H2 generation system consisting of earth-abundant elements only by coupling graphitic carbon nitride (g-C3N4) with Ni(dmgH)2 sub-microwires that serve as effective co-catalysts for H2 evolution. This composite photocatalyst exhibits efficient hydrogen evolution under visible-light irradiation in the presence of triethanolamine as electron donor. The optimal coupling of 3.5 wt% Ni(dmgH)2 to g-C3N4 (5 mg composite) allows for a steady H2 generation rate of 1.18 μmol/h with excellent stability. This study demonstrates that the combination of polymeric g-C3N4 semiconductor and small proportion of transition-metal-based co-catalyst could serve as a stable, earth-abundant and low-cost system for solar-to-hydrogen conversion.

Microstructural evolution of AZ31 magnesium alloy subjected to sliding friction treatment

NASA Astrophysics Data System (ADS)

Zhang, Wei; Lu, Jinwen; Huo, Wangtu; Zhang, Yusheng; Wei, Q.

2018-06-01

Microstructural evolution and grain refinement mechanism in AZ31 magnesium alloy subjected to sliding friction treatment were investigated by means of transmission electron microscopy. The process of grain refinement was found to involve the following stages: (I) coarse grains were divided into fine twin plates through mechanical twinning; then the twin plates were transformed to lamellae with the accumulation of residual dislocations at the twin boundaries; (II) the lamellae were separated into subgrains with increasing grain boundary misorientation and evolution of high angle boundaries into random boundaries by continuous dynamic recrystallisation (cDRX); (III) the formation of nanograins. The mechanisms for the final stage, the formation of nanograins, can be classified into three types: (i) cDRX; (ii) discontinuous dynamic recrystallisation (dDRX); (iii) a combined mechanism of prior shear-band and subsequent dDRX. Stored strain energy plays an important role in determining deformation mechanisms during plastic deformation.

Membrane tension feedback on shape and motility of eukaryotic cells

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

Winkler, Benjamin; Aranson, Igor S.; Ziebert, Falko

2016-04-01

In the framework of a phase field model of a single cell crawling on a substrate, we investigate how the properties of the cell membrane affect the shape and motility of the cell. Since the membrane influences the cell dynamics on multiple levels and provides a nontrivial feedback, we consider the following fundamental interactions: (i) the reduction of the actin polymerization rate by membrane tension; (ii) area conservation of the cell’s two-dimensional cross-section vs. conservation of the circumference (i.e. membrane inextensibility); and (iii) the contribution from the membrane’s bending energy to the shape and integrity of the cell. As inmore » experiments, we investigate two pertinent observables — the cell’s velocity and its aspect ratio. We find that the most important effect is the feedback of membrane tension on the actin polymerization. Bending rigidity has only minor effects, visible mostly in dynamic reshaping events, as exemplified by collisions of the cell with an obstacle.« less

Nanowires and Nanostructures That Grow Like Polymer Molecules

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

Shaw, Santosh; Cademartiri, Ludovico

Unique properties (e.g., rubber elasticity, viscoelasticity, folding, reptation) determine the utility of polymer molecules and derive from their morphology (i.e., one-dimensional connectivity and large aspect ratios) and flexibility. Crystals do not display similar properties because they have smaller aspect ratios, they are rigid, and they are often too large and heavy to be colloidally stable. We argue, with the support of recent experimental studies, that these limitations are not fundamental and that they might be overcome by growth processes that mimic polymerization. Furthermore, we (i) discuss the similarities between crystallization and polymerization, (ii) critically review the existing experimental evidence ofmore » polymer-like growth kinetic and behavior in crystals and nanostructures, and (iii) propose heuristic guidelines for the synthesis of “polymer-like” crystals and assemblies. Understanding these anisotropic materials at the boundary between molecules and solids will determine whether we can confer the unique properties of polymer molecules to crystals, expanding them with topology, dynamics, and information and not just tuning them with size.« less

Is Ammonium Peroxydisulate Indispensable for Preparation of Aniline-Derived Iron-Nitrogen-Carbon Electrocatalysts?

PubMed

Xie, Nan-Hong; Yan, Xiang-Hui; Xu, Bo-Qing

2016-09-08

Iron and nitrogen co-doped carbon (Fe-N-C) materials are among the most active non-precious metal catalysts that could replace Pt-based electrocatalysts for the oxygen reduction reaction (ORR) in fuel cells and metal-air batteries. The synthesis of the Fe-N-C catalysts often involves the use of aniline as the precursor for both N and C and ammonium peroxydisulfate (APS) as an indispensable oxidative initiator for aniline polymerization. Herein, a detailed structure and catalytic ORR performance comparison of aniline-derived Fe-N-C catalysts synthesized with and without the use of APS is reported. The APS-free preparation, which uses Fe(III) ions as the Fe source as well as the aniline polymerization initiator, results in a simple Fe-N-C catalyst with a high activity for the ORR. We show that APS is not necessary for the preparation and even detrimental to the performance of the catalyst. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Phase diagram and transformations of iron pentacarbonyl to nm layered hematite and carbon-oxygen polymer under pressure

DOE PAGES

Ryu, Young Jay; Kim, Minseob; Yoo, Choong -Shik

2015-10-12

In this study, we present the phase diagram of Fe(CO) 5, consisting of three molecular polymorphs (phase I, II and III) and an extended polymeric phase that can be recovered at ambient condition. The phase diagram indicates a limited stability of Fe(CO) 5 within a pressure-temperature dome formed below the liquid- phase II- polymer triple point at 4.2 GPa and 580 K. The limited stability, in turn, signifies the temperature-induced weakening of Fe-CO back bonds, which eventually leads to the dissociation of Fe-CO at the onset of the polymerization of CO. The recovered polymer is a composite of novel nm-lamellarmore » layers of crystalline hematite Fe 2O 3 and amorphous carbon-oxygen polymers. These results, therefore, demonstrate the synthesis of carbon-oxygen polymer by compressing Fe(CO) 5, which advocates a novel synthetic route to develop atomistic composite materials by compressing organometallic compounds.« less

Use of Monte-Carlo Simulations in Polyurethane Polymerization Processes

DTIC Science & Technology

1995-11-01

situations, the mechanisms of molecular species diffusion must be considered. Gupta et al (Ref. 10) have demonstrated the use of Monte-Carlo simulations in...many thoughtful discussions. P154742.PDF [Page: 41 of 78] UNCLASSIFIED 29 9. 0 REFERENCES 1. Muthiah, R. M.; Krishnamurthy, V. N.; Gupta , B. R...Time Evolution of Coupled Chemical Reactions", Journal of Computational Physics, Vol. 22, 1976, pg. 403 7. Pandit,Shubhangi S.; Juvekar, Vinay A

Interactions of the Human LIP5 Regulatory Protein with Endosomal Sorting Complexes Required for Transport*♦

PubMed Central

Skalicky, Jack J.; Arii, Jun; Wenzel, Dawn M.; Stubblefield, William-May B.; Katsuyama, Angela; Uter, Nathan T.; Bajorek, Monika; Myszka, David G.; Sundquist, Wesley I.

2012-01-01

The endosomal sorting complex required for transport (ESCRT) pathway remodels membranes during multivesicular body biogenesis, the abscission stage of cytokinesis, and enveloped virus budding. The ESCRT-III and VPS4 ATPase complexes catalyze the membrane fission events associated with these processes, and the LIP5 protein helps regulate their interactions by binding directly to a subset of ESCRT-III proteins and to VPS4. We have investigated the biochemical and structural basis for different LIP5-ligand interactions and show that the first microtubule-interacting and trafficking (MIT) module of the tandem LIP5 MIT domain binds CHMP1B (and other ESCRT-III proteins) through canonical type 1 MIT-interacting motif (MIM1) interactions. In contrast, the second LIP5 MIT module binds with unusually high affinity to a novel MIM element within the ESCRT-III protein CHMP5. A solution structure of the relevant LIP5-CHMP5 complex reveals that CHMP5 helices 5 and 6 and adjacent linkers form an amphipathic “leucine collar” that wraps almost completely around the second LIP5 MIT module but makes only limited contacts with the first MIT module. LIP5 binds MIM1-containing ESCRT-III proteins and CHMP5 and VPS4 ligands independently in vitro, but these interactions are coupled within cells because formation of stable VPS4 complexes with both LIP5 and CHMP5 requires LIP5 to bind both a MIM1-containing ESCRT-III protein and CHMP5. Our studies thus reveal how the tandem MIT domain of LIP5 binds different types of ESCRT-III proteins, promoting assembly of active VPS4 enzymes on the polymeric ESCRT-III substrate. PMID:23105106

[Sublethal microcephalic chondrodysplasia. Taybi-Linder syndrome, primordial microcephalic nanism types I and III].

PubMed

Maroteaux, P; Badoual, J

1990-02-01

The authors describe a case of microcephalic dwarfism observed in a newborn until 10 months of age and discuss the diagnostic challenge. They show that the Taybi-Linder syndrome and the primordial dwarfism type I and type III of Majewski are an identical recessive autosomal entity. The radiological evolution explains the initial separation of type I and type III. Because of the skeletal lesions, lacking in the Seckel syndrome, the name of sublethal microcephalic chondrodysplasia is proposed for this disease.

Neutrino Background from Population III Stars

NASA Astrophysics Data System (ADS)

Iocco, Fabio

2011-12-01

Population III Stars (PopIII) are the first generation of stars formed from the collapse of the very first structures in the Universe. Their peculiar chemical composition (metal-free, resembling the Primordial Nucleosynthesis yields) affects their formation and evolution and makes them unusually big and hot stars. They are good candidates for the engines of Reionization of the Universe although their direct observation is extremely difficult. Here we summarize a study of their expected diffuse low-energy neutrino background flux at Earth.

Room temperature synthesis of heptazine-based microporous polymer networks as photocatalysts for hydrogen evolution.

PubMed

Kailasam, Kamalakannan; Schmidt, Johannes; Bildirir, Hakan; Zhang, Guigang; Blechert, Siegfried; Wang, Xinchen; Thomas, Arne

2013-06-25

Two emerging material classes are combined in this work, namely polymeric carbon nitrides and microporous polymer networks. The former, polymeric carbon nitrides, are composed of amine-bridged heptazine moieties and showed interesting performance as a metal-free photocatalyst. These materials have, however, to be prepared at high temperatures, making control of their chemical structure difficult. The latter, microporous polymer networks have received increasing interest due to their high surface area, giving rise to interesting applications in gas storage or catalysis. Here, the central building block of carbon nitrides, a functionalized heptazine as monomer, and tecton are used to create microporous polymer networks. The resulting heptazine-based microporous polymers show high porosity, while their chemical structure resembles the ones of carbon nitrides. The polymers show activity for the photocatalytic production of hydrogen from water, even under visible light illumination. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Organic arsenicals as efficient and highly specific linkers for protein/peptide-polymer conjugation.

PubMed

Wilson, Paul; Anastasaki, Athina; Owen, Matthew R; Kempe, Kristian; Haddleton, David M; Mann, Sarah K; Johnston, Angus P R; Quinn, John F; Whittaker, Michael R; Hogg, Philip J; Davis, Thomas P

2015-04-01

The entropy-driven affinity of trivalent (in)organic arsenicals for closely spaced dithiols has been exploited to develop a novel route to peptide/protein-polymer conjugation. A trivalent arsenous acid (As(III)) derivative (1) obtained from p-arsanilic acid (As(V)) was shown to readily undergo conjugation to the therapeutic peptide salmon calcitonin (sCT) via bridging of the Cys(1)-Cys(7) disulfide, which was verified by RP-HPLC and MALDI-ToF-MS. Conjugation was shown to proceed rapidly (t < 2 min) in situ and stoichiometrically through sequential reduction-conjugation protocols, therefore exhibiting conjugation efficiencies equivalent to those reported for the current leading disulfide-bond targeting strategies. Furthermore, using bovine serum albumin as a model protein, the trivalent organic arsenical 1 was found to demonstrate enhanced specificity for disulfide-bond bridging in the presence of free cysteine residues relative to established maleimide functional reagents. This specificity represents a shift toward potential orthogonality, by clearly distinguishing between the reactivity of mono- and disulfide-derived (vicinal or neighbors-through-space) dithiols. Finally, p-arsanilic acid was transformed into an initiator for aqueous single electron-transfer living radical polymerization, allowing the synthesis of hydrophilic arsenic-functional polymers which were shown to exhibit negligible cytotoxicity relative to a small molecule organic arsenical, and an unfunctionalized polymer control. Poly(poly[ethylene glycol] methyl ether acrylate) (PPEGA480, DPn = 10, Mn,NMR = 4900 g·mol(-1), Đ = 1.07) possessing a pentavalent arsenic acid (As(V)) α-chain end was transformed into trivalent As(III) post-polymerization via initial reduction by biological reducing agent glutathione (GSH), followed by binding of GSH. Conjugation of the resulting As(III)-functional polymer to sCT was realized within 35 min as indicated by RP-HPLC and verified later by thermodynamically driven release of sCT, from the conjugate, in the presence of strong chelating reagent ethanedithiol.

Structural Characterization of the Yersinia pestis Type III Secretion System Needle Protein YscF in Complex with Its Heterodimeric Chaperone YscE/YscG

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

Sun, Ping; Tropea, Joseph E.; Austin, Brian P.

2008-05-03

The plague-causing bacterium Yersinia pestis utilizes a type III secretion system to deliver effector proteins into mammalian cells where they interfere with signal transduction pathways that mediate phagocytosis and the inflammatory response. Effector proteins are injected through a hollow needle structure composed of the protein YscF. YscG and YscE act as 'chaperones' to prevent premature polymerization of YscF in the cytosol of the bacterium prior to assembly of the needle. Here, we report the crystal structure of the YscEFG protein complex at 1.8 {angstrom} resolution. Overall, the structure is similar to that of the analogous PscEFG complex from the Pseudomonasmore » aeruginosa type III secretion system, but there are noteworthy differences. The structure confirms that, like PscG, YscG is a member of the tetratricopeptide repeat family of proteins. YscG binds tightly to the C-terminal half of YscF, implying that it is this region of YscF that controls its polymerization into the needle structure. YscE interacts with the N-terminal tetratricopeptide repeat motif of YscG but makes very little direct contact with YscF. Its function may be to stabilize the structure of YscG and/or to participate in recruiting the complex to the secretion apparatus. No electron density could be observed for the 49 N-terminal residues of YscF. This and additional evidence suggest that the N-terminus of YscF is disordered in the complex with YscE and YscG. As expected, conserved residues in the C-terminal half of YscF mediate important intra- and intermolecular interactions in the complex. Moreover, the phenotypes of some previously characterized mutations in the C-terminal half of YscF can be rationalized in terms of the structure of the heterotrimeric YscEFG complex.« less

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

Chumakov, Yu. M.; Paholnitcaia, A. Yu.; Petrenko, P. A.

Two crystal modifications of nitrato-(2-[2-(1-pyridine-2-ylethylidene)hydrazine]-1,3-benzothiazolo) aquacopper (I and II) and two modifications of chloro-(2-[2-phenyl(pyridine-2-ylethylidene)hydrazine]-1,3-benzothiazolo) copper (III and IV) have been synthesized and studied by X-ray diffraction. In structures I and II, the copper atoms coordinate a monodeprotonated molecule of the organic ligand, nitrate ions, and a water molecule. In crystals of I, the complexes are monomeric, whereas complexes II are linked via nitrate ions to form polymeric chains. In both structures the coordination polyhedron of the copper atom can be described as a distorted tetragonal bipyramid—(4 + 1 + 1) in I and (4 + 2) in II. These coordinationmore » polyherdra have different compositions. In structures III and IV, the metal atoms coordinate a monodeprotonated (2-[2-phenyl(pyridine-2-ylethylidene)hydrazine]-1,3-benzothiazole molecule and chloride ions. In III the complex-forming ion has square-planar coordination geometry, whereas structure IV consists of centrosymmetric dimers with two bridging chlorine atoms. It was found that nitrato-(2-[2-(1-pyridine-2-ylethylidene)hydrazine]-1,3-benzothiazolo) aquacopper possesses antitumor activity.« less

Synthetic nebular emission from massive galaxies - I: origin of the cosmic evolution of optical emission-line ratios

NASA Astrophysics Data System (ADS)

Hirschmann, Michaela; Charlot, Stephane; Feltre, Anna; Naab, Thorsten; Choi, Ena; Ostriker, Jeremiah P.; Somerville, Rachel S.

2017-12-01

Galaxies occupy different regions of the [O III]λ5007/H β-versus-[N II]λ6584/H α emission-line ratio diagram in the distant and local Universe. We investigate the origin of this intriguing result by modelling self-consistently, for the first time, nebular emission from young stars, accreting black holes (BHs) and older, post-asymptotic giant branch (post-AGB) stellar populations in galaxy formation simulations in a full cosmological context. In post-processing, we couple new-generation nebular-emission models with high-resolution, cosmological zoom-in simulations of massive galaxies to explore which galaxy physical properties drive the redshift evolution of the optical-line ratios [O III]λ5007/H β, [N II]λ6584/H α, [S II]λλ6717, 6731/H α and [O I]λ6300/H α. The line ratios of simulated galaxies agree well with observations of both star-forming and active local Sloan Digital Sky Survey galaxies. Towards higher redshifts, at fixed galaxy stellar mass, the average [O III]/H β is predicted to increase and [N II]/H α, [S II]/H α and [O I]/H α to decrease - widely consistent with observations. At fixed stellar mass, we identify star formation history, which controls nebular emission from young stars via the ionization parameter, as the primary driver of the cosmic evolution of [O III]/H β and [N II]/H α. For [S II]/H α and [O I]/H α, this applies only to redshifts greater than z = 1.5, the evolution at lower redshift being driven in roughly equal parts by nebular emission from active galactic nuclei and post-AGB stellar populations. Instead, changes in the hardness of ionizing radiation, ionized-gas density, the prevalence of BH accretion relative to star formation and the dust-to-metal mass ratio (whose impact on the gas-phase N/O ratio we model at fixed O/H) play at most a minor role in the cosmic evolution of simulated galaxy line ratios.

Fast preparation of hybrid monolithic columns via photo-initiated thiol-yne polymerization for capillary liquid chromatography.

PubMed

Ma, Shujuan; Zhang, Haiyang; Li, Ya; Li, Yanan; Zhang, Na; Ou, Junjie; Ye, Mingliang; Wei, Yinmao

2018-02-23

Although several approaches have been developed to fabricate hybrid monoliths, it would still take a few hours to finish the formation of monoliths. Herein, photo-initiated thiol-yne polymerization was first adopted to in situ fabricate hybrid monoliths within the confines of UV-transparent fused-silica capillary. A silicon-containing diyne (1,3-diethynyltetramethyl-disiloxane, DYDS) was copolymerized with three multithiols, 1,6-hexanedithiol, trimethylolpropane tris(3-mercaptopropionate) and pentaerythriol tetrakis(3-mercaptopropionate), by using a binary porogenic system of diethylene glycol diethyl ether (DEGDE)/poly(ethylene glycol) (PEG200) within 10 min. Several characterizations of three hybrid monoliths (assigned as I, II and III, respectively) were performed. The results showed that these hybrid monoliths possessed bicontinuous porous structure, which was remarkably different from that via typical free-radical polymerization. The highest column efficiency of 76,000 plates per meter for butylbenzene was obtained on the column I in reversed-phase liquid chromatography (RPLC). It was observed that the efficiencies for strong-retained butylbenzene were almost close to those of weak-retained benzene, indicating a retention-independent efficient performance of small molecules on hybrid column I. The surface area of this hybrid monolith was very small in the dry state (less than 10.0 m 2 /g), and the chromatographic behavior of hybrid monolithic columns would be possibly explained by radical-mediated step-growth process of thiol-yne polymerization. Finally, the column I was applied for separation of BSA tryptic digest by cLC-MS/MS, indicating satisfactory separation ability for complicated samples. Copyright © 2018 Elsevier B.V. All rights reserved.

Polymerization of 3-Methyl-2,5-Dibromothiophene Utilizing n-Butyl Lithium and Copper(II) Chloride.

DTIC Science & Technology

1984-01-06

condition for good conductivity.9 In conclusion, our new method yields an excellent Mg-free polymer. An exploration- al investigation utilizing n- Buli ...Cincinnati Cincinnati, Ohio 45221 Stanley Pons and Jerome F. McAleer Department of Chemistry University of Alberta Edmonton, Alberta 1.n- BuLi Me e M -Z2...l ll III ,) op€)1 Synthesized by.... ... . *I *1 l IS I I S. # I | I I ll I l 111.10 IdIOS I Ion’lI , n- BuLi + CuC1

In-situ polymerized PLOT columns III: divinylbenzene copolymers and dimethacrylate homopolymers

NASA Technical Reports Server (NTRS)

Shen, T. C.; Fong, M. M.

1994-01-01

Studies of divinylbenzene copolymers and dimethacrylate homopolymers indicate that the polymer pore size controls the separation of water and ammonia on porous-layer-open-tubular (PLOT) columns. To a lesser degree, the polarity of the polymers also affects the separation of a water-ammonia gas mixture. Our results demonstrate that the pore size can be regulated by controlling the cross-linking density or the chain length between the cross-linking functional groups. An optimum pore size will provide the best separation of water and ammonia.

Soluble silylated polyacetylene derivatives, their preparation and their use as precursors to novel polyacetylene-type polymers

DOEpatents

Zeigler, J.M.

1985-07-30

Polymerization of acetylenic monomers is achieved by using a catalyst which is the reaction product of a tungsten compound and a reducing agent effective to reduce W(VI) to W(III and/or IV), e.g., WCl/sub 6/ x (organo-Li, organo-Mg or polysilanes). The resultant silylated polymers are of heretofore unachievable, high molecular weight and can be used as precursors to a wide variety of new acetylenic polymers by application of substitution reactions. They can be used as electrodes in batteries.

Radical-induced generation of small silver particles in SPEEK/PVA polymer films and solutions: UV-Vis, EPR, and FT-IR studies.

PubMed

Korchev, A S; Konovalova, T; Cammarata, V; Kispert, L; Slaten, L; Mills, G

2006-01-03

The present study is centered on the processes involved in the photochemical generation of nanometer-sized Ag particles via illumination at 350 nm of aqueous solutions and cross linked films containing sulfonated poly(ether ether ketone) and poly(vinyl alcohol). Optical and electron paramagnetic resonance experiments, including electron nuclear double resonance data, proved conclusively that the photogenerated chromophore exhibiting a band with lambda(max) = 565 nm is an alpha-hydroxy aromatic (ketyl) radical of the polymeric ketone. This reducing species was produced by illumination of either solutions or films, but the radical lifetime extended from minutes in the fluid phase to hours in the solid. Direct evidence is presented that this long-lived chromophore reduces Ag(I), Cu(II), and Au(III) ions in solution. A rate constant of k = 1.4 x 10(3) M(-)(1) s(-)(1) was obtained for the reduction of Ag(+) by the ketyl radical from the post-irradiation formation of Ag crystallites. FTIR results confirmed that the photoprocess yielding polymeric ketyl radicals involves a reaction between the macromolecules. The photochemical oxidation of the polymeric alcohol, as well as the formation of light-absorbing macromolecular products and polyols, indicates that the sulfonated polyketone experienced transformations similar to those encountered during illumination of the benzophenone/2-propanol system.

Eu(III)-Fulvic Acid Complexation: Evidence of Fulvic Acid Concentration Dependent Interactions by Time-Resolved Luminescence Spectroscopy.

PubMed

Kouhail, Yasmine Z; Benedetti, Marc F; Reiller, Pascal E

2016-04-05

Europium speciation is investigated by time-resolved luminescence spectroscopy (TRLS) in the presence of Suwannee River fulvic acid (SRFA). From complexation isotherms built at different total Eu(III) concentrations, pH values, ionic strength, and SRFA concentrations, it appears that two luminescence behaviors of Eu(III) are occurring. The first part, at the lowest CSRFA values, is showing the typical luminescence evolution of Eu(III) complexed by humic substances--that is, the increase of the asymmetry ratio between the (5)D0 → (7)F2 and (5)D0 → (7)F1 transitions up to a plateau--, and the occurrence of a biexponential decay--the first decay being faster than free Eu(3+). At higher CSRFA, a second luminescence mode is detected as the asymmetry ratio is increasing again after the previous plateau, and could correspond to the formation of another type of complex, and/or it can reflect a different spatial organization of complexed europium within the SRFA structure. The luminescence decay keeps on evolving but link to hydration number is not straightforward due to quenching mechanisms. The Eu(III) chemical environment evolution with CSRFA is also ionic strength dependent. These observations suggest that in addition to short-range interactions--intraparticulate complexation--, there might be interactions at longer range--interparticulate repulsion--between particles that are complexing Eu(III) at high CSRFA. These interactions are not yet accounted by the different complexation models.

Stress evolution of GaN/AlN heterostructure grown on 6H-SiC substrate by plasma assisted molecular beam epitaxy

NASA Astrophysics Data System (ADS)

Agrawal, M.; Ravikiran, L.; Dharmarasu, N.; Radhakrishnan, K.; Karthikeyan, G. S.; Zheng, Y.

2017-01-01

The stress evolution of GaN/AlN heterostructure grown on 6H-SiC substrate by plasma assisted molecular beam epitaxy (PA-MBE) has been studied. AlN nucleation layer and GaN layer were grown as a function of III/V ratio. GaN/AlN structure is found to form buried cracks when AlN is grown in the intermediate growth regime(III/V˜1)and GaN is grown under N-rich growth regime (III/V<1). The III/V ratio determines the growth mode of the layers that influences the lattice mismatch at the GaN/AlN interface. The lattice mismatch induced interfacial stress at the GaN/AlN interface relaxes by the formation of buried cracks in the structure. Additionally, the stress also relaxes by misorienting the AlN resulting in two misorientations with different tilts. Crack-free layers were obtained when AlN and GaN were grown in the N-rich growth regime (III/V<1) and metal rich growth regime (III/V≥1), respectively. AlGaN/GaN high electron mobility transistor (HEMT) heterostructure was demonstrated on 2-inch SiC that showed good two dimensional electron gas (2DEG) properties with a sheet resistance of 480 Ω/sq, mobility of 1280 cm2/V.s and sheet carrier density of 1×1013 cm-2.

RAFT Aqueous Dispersion Polymerization of N-(2-(Methacryloyloxy)ethyl)pyrrolidone: A Convenient Low Viscosity Route to High Molecular Weight Water-Soluble Copolymers

PubMed Central

2016-01-01

RAFT solution polymerization of N-(2-(methacryoyloxy)ethyl)pyrrolidone (NMEP) in ethanol at 70 °C was conducted to produce a series of PNMEP homopolymers with mean degrees of polymerization (DP) varying from 31 to 467. Turbidimetry was used to assess their inverse temperature solubility behavior in dilute aqueous solution, with an LCST of approximately 55 °C being observed in the high molecular weight limit. Then a poly(glycerol monomethacylate) (PGMA) macro-CTA with a mean DP of 63 was chain-extended with NMEP using a RAFT aqueous dispersion polymerization formulation at 70 °C. The target PNMEP DP was systematically varied from 100 up to 6000 to generate a series of PGMA63–PNMEPx diblock copolymers. High conversions (≥92%) could be achieved when targeting up to x = 5000. GPC analysis confirmed high blocking efficiencies and a linear evolution in Mn with increasing PNMEP DP. A gradual increase in Mw/Mn was also observed when targeting higher DPs. However, this problem could be minimized (Mw/Mn < 1.50) by utilizing a higher purity grade of NMEP (98% vs 96%). This suggests that the broader molecular weight distributions observed at higher DPs are simply the result of a dimethacrylate impurity causing light branching, rather than an intrinsic side reaction such as chain transfer to polymer. Kinetic studies confirmed that the RAFT aqueous dispersion polymerization of NMEP was approximately four times faster than the RAFT solution polymerization of NMEP in ethanol when targeting the same DP in each case. This is perhaps surprising because both 1H NMR and SAXS studies indicate that the core-forming PNMEP chains remain relatively solvated at 70 °C in the latter formulation. Moreover, dissolution of the initial PGMA63–PNMEPx particles occurs on cooling from 70 to 20 °C as the PNMEP block passes through its LCST. Hence this RAFT aqueous dispersion polymerization formulation offers an efficient route to a high molecular weight water-soluble polymer in a rather convenient low-viscosity form. Finally, the relatively expensive PGMA macro-CTA was replaced with a poly(methacrylic acid) (PMAA) macro-CTA. High conversions were also achieved for PMAA85–PNMEPx diblock copolymers prepared via RAFT aqueous dispersion polymerization for x ≤ 4000. Again, better control was achieved when using the 98% purity NMEP monomer in such syntheses. PMID:27375300

RAFT Aqueous Dispersion Polymerization of N-(2-(Methacryloyloxy)ethyl)pyrrolidone: A Convenient Low Viscosity Route to High Molecular Weight Water-Soluble Copolymers.

PubMed

Cunningham, Victoria J; Derry, Matthew J; Fielding, Lee A; Musa, Osama M; Armes, Steven P

2016-06-28

RAFT solution polymerization of N -(2-(methacryoyloxy)ethyl)pyrrolidone (NMEP) in ethanol at 70 °C was conducted to produce a series of PNMEP homopolymers with mean degrees of polymerization (DP) varying from 31 to 467. Turbidimetry was used to assess their inverse temperature solubility behavior in dilute aqueous solution, with an LCST of approximately 55 °C being observed in the high molecular weight limit. Then a poly(glycerol monomethacylate) (PGMA) macro-CTA with a mean DP of 63 was chain-extended with NMEP using a RAFT aqueous dispersion polymerization formulation at 70 °C. The target PNMEP DP was systematically varied from 100 up to 6000 to generate a series of PGMA 63 -PNMEP x diblock copolymers. High conversions (≥92%) could be achieved when targeting up to x = 5000. GPC analysis confirmed high blocking efficiencies and a linear evolution in M n with increasing PNMEP DP. A gradual increase in M w / M n was also observed when targeting higher DPs. However, this problem could be minimized ( M w / M n < 1.50) by utilizing a higher purity grade of NMEP (98% vs 96%). This suggests that the broader molecular weight distributions observed at higher DPs are simply the result of a dimethacrylate impurity causing light branching, rather than an intrinsic side reaction such as chain transfer to polymer. Kinetic studies confirmed that the RAFT aqueous dispersion polymerization of NMEP was approximately four times faster than the RAFT solution polymerization of NMEP in ethanol when targeting the same DP in each case. This is perhaps surprising because both 1 H NMR and SAXS studies indicate that the core-forming PNMEP chains remain relatively solvated at 70 °C in the latter formulation. Moreover, dissolution of the initial PGMA 63 -PNMEP x particles occurs on cooling from 70 to 20 °C as the PNMEP block passes through its LCST. Hence this RAFT aqueous dispersion polymerization formulation offers an efficient route to a high molecular weight water-soluble polymer in a rather convenient low-viscosity form. Finally, the relatively expensive PGMA macro-CTA was replaced with a poly(methacrylic acid) (PMAA) macro-CTA. High conversions were also achieved for PMAA 85 -PNMEP x diblock copolymers prepared via RAFT aqueous dispersion polymerization for x ≤ 4000. Again, better control was achieved when using the 98% purity NMEP monomer in such syntheses.

Design and synthesis of heterobimetallic Ru(II)-Ln(III) complexes as chemodosimetric ensembles for the detection of biogenic amine odorants.

PubMed

Chow, Cheuk-Fai; Lam, Michael H W; Wong, Wai-Yeung

2013-09-03

The detection of neutral biogenic amines plays a crucial role in food safety. Three new heterobimetallic Ru(II)-Ln(III) donor-acceptor complexes, KPrRu, KNdRu, and KSmRu, K{[Ru((II))((t)Bubpy)(CN)4]2-Ln((III))(H2O)4} (where (t)Bubpy = 4,4'-di-tert-butyl-2,2'-bipyridine), have been synthesized and characterized. Their photophysical and X-ray crystallographic data were reported in this study. These complexes were found to be selective for biogenic amine vapors, such as histamine, putrescine, and spermidine, with a detection limit down to the ppb level. The sensitivities of these complexes to the amines were recorded as ~log K = 3.6-5.0. Submicron rods of the complexes, with a nanoscale diameter and microscale length, were obtained through a simple precipitation process. Free-standing polymeric films with different degrees of porosity were fabricated by blending the submicron rods with polystyrene polymer. The polymer with the highest level of porosity exhibited the strongest luminescence enhancement after amine exposure. Real time monitoring of gaseous biogenic amines was applied to real fish samples (Atlantic mackerel) by studying the spectrofluorimetric responses of the Ru(II)-Ln(III) blended polymer film.

Effect of aqueous Si/Mg ratio and pH on the nucleation and growth of sepiolite at 25 °C

NASA Astrophysics Data System (ADS)

Baldermann, Andre; Mavromatis, Vasileios; Frick, Paula M.; Dietzel, Martin

2018-04-01

Sepiolite [Mg4Si6O15(OH)2·6H2O] is a trioctahedral 2:1 Mg-silicate that has been often used to reconstruct the evolution of sedimentary environments and facies in the geological record. To date, however, the reaction paths underlying sepiolite formation are poorly constrained and most of the existing models are based on empirical observations. In order to shed light on the mechanisms controlling the formation of this mineral phase, in the present study, sepiolite was precipitated at 25 ± 1 °C from modified seawater and MgCl2 solutions undersaturated with respect to brucite and amorphous silica. Although a suite of hydrous Mg-silicates, such as kerolite, saponite, stevensite and talc, were oversaturated in the solutions at a higher level relative to sepiolite at any time of reaction, poorly crystallized, aluminous sepiolite was the only precipitate after 91 days. The precipitated sepiolite [Mg3.4-3.8Al0.1-0.4)∑3.8-3.9(Si5.9-6.0Al0-0.1)O15(OH)2·nH2O] shares a number of structural and chemical similarities with natural sepiolite, such as a fibrous crystal shape and an atomic Si/(Si + Mg+Al) ratio of ∼0.61. The proposed reaction path for the formation of sepiolite is based on the temporal evolution of the chemical compositions of the experimental solution and solids: (i) Nucleation and growth of Al-sepiolite occurred during the first 8 days of the experimental runs via condensation and polymerization of Sisbnd OH tetrahedra onto Mg-Al-O-OH template sheets at a precipitation rate of ∼2.19 ± 0.01 × 10-10 mol s-1. (ii) At decreasing pH and in the absence of [Al]aq this intermediate phase transformed into aluminous sepiolite at a slower crystal growth rate of ∼1.08 ± 0.02 × 10-12 mol s-1. This finding explains the high abundances of sepiolite in highly alkaline, evaporitic, lacustrine and soil environments, where the growth rates of sepiolite are considered faster (10-11 to 10-10 mol s-1, Brady, 1992). We propose that (i) low rates of Mg2+ ion dehydration and silica condensation and polymerization at the surface of the initial precipitate, (ii) the formation of MgS 040 aquo-complexes and (iii) the reduced sorption rates of [Si]aq and [Mg]aq at the active growth sites on sepiolite surfaces at pH ≤ 8.3 retard the precipitation of sepiolite in marine-diagenetic environments.

Distribution of Particles, Small Molecules and Polymeric Formulation Excipients in the Suprachoroidal Space after Microneedle Injection

PubMed Central

Chiang, Bryce; Venugopal, Nitin; Edelhauser, Henry F.; Prausnitz, Mark R.

2016-01-01

The purpose of this work was to determine the effect of injection volume, formulation composition, and time on circumferential spread of particles, small molecules and polymeric formulation excipients in the suprachoroidal space (SCS) after microneedle injection into New Zealand White rabbit eyes ex vivo and in vivo. Microneedle injections of 25–150 μL Hank’s Balanced Salt Solution (HBSS) containing 0.2 μm red-fluorescent particles and a model small molecule (fluorescein) were performed in rabbit eyes ex vivo, and visualized via flat mount. Particles with diameters of 0.02 – 2 μm were co-injected into SCS in vivo with fluorescein or a polymeric formulation excipient: fluorescein isothiocyanate (FITC)-labeled Discovisc or FITC-labeled carboxymethyl cellulose (CMC). Fluorescent fundus images were acquired over time to determine area of particle, fluorescein and polymeric formulation excipient spread, as well as their co-localization. We found that fluorescein covered a significantly larger area than co-injected particles when suspended in HBSS, and that this difference was present from 3 min post-injection onwards. We further showed that there was no difference in initial area covered by FITC-Discovisc and particles; the transport time (i.e., the time until the FITC-Discovisc and particle area began dissociating) was 2 d. There was also no difference in initial area covered by FITC-CMC and particles; the transport time in FITC-CMC was 4 d. We also found that particle size (20 nm – 2 μm) had no effect on spreading area when delivered in HBSS or Discovisc. We conclude that (i) the area of particle spread in SCS during injection generally increased with increasing injection volume, was unaffected by particle size and was significantly less than the area of fluorescein spread, (ii) particles suspended in low-viscosity HBSS formulation were entrapped in the SCS after injection, whereas fluorescein was not and (iii) particles co-injected with viscous polymeric formulation excipients co-localized near the site of injection in the SCS, continued to co-localize while spreading over larger areas for 2 – 4 days, and then no longer co-localized as the polymeric formulation excipients were cleared within 1 – 3 weeks and the particles remained largely in place. These data suggest that particles encounter greater barriers to flow in SCS compared to molecules and that co-localization of particles and polymeric formulation excipients allow spreading over larger areas of the SCS until the particles and excipients dissociate. PMID:27742547

Distribution of particles, small molecules and polymeric formulation excipients in the suprachoroidal space after microneedle injection.

PubMed

Chiang, Bryce; Venugopal, Nitin; Edelhauser, Henry F; Prausnitz, Mark R

2016-12-01

The purpose of this work was to determine the effect of injection volume, formulation composition, and time on circumferential spread of particles, small molecules, and polymeric formulation excipients in the suprachoroidal space (SCS) after microneedle injection into New Zealand White rabbit eyes ex vivo and in vivo. Microneedle injections of 25-150 μL Hank's Balanced Salt Solution (HBSS) containing 0.2 μm red-fluorescent particles and a model small molecule (fluorescein) were performed in rabbit eyes ex vivo, and visualized via flat mount. Particles with diameters of 0.02-2 μm were co-injected into SCS in vivo with fluorescein or a polymeric formulation excipient: fluorescein isothiocyanate (FITC)-labeled Discovisc or FITC-labeled carboxymethyl cellulose (CMC). Fluorescent fundus images were acquired over time to determine area of particle, fluorescein, and polymeric formulation excipient spread, as well as their co-localization. We found that fluorescein covered a significantly larger area than co-injected particles when suspended in HBSS, and that this difference was present from 3 min post-injection onwards. We further showed that there was no difference in initial area covered by FITC-Discovisc and particles; the transport time (i.e., the time until the FITC-Discovisc and particle area began dissociating) was 2 d. There was also no difference in initial area covered by FITC-CMC and particles; the transport time in FITC-CMC was 4 d. We also found that particle size (20 nm-2 μm) had no effect on spreading area when delivered in HBSS or Discovisc. We conclude that (i) the area of particle spread in SCS during injection generally increased with increasing injection volume, was unaffected by particle size, and was significantly less than the area of fluorescein spread, (ii) particles suspended in low-viscosity HBSS formulation were entrapped in the SCS after injection, whereas fluorescein was not and (iii) particles co-injected with viscous polymeric formulation excipients co-localized near the site of injection in the SCS, continued to co-localize while spreading over larger areas for 2-4 days, and then no longer co-localized as the polymeric formulation excipients were cleared within 1-3 weeks and the particles remained largely in place. These data suggest that particles encounter greater barriers to flow in SCS compared to molecules and that co-localization of particles and polymeric formulation excipients allows spreading over larger areas of the SCS until the particles and excipients dissociate. Copyright © 2016 Elsevier Ltd. All rights reserved.

A mutation in the receptor Methoprene-tolerant alters juvenile hormone response in insects and crustaceans.

PubMed

Miyakawa, Hitoshi; Toyota, Kenji; Hirakawa, Ikumi; Ogino, Yukiko; Miyagawa, Shinichi; Oda, Shigeto; Tatarazako, Norihisa; Miura, Toru; Colbourne, John K; Iguchi, Taisen

2013-01-01

Juvenile hormone is an essential regulator of major developmental and life history events in arthropods. Most of the insects use juvenile hormone III as the innate juvenile hormone ligand. By contrast, crustaceans use methyl farnesoate. Despite this difference that is tied to their deep evolutionary divergence, the process of this ligand transition is unknown. Here we show that a single amino-acid substitution in the receptor Methoprene-tolerant has an important role during evolution of the arthropod juvenile hormone pathway. Microcrustacea Daphnia pulex and D. magna share a juvenile hormone signal transduction pathway with insects, involving Methoprene-tolerant and steroid receptor coactivator proteins that form a heterodimer in response to various juvenoids. Juvenile hormone-binding pockets of the orthologous genes differ by only two amino acids, yet a single substitution within Daphnia Met enhances the receptor's responsiveness to juvenile hormone III. These results indicate that this mutation within an ancestral insect lineage contributed to the evolution of a juvenile hormone III receptor system.

Mechanistic Studies of Hafnium-Pyridyl Amido-Catalyzed 1-Octene Polymerization and Chain Transfer Using Quench-Labeling Methods.

PubMed

Cueny, Eric S; Johnson, Heather C; Anding, Bernie J; Landis, Clark R

2017-08-30

Chromophore quench-labeling applied to 1-octene polymerization as catalyzed by hafnium-pyridyl amido precursors enables quantification of the amount of active catalyst and observation of the molecular weight distribution (MWD) of Hf-bound polymers via UV-GPC analysis. Comparison of the UV-detected MWD with the MWD of the "bulk" (all polymers, from RI-GPC analysis) provides important mechanistic information. The time evolution of the dual-detection GPC data, concentration of active catalyst, and monomer consumption suggests optimal activation conditions for the Hf pre-catalyst in the presence of the activator [Ph 3 C][B(C 6 F 5 ) 4 ]. The chromophore quench-labeling agents do not react with the chain-transfer agent ZnEt 2 under the reaction conditions. Thus, Hf-bound polymeryls are selectively labeled in the presence of zinc-polymeryls. Quench-labeling studies in the presence of ZnEt 2 reveal that ZnEt 2 does not influence the rate of propagation at the Hf center, and chain transfer of Hf-bound polymers to ZnEt 2 is fast and quasi-irreversible. The quench-label techniques represent a means to study commercial polymerization catalysts that operate with high efficiency at low catalyst concentrations without the need for specialized equipment.

Synthesis and hydration behavior of calcium zirconium aluminate (Ca{sub 7}ZrAl{sub 6}O{sub 18}) cement

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

Kang, Eun-Hee; Yoo, Jun-Sang; Kim, Bo-Hye

2014-02-15

Calcium zirconium aluminate (Ca{sub 7}ZrAl{sub 6}O{sub 18}) cements were prepared by solid state reaction and polymeric precursor methods, and their phase evolution, morphology, and hydration behavior were investigated. In polymeric precursor method, a nearly single phase Ca{sub 7}ZrAl{sub 6}O{sub 18} was obtained at relatively lower temperature (1200 °C) whereas in solid state reaction, a small amount of CaZrO{sub 3} coexisted with Ca{sub 7}ZrAl{sub 6}O{sub 18} even at higher temperature (1400 °C). Unexpectedly, Ca{sub 7}ZrAl{sub 6}O{sub 18} synthesized by polymeric precursor process was the large-sized and rough-shaped powder. The planetary ball milling was employed to control the particle size and shape.more » The hydration behavior of Ca{sub 7}ZrAl{sub 6}O{sub 18} was similar to that of Ca{sub 3}Al{sub 2}O{sub 6} (C3A), but the hydration products were Ca{sub 3}Al{sub 2}O{sub 6}·6H{sub 2}O (C3AH6) and several intermediate products. Thus, Zr (or ZrO{sub 2}) stabilized the intermediate hydration products of C3A.« less

Beam width evolution of astigmatic hollow Gaussian beams in highly nonlocal nonlinear media

NASA Astrophysics Data System (ADS)

Yang, Zhen-Feng; Jiang, Xue-Song; Yang, Zhen-Jun; Li, Jian-Xing; Zhang, Shu-Min

We investigate the beam width evolution of astigmatic hollow Gaussian beams propagating in highly nonlocal nonlinear media. The input-power-induced different evolutions of the beam width are illustrated: (i) the beam widths in two transverse directions are compressed or broadened at the same time; (ii) the beam width in one transverse direction keeps invariant, and the other is compressed or broadened; (iii) furthermore, the beam width in one transverse direction is compressed, whereas it in the other transverse direction is broadened.

Hybrid density functional study of organic magnetic crystals: bi-metallic CrIII cyanides and rhombohedral C60

NASA Astrophysics Data System (ADS)

Chan, J. A.; Montanari, B.; Chan, W. L.; Harrison, N. M.

Periodic hybrid-exchange density functional theory calculations have been used to investigate the magnetic properties of two classes of organic magnets, namely the bi-metallic CrIII cyanides and the polymerized rhombohedral C60 fullerenes (Rh-C60). For the systems KMII[CrIII(CN)6] with M II=V, Mn, Ni and CrIII[CrIII(CN)6], the magnetic ordering energies, Mulliken populations, and spin density plots are reported for the optimized geometries. The qualitative nature of the magnetic coupling mechanism is consistent with that observed in previous unrestricted Hartree-Fock calculations, but the coupling energies computed here are significantly higher. The increased coupling is found to be a result of both changes in the geometry and the electronic structure resulting from the more reliable treatment of electronic exchange and correlation effects. The existence of long-range coupling between local spin moments is investigated in three different defective Rh-C60 structures: (i) a previously proposed prototype structure, where an atom is removed from the C60 cage; (ii) a related structure in which vacancies in nearby cages are brought closer together in pairs; and (iii) a structure where the intra-fullerene bond between the two inter-fullerene bonds is broken spontaneously after applying isotropic pressure to one layer of the Rh-C60 structure. All of these structures are characterized by low flat spin polarized bands at the Fermi edge and localized spin moments around the defects, but no evidence of long-range magnetic coupling is found.

Lenalidomide enhances the function of chimeric antigen receptor T cells against the epidermal growth factor receptor variant III by enhancing immune synapses.

PubMed

Kuramitsu, S; Ohno, M; Ohka, F; Shiina, S; Yamamichi, A; Kato, A; Tanahashi, K; Motomura, K; Kondo, G; Kurimoto, M; Senga, T; Wakabayashi, T; Natsume, A

2015-10-01

The epidermal growth factor receptor variant III (EGFRvIII) is exclusively expressed on the cell surface in ~50% of glioblastoma multiforme (GBM). This variant strongly and persistently activates the phosphatidylinositol 3-kinase-Akt signaling pathway in a ligand-independent manner resulting in enhanced tumorigenicity, cellular motility and resistance to chemoradiotherapy. Our group generated a recombinant single-chain variable fragment (scFv) antibody specific to the EGFRvIII, referred to as 3C10-scFv. In the current study, we constructed a lentiviral vector transducing the chimeric antigen receptor (CAR) that consisted of 3C10-scFv, CD3ζ, CD28 and 4-1BB (3C10-CAR). The 3C10-CAR-transduced peripheral blood mononuclear cells (PBMCs) and CD3(+) T cells specifically lysed the glioma cells that express EGFRvIII. Moreover, we demonstrated that CAR CD3(+) T cells migrated to the intracranial xenograft of GBM in the mice treated with 3C10-CAR PBMCs. An important and novel finding of our study was that a thalidomide derivative lenalidomide induced 3C10-CAR PBMC proliferation and enhanced the persistent antitumor effect of the cells in vivo. Lenalidomide also exhibited enhanced immunological synapses between the effector cells and the target cells as determined by CD11a and F-actin polymerization. Collectively, lentiviral-mediated transduction of CAR effectors targeting the EGFRvIII showed specific efficacy, and lenalidomide even intensified CAR cell therapy by enhanced formation of immunological synapses.

Precision synthesis of functional materials via RAFT polymerization and click-type chemical reactions

NASA Astrophysics Data System (ADS)

Flores, Joel Diez

2011-12-01

The need to tailor polymeric architectures with specific physico-chemical properties via the simplest, cleanest, and most efficient synthetic route possible has become the ultimate goal in polymer synthesis. Recent progress in macromolecular science, such as the discoveries of controlled/"living" free radical polymerization (CRP) methods, has brought about synthetic capabilities to prepare (co)polymers with advanced topologies, predetermined molecular weights, narrow molecular weight distributions, and precisely located functional groups. In addition, the establishment of click chemistry has redefined the selected few highly efficient chemical reactions that become highly useful in post-polymerization modification strategies. Hence, the ability to make well-defined topologies afforded by controlled polymerization techniques and the facile incorporation of functionalities along the chain via click-type reactions have yielded complex architectures, allowing the investigation of physical phenomena which otherwise could not be studied with systems prepared via conventional methods. The overarching theme of the research work described in this dissertation is the fusion of the excellent attributes of reversible addition-fragmentation chain transfer (RAFT) polymerization method, which is one of the CRP techniques, and click-type chemical reactions in the precision of synthesis of advanced functional materials. Chapter IV is divided into three sections. In Section I, the direct RAFT homopolymerization of 2-(acryloyloxy)ethyl isocyanate (AOI) and subsequent post-polymerization modifications are described. The polymerization conditions were optimized in terms of the choice of RAFT chain transfer agent (CTA), polymerization temperature and the reaction medium. Direct RAFT polymerization of AOI requires a neutral CTA, and relatively low reaction temperature to yield AOI homopolymers with low polydispersities. Efficient side-chain functionalization of PAOI homopolymers was achieved via reaction with model amine, thiol and alcohol compounds yielding urea, thiourethane and urethane derivatives, respectively. Reactions with amines and thiols (in the presence of base) were rapid, quantitative and efficient. However, the reaction with alcohols catalyzed by dibutyltin dilaurate (DBTDL) was relatively slow but proceeded to completion. Selective reaction pathways for the addition of difunctional ethanolamine and mercaptoethanol were also investigated. A related strategy is described in Section II wherein a hydroxyl-containing diblock copolymer precursor was transformed into a library of functional copolymers via two sequential post-polymerization modification reactions. A diblock copolymer scaffold, poly[(N,N-dimethylacrylamide)-b-( N-(2-hydroxyethyl)acrylamide] (PDMA-b-PHEA) was first prepared. The hydroxyl groups of the HEA block were then reacted with 2-(acryloyloxy)ethylisocyanate (AOI) and allylisocyanate (AI) resulting in acrylate- and allyl-functionalized copolymer precursors, respectively. The efficiencies of Michael-type and free radical thiol addition reactions were investigated using selected thiols having alkyl, aryl, hydroxyl, carboxylic acid, amine and amino acid functionalities. The steps of RAFT polymerization, isocyanate-hydroxyl coupling and thiol-ene addition are accomplished under mild conditions, thus offering facile and modular routes to synthesize functional copolymers. The synthesis and solution studies of pH- and salt-responsive triblock copolymer are described in Section III. This system is capable of forming self-locked micellar structures which may be controlled by changing solution pH as well as ionic strength. A triblock copolymer containing a permanently hydrophilic poly(N,N-dimethylacrylamide) (PDMA) outer block, a salt-sensitive zwitterionic poly(3[2-(N-methylacrylamido)ethyl dimethylammonio]propanesulfonate) (PMAEDAPS) middle block and a pH-responsive 3-acrylamido-3-methylbutanoic acid (PAMBA) core block was synthesized using aqueous RAFT polymerization. A facile formation of "self-locking" shell cross-linked micelles is achieved by changing solution pH and salt concentration. The reversible "self-locking" is attained from the interactions of zwitterionic groups in the middle block that constitutes the shell of the micelles. The structure slowly dissociates into unimers in 2-3 days at pH above the pKa of the PAMBA block.

From polyethylene waxes to HDPE using an α,α'-bis(arylimino)-2,3:5,6-bis(pentamethylene)pyridyl-chromium(iii) chloride pre-catalyst in ethylene polymerisation.

PubMed

Huang, Chuanbing; Du, Shizhen; Solan, Gregory A; Sun, Yang; Sun, Wen-Hua

2017-05-30

Five examples of α,α'-bis(arylimino)-2,3:5,6-bis(pentamethylene)pyridyl-chromium(iii) chlorides (aryl = 2,6-Me 2 Ph Cr1, 2,6-Et 2 Ph Cr2, 2,6-i-Pr 2 Ph Cr3, 2,4,6-Me 3 Ph Cr4, 2,6-Et 2 -4-MePh Cr5) have been synthesized by the one-pot template reaction of α,α'-dioxo-2,3:5,6-bis(pentamethylene)pyridine, CrCl 3 ·6H 2 O and the corresponding aniline. The molecular structures of Cr1 and Cr4 reveal distorted octahedral geometries with the N,N,N-ligand adopting a mer-configuration. On activation with an aluminium alkyl co-catalyst, Cr1-Cr5 exhibited high catalytic activities in ethylene polymerization and showed outstanding thermal stability operating effectively at 80 °C with activities up to 1.49 × 10 7 g of PE (mol of Cr) -1 h -1 . Significantly, the nature of the co-catalyst employed had a dramatic effect on the molecular weight of the polymeric material obtained. For example, using diethylaluminium chloride (Et 2 AlCl) in combination with Cr4 gave high density/high molecular weight polyethylene with broad molecular weight distributions (30.9-39.3). By contrast, using modified methylaluminoxane (MMAO), strictly linear polyethylene waxes of lower molecular weight and narrow molecular weight distribution (1.6-2.0) were obtained with vinyl end-groups.

Electronic structure of carbon dioxide under pressure and insights into the molecular-to-nonmolecular transition

PubMed Central

Shieh, Sean R.; Jarrige, Ignace; Wu, Min; Hiraoka, Nozomu; Tse, John S.; Mi, Zhongying; Kaci, Linada; Jiang, Jian-Zhong; Cai, Yong Q.

2013-01-01

Knowledge of the high-pressure behavior of carbon dioxide (CO2), an important planetary material found in Venus, Earth, and Mars, is vital to the study of the evolution and dynamics of the planetary interiors as well as to the fundamental understanding of the C–O bonding and interaction between the molecules. Recent studies have revealed a number of crystalline polymorphs (CO2-I to -VII) and an amorphous phase under high pressure–temperature conditions. Nevertheless, the reported phase stability field and transition pressures at room temperature are poorly defined, especially for the amorphous phase. Here we shed light on the successive pressure-induced local structural changes and the molecular-to-nonmolecular transition of CO2 at room temperature by performing an in situ study of the local electronic structure using X-ray Raman scattering, aided by first-principle exciton calculations. We show that the transition from CO2-I to CO2-III was initiated at around 7.4 GPa, and completed at about 17 GPa. The present study also shows that at ∼37 GPa, molecular CO2 starts to polymerize to an extended structure with fourfold coordinated carbon and minor CO3 and CO-like species. The observed pressure is more than 10 GPa below previously reported. The disappearance of the minority species at 63(±3) GPa suggests that a previously unknown phase transition within the nonmolecular phase of CO2 has occurred. PMID:24167283

Dynamics of Bottlebrush Networks

NASA Astrophysics Data System (ADS)

Cao, Zhen; Daniel, William; Vatankhah-Varnosfaderani, Mohammad; Sheiko, Sergei; Dobrynin, Andrey

The deformation dynamics of bottlebrush networks in a melt state is studied using a combination of theoretical, computational, and experimental techniques. Three main molecular relaxation processes are identified in these systems: (i) relaxation of the side chains, (ii) relaxation of the bottlebrush backbones on length scales shorter than the bottlebrush Kuhn length (bK) , and (iii) relaxation of the bottlebrush network strands between cross-links. The relaxation of side chains having a degree of polymerization (DP), nsc, dominates the network dynamics on the time scales τ0 < t <=τsc , where τ0 and τsc τ0 (nsc + 1)2 are the characteristic relaxation times of monomeric units and side chains, respectively. In this time interval, the shear modulus at small deformations decays with time as G0BB (t) t - 1 / 2. On time scales t >τsc, bottlebrush elastomers behave as networks of filaments with a shear modulus G0BB (t) (nsc + 1)- 1 / 4t - 1 / 2 . Finally, the response of the bottlebrush networks becomes time independent at times scales longer than the Rouse time of the bottlebrush network strands. In this time interval, the network shear modulus depends on the network molecular parameters as G0BB (t) (nsc + 1)-1N-1 . Analysis of the simulation data shows that the stress evolution in the bottlebrush networks during constant strain-rate deformation can be described by a universal function. NSF DMR-1409710, DMR-1407645, DMR-1624569, DMR-1436201.

Photopolymerization of N,N-dimethylaminobenzyl alcohol as amine co-initiator for light-cured dental resins.

PubMed

Schroeder, Walter F; Cook, Wayne D; Vallo, Claudia I

2008-05-01

The present study was carried out in order to assess the suitability of N,N-dimethylaminobenzyl alcohol (DMOH) as co-initiator of camphorquinone (CQ) and 1-phenyl-1,2-propanedione (PPD) in light-cured dental resins. DMOH was synthesized and used as co-initiator for the photopolymerization of a model resin based on {2,2-bis[4-(2-hydroxy-3-methacryloxyprop-1-oxy)phenyl]propane} (Bis-GMA)/triethylene glycol dimethacrylate (TEGDMA). Experimental formulations containing CQ or PPD in combination with DMOH at different concentrations were studied. The photopolymerization was carried out by means of a commercial light-emitting diode (LED) curing unit. The evolution of double bonds consumption versus irradiation time was followed by near-infrared spectroscopy (NIR). The photon absorption efficiency (PAE) of the photopolymerization process was calculated from the spectral distribution of the LED unit and the molar absorption coefficient distributions of PPD and CQ. DMOH is an efficient photoreducer of CQ and PPD resulting in higher polymerization rate and higher double bond conversion compared with dimethylaminoethylmethacrylate. The PAE for PPD was higher than that for CQ. However, the polymerization initiated by PPD progressed at a lower rate and exhibited lower values of final conversion compared with the resins containing CQ. This observation indicates that the lower polymerization rate of the PPD/amine system should be explained in terms of the mechanism of generating primary radicals by PPD, which is less efficient compared with CQ. The DMOH/benzoyl peroxide redox system, has recently been proposed as a more biocompatible accelerator for the polymerization of bone cements based on poly(methyl methacrylate), because cytotoxity tests have demonstrated that DMOH possesses better biocompatibility properties compared with traditional tertiary amines. The results obtained in the present study reveal the suitability of the CQ/DMOH initiator system for the polymerization of light-cured dental composites.

Heptanuclear CoII5CoIII2 Cluster as Efficient Water Oxidation Catalyst.

PubMed

Xu, Jia-Heng; Guo, Ling-Yu; Su, Hai-Feng; Gao, Xiang; Wu, Xiao-Fan; Wang, Wen-Guang; Tung, Chen-Ho; Sun, Di

2017-02-06

Inspired by the transition-metal-oxo cubical Mn 4 CaO 5 in photosystem II, we herein report a disc-like heptanuclear mixed-valent cobalt cluster, [Co II 5 Co III 2 (mdea) 4 (N 3 ) 2 (CH 3 CN) 6 (OH) 2 (H 2 O) 2 ·4ClO 4 ] (1, H 2 mdea = N-methyldiethanolamine), for photocatalytic oxygen evolution. The topology of the Co 7 core resembles a small piece of cobaltate protected by terminal H 2 O, N 3 - , CH 3 CN, and multidentate N-methyldiethanolamine at the periphery. Under the optimal photocatalytic conditions, 1 exhibits water oxidation activity with a turnover number (TON) of 210 and a turnover frequency (TOF initial ) of 0.23 s -1 . Importantly, electrospray mass spectrometry (ESI-MS) was used to not only identify the possible main active species in the water oxidation reaction but also monitor the evolutions of oxidation states of cobalt during the photocatalytic reactions. These results shed light on the design concept of new water oxidation catalysts and mechanism-related issues such as the key active intermediate and oxidation state evolution in the oxygen evolution process. The magnetic properties of 1 were also discussed in detail.

Dynamic evolution of Rayleigh-Taylor bubbles from sinusoidal, W-shaped, and random perturbations

NASA Astrophysics Data System (ADS)

Zhou, Zhi-Rui; Zhang, You-Sheng; Tian, Bao-Lin

2018-03-01

Implicit large eddy simulations of two-dimensional Rayleigh-Taylor instability at different density ratios (i.e., Atwood number A =0.05 , 0.5, and 0.9) are conducted to investigate the late-time dynamics of bubbles. To produce a flow field full of bounded, semibounded, and chaotic bubbles, three problems with distinct perturbations are simulated: (I) periodic sinusoidal perturbation, (II) isolated W-shaped perturbation, and (III) random short-wave perturbations. The evolution of height h , velocity v , and diameter D of the (dominant) bubble with time t are formulated and analyzed. In problem I, during the quasisteady stage, the simulations confirm Goncharov's prediction of the terminal speed v∞=Fr√{A g λ /(1 +A ) } , where Fr=1 /√{3 π } . Moreover, the diameter D at this stage is found to be proportional to the initial perturbation wavelength λ as D ≈λ . This differed from Daly's simulation result of D =λ (1 +A )/2 . In problem II, a W-shaped perturbation is designed to produce a bubble environment similar to that of chaotic bubbles in problem III. We obtain a similar terminal speed relationship as above, but Fr is replaced by Frw≈0.63 . In problem III, the simulations show that h grows quadratically with the bubble acceleration constant α ≡h /(A g t2)≈0.05 , and D expands self-similarly with a steady aspect ratio β ≡D /h ≈(1 +A )/2 , which differs from existing theories. Therefore, following the mechanism of self-similar growth, we derive a relationship of β =4 α (1 +A ) /Frw2 to relate the evolution of chaotic bubbles in problem III to that of semibounded bubbles in problem II. The validity of this relationship highlights the fact that the dynamics of chaotic bubbles in problem III are similar to the semibounded isolated bubbles in problem II, but not to that of bounded periodic bubbles in problem I.

Abundance of nitrogen in QSOs

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

Shields, G.A.

1976-03-01

Models of photoionized QSO emission-line regions show that measurements of O iii/N iv/C iv or N iii/C iii can yield the C/N/O ratios to an accuracy of a factor 2 or better. The N iii/C iii intensity ratios observed for the QSO PKS 1756+237 (z=1.72) implies a N/C abundance ratio 5 times larger than the solar value. This is comparable with the nitrogen overabundance in the nuclei of nearby galaxies, and it points to advanced chemical evolution in this QSO, with Zapproximately-greater-thanZ/sub sun/. Such a large abundance of nitrogen appears to be exceptional; composite spectra indicate that most QSOs havemore » (N/O) approximately one-fourth to one-half the solar value. (AIP)« less

The evolution of culture (or the lack thereof): mapping the conceptual space.

PubMed

Gadagkar, Raghavendra

2017-07-01

This short essay is based on a lecture that I gave at short notice on a subject in which I am by no means an expert. The combination of lack of expertise and time for preparation, created an unexpectedly unique opportunity for thinking outside the box. I decided not to try to read up (as there was no time in any case) but instead to organize the little that I already knew about cultural evolution in a systematic schema-I attempted to create a scaffolding, on which I could hang everything I knew about cultural evolution, and hopefully, everything I might ever discover about cultural evolution in the future. I considered three dimensions of the study of cultural evolution, namely (i) the phenomenon of cultural evolution, (ii) production of knowledge in the field of cultural evolution, and (iii) the consequences or applications of an understanding of the evolution of culture.

Self-assembled polymeric nanoparticles as new, smart contrast agents for cancer early detection using magnetic resonance imaging.

PubMed

Mouffouk, Fouzi; Simão, Teresa; Dornelles, Daniel F; Lopes, André D; Sau, Pablo; Martins, Jorge; Abu-Salah, Khalid M; Alrokayan, Salman A; Rosa da Costa, Ana M; dos Santos, Nuno R

2015-01-01

Early cancer detection is a major factor in the reduction of mortality and cancer management cost. Here we developed a smart and targeted micelle-based contrast agent for magnetic resonance imaging (MRI), able to turn on its imaging capability in the presence of acidic cancer tissues. This smart contrast agent consists of pH-sensitive polymeric micelles formed by self-assembly of a diblock copolymer (poly(ethyleneglycol-b-trimethylsilyl methacrylate)), loaded with a gadolinium hydrophobic complex ((t)BuBipyGd) and exploits the acidic pH in cancer tissues. In vitro MRI experiments showed that (t)BuBipyGd-loaded micelles were pH-sensitive, as they turned on their imaging capability only in an acidic microenvironment. The micelle-targeting ability toward cancer cells was enhanced by conjugation with an antibody against the MUC1 protein. The ability of our antibody-decorated micelles to be switched on in acidic microenvironments and to target cancer cells expressing specific antigens, together with its high Gd(III) content and its small size (35-40 nm) reveals their potential use for early cancer detection by MRI.

Mutations in Human Tubulin Proximal to the Kinesin-Binding Site Alter Dynamic Instability at Microtubule Plus- and Minus-Ends

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

Ti, Shih-Chieh; Pamula, Melissa C.; Howes, Stuart C.

The assembly of microtubule-based cellular structures depends on regulated tubulin polymerization and directional transport. In this research, we have purified and characterized tubulin heterodimers that have human β-tubulin isotype III (TUBB3), as well as heterodimers with one of two β-tubulin mutations (D417H or R262H). Both point mutations are proximal to the kinesin-binding site and have been linked to an ocular motility disorder in humans. Compared to wild-type, microtubules with these mutations have decreased catastrophe frequencies and increased average lifetimes of plus- and minus-end-stabilizing caps. Importantly, the D417H mutation does not alter microtubule lattice structure or Mal3 binding to growing filaments.more » Instead, this mutation reduces the affinity of tubulin for TOG domains and colchicine, suggesting that the distribution of tubulin heterodimer conformations is changed. Together, our findings reveal how residues on the surface of microtubules, distal from the GTP-hydrolysis site and inter-subunit contacts, can alter polymerization dynamics at the plus- and minus-ends of microtubules.« less

The natural history of achalasia: Evidence of a continuum-"The evolutive pattern theory".

PubMed

Salvador, Renato; Voltarel, Guerrino; Savarino, Edoardo; Capovilla, Giovanni; Pesenti, Elisa; Perazzolo, Anna; Nicoletti, Loredana; Costantini, Andrea; Merigliano, Stefano; Costantini, Mario

2018-04-01

It is currently unclear if the three manometric patterns of esophageal achalasia represent distinct entities or part of a disease continuum. The study's aims were: a) to test the hypothesis that the three patterns represent different stages in the evolution of achalasia; b) to investigate whether manometric patterns change after Laparoscopic-Heller-Dor (LHD). We assessed the patients diagnosed with achalasia who underwent LHD as their first treatment from 1992 to 2016. Their symptoms were scored using a detailed questionnaire for dysphagia, food-regurgitation, and chest pain. Barium-swallow, endoscopy, and esophageal-manometry were performed before and 6 months after surgery. The study population consisted of 511 patients (M:F=283:228). Patients' demographic and clinical data showed that those with pattern III had a shorter history of symptoms, a higher incidence of chest pain, and a less dilated gullet (p<0.001). All patients with a sigmoid-shaped mega-esophagus had pattern I achalasia. One patient with a diagnosis of pattern III achalasia developed pattern II at a follow-up manometry before surgery. At a median follow-up of 30 months (IQR 12-56), the outcome of surgery was positive in 479 patients (91.7%). All patients with pattern I preoperatively had the same pattern after LHD, whereas more than 50% of patients with pattern III before treatment showed pattern I or II after surgery. This study supports the hypothesis/theory that the different manometric patterns represent different stages in the evolution of the disease-where pattern III is the earliest stage, pattern II an intermediate stage, and pattern I the final stage. Copyright © 2017 Editrice Gastroenterologica Italiana S.r.l. Published by Elsevier Ltd. All rights reserved.

The luminescent properties of polyethylene films with admixtures of luminophores based on europium compounds

NASA Astrophysics Data System (ADS)

Kalinovskaya, I. V.; Zadorozhnaya, A. N.; Karasev, V. E.

2008-11-01

Polyethylene films activated with europium(III) complexes with carboxylic acids and Eu(L)3 · nD · xH2O + ANT compositions, where L is the trifluoroacetic, toluyl, or cinnamic acid anion and ANT is anthranilic acid, were prepared. The intensity of luminescence of the polymeric compositions depended on the content of luminophores (molar ratio between europium compounds and anthranilic acid). An analysis of the excitation spectra showed that, in polymer—Eu(L)3 · nPhen · xH2O + ANT compositions, there was effective energy transfer from phenanthroline to anthranilic acid levels.

Solar type III radio burst time characteristics at LOFAR frequencies and the implications for electron beam transport

NASA Astrophysics Data System (ADS)

Reid, Hamish A. S.; Kontar, Eduard P.

2018-06-01

Context. Solar type III radio bursts contain a wealth of information about the dynamics of electron beams in the solar corona and the inner heliosphere; this information is currently unobtainable through other means. However, the motion of different regions of an electron beam (front, middle, and back) have never been systematically analysed before. Aims: We characterise the type III burst frequency-time evolution using the enhanced resolution of LOFAR (LOw Frequency ARray) in the frequency range 30-70 MHz and use this to probe electron beam dynamics. Methods: The rise, peak, and decay times with a 0.2 MHz spectral resolution were defined for a collection of 31 type III bursts. The frequency evolution was used to ascertain the apparent velocities of the front, middle, and back of the type III sources, and the trends were interpreted using theoretical and numerical treatments. Results: The type III time profile was better approximated by an asymmetric Gaussian profile and not an exponential, as was used previously. Rise and decay times increased with decreasing frequency and showed a strong correlation. Durations were shorter than previously observed. Drift rates from the rise times were faster than from the decay times, corresponding to inferred mean electron beam speeds for the front, middle, and back of 0.2, 0.17, 0.15 c, respectively. Faster beam speeds correlate with shorter type III durations. We also find that the type III frequency bandwidth decreases as frequency decreases. Conclusions: The different speeds naturally explain the elongation of an electron beam in space as it propagates through the heliosphere. The expansion rate is proportional to the mean speed of the exciter; faster beams expand faster. Beam speeds are attributed to varying ensembles of electron energies at the front, middle, and back of the beam.

Molecular Gene Profiling of Clostridium botulinum Group III and Its Detection in Naturally Contaminated Samples Originating from Various European Countries

PubMed Central

Woudstra, Cedric; Le Maréchal, Caroline; Souillard, Rozenn; Bayon-Auboyer, Marie-Hélène; Anniballi, Fabrizio; Auricchio, Bruna; De Medici, Dario; Bano, Luca; Koene, Miriam; Sansonetti, Marie-Hélène; Desoutter, Denise; Hansbauer, Eva-Maria; Dorner, Martin B.; Dorner, Brigitte G.

2015-01-01

We report the development of real-time PCR assays for genotyping Clostridium botulinum group III targeting the newly defined C. novyi sensu lato group; the nontoxic nonhemagglutinin (NTNH)-encoding gene ntnh; the botulinum neurotoxin (BoNT)-encoding genes bont/C, bont/C/D, bont/D, and bont/D/C; and the flagellin (fliC) gene. The genetic diversity of fliC among C. botulinum group III strains resulted in the definition of five major subgroups named fliC-I to fliC-V. Investigation of fliC subtypes in 560 samples, with various European origins, showed that fliC-I was predominant and found exclusively in samples contaminated by C. botulinum type C/D, fliC-II was rarely detected, no sample was recorded as fliC-III or fliC-V, and only C. botulinum type D/C samples tested positive for fliC-IV. The lack of genetic diversity of the flagellin gene of C. botulinum type C/D would support a clonal spread of type C/D strains in different geographical areas. fliC-I to fliC-III are genetically related (87% to 92% sequence identity), whereas fliC-IV from C. botulinum type D/C is more genetically distant from the other fliC types (with only 50% sequence identity). These findings suggest fliC-I to fliC-III have evolved in a common environment and support a different genetic evolution for fliC-IV. A combination of the C. novyi sensu lato, ntnh, bont, and fliC PCR assays developed in this study allowed better characterization of C. botulinum group III and showed the group to be less genetically diverse than C. botulinum groups I and II, supporting a slow genetic evolution of the strains belonging to C. botulinum group III. PMID:25636839

Polymeric materials from renewable resources

NASA Astrophysics Data System (ADS)

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

2016-05-01

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

Pathogenic Roles for Fungal Melanins

PubMed Central

Jacobson, Eric S.

2000-01-01

Melanins represent virulence factors for several pathogenic fungi; the number of examples is growing. Thus, albino mutants of several genera (in one case, mutated precisely in the melanizing enzyme) exhibit decreased virulence in mice. We consider the phenomenon in relation to known chemical properties of melanin, beginning with biosynthesis from ortho-hydroquinone precursors which, when oxidized enzymatically to quinones, polymerize spontaneously to melanin. It follows that melanizing intermediates are cross-linking reagents; melanization stabilizes the external cell wall against hydrolysis and is thought to determine semipermeability in the osmotic ram (the appressorium) of certain plant pathogens. Polymeric melanins undergo reversible oxidation-reduction reactions between cell wall-penetrating quinone and hydroquinone oxidation states and thus represent polymeric redox buffers; using strong oxidants, it is possible to titrate the melanin on living cells and thereby demonstrate protection conferred by melanin in several species. The amount of buffering per cell approximately neutralizes the amount of oxidant generated by a single macrophage. Moreover, the intermediate oxidation state, the semiquinone, is a very stable free radical and is thought to trap unpaired electrons. We have suggested that the oxidation state of external melanin may be regulated by external Fe(II). An independent hypothesis holds that in Cryptococcus neoformans, an important function of the melanizing enzyme (apart from melanization) is the oxidation of Fe(II) to Fe(III), thereby forestalling generation of the harmful hydroxyl radical from H2O2. Thus, problems in fungal pathogenesis have led to evolving hypotheses regarding melanin functioning. PMID:11023965

Permanganate/bisulfite (PM/BS) conditioning-horizontal electro-dewatering (HED) of activated sludge: Effect of reactive Mn(III) species.

PubMed

Guo, Xinxin; Wang, Yili; Wang, Dongsheng

2017-11-01

A novel activated sludge (AS) conditioning method through permanganate/bisulfate (PM/BS) process was proposed. The method involved a new conditioner of reactive Mn(III) intermediate. Moreover, a Mn(III) conditioning-horizontal electro-dewatering (Mn(III) C-HED) process was established to improve AS dewatering performance. Underlying mechanisms were unraveled by investigating changes in physicochemical characteristics, scanning electron microscope (SEM) morphology, and transformation of water and organic matters. The optimum dewatering conditions for Mn(III) C-HED process with the final water content of 86.94% were determined as the combination of KMnO 4 0.01 mol/L AS and NaHSO 3 0.05 mol/L AS at 20 V for 120 min. Results showed that Mn(III) C-HED process effectively reduced free water and bound water with the corresponding removal ratios of 51.68% and 87.62% at the anode-side as well as 36.55% and 85.08% at the cathode-side, respectively. During the PM/BS process, the produced Mn(III), Mn 2+ , and MnO 2 exerted chemical and physical effects on AS conditioning and dewatering. Mn(III) disintegrated extracellular polymeric substances (EPS) fractions and cells in AS, as well as induced partial bound water release. Additionally, flocculation effect induced by Mn 2+ and MnO 2 skeleton building also benefited AS dewatering. AS cells were further disrupted under the effect of a horizontal electric field. Accordingly, EPS within the AS matrix was solubilized, tightly bound (TB)-EPS or loosely bound (LB)-EPS was converted to their corresponding outer EPS fractions, and AS dewaterability improved. Additionally, changes in pH and temperature at HED stage damaged the AS cells and changed the floc properties, thereby leading to easy separation of liquid and AS particles. Copyright © 2017 Elsevier Ltd. All rights reserved.

The reciprocity law concerning light dose relationships applied to BisGMA/TEGDMA photopolymers: theoretical analysis and experimental characterization.

PubMed

Wydra, James W; Cramer, Neil B; Stansbury, Jeffrey W; Bowman, Christopher N

2014-06-01

A model BisGMA/TEGDMA unfilled resin was utilized to investigate the effect of varied irradiation intensity on the photopolymerization kinetics and shrinkage stress evolution, as a means for evaluation of the reciprocity relationship. Functional group conversion was determined by FTIR spectroscopy and polymerization shrinkage stress was obtained by a tensometer. Samples were polymerized with UV light from an EXFO Acticure with 0.1wt% photoinitiator. A one-dimensional kinetic model was utilized to predict the conversion-dose relationship. As irradiation intensity increased, conversion decreased at a constant irradiation dose and the overall dose required to achieve full conversion increased. Methacrylate conversion ranged from 64±2% at 3mW/cm(2) to 78±1% at 24mW/cm(2) while the final shrinkage stress varied from 2.4±0.1MPa to 3.0±0.1MPa. The ultimate conversion and shrinkage stress levels achieved were dependent not only upon dose but also the irradiation intensity, in contrast to an idealized reciprocity relationship. A kinetic model was utilized to analyze this behavior and provide theoretical conversion profiles versus irradiation time and dose. Analysis of the experimental and modeling results demonstrated that the polymerization kinetics do not and should not be expected to follow the reciprocity law behavior. As irradiation intensity is increased, the overall dose required to achieve full conversion also increased. Further, the ultimate conversion and shrinkage stress that are achieved are not dependent only upon dose but rather upon the irradiation intensity and corresponding polymerization rate. Copyright © 2014 Academy of Dental Materials. Published by Elsevier Ltd. All rights reserved.

The evolutionary life cycle of the polysaccharide biosynthetic gene cluster based on the Sphingomonadaceae.

PubMed

Wu, Mengmeng; Huang, Haidong; Li, Guoqiang; Ren, Yi; Shi, Zhong; Li, Xiaoyan; Dai, Xiaohui; Gao, Ge; Ren, Mengnan; Ma, Ting

2017-04-21

Although clustering of genes from the same metabolic pathway is a widespread phenomenon, the evolution of the polysaccharide biosynthetic gene cluster remains poorly understood. To determine the evolution of this pathway, we identified a scattered production pathway of the polysaccharide sanxan by Sphingomonas sanxanigenens NX02, and compared the distribution of genes between sphingan-producing and other Sphingomonadaceae strains. This allowed us to determine how the scattered sanxan pathway developed, and how the polysaccharide gene cluster evolved. Our findings suggested that the evolution of microbial polysaccharide biosynthesis gene clusters is a lengthy cyclic process comprising cluster 1 → scatter → cluster 2. The sanxan biosynthetic pathway proved the existence of a dispersive process. We also report the complete genome sequence of NX02, in which we identified many unstable genetic elements and powerful secretion systems. Furthermore, nine enzymes for the formation of activated precursors, four glycosyltransferases, four acyltransferases, and four polymerization and export proteins were identified. These genes were scattered in the NX02 genome, and the positive regulator SpnA of sphingans synthesis could not regulate sanxan production. Finally, we concluded that the evolution of the sanxan pathway was independent. NX02 evolved naturally as a polysaccharide producing strain over a long-time evolution involving gene acquisitions and adaptive mutations.

Evolution of material properties during free radical photopolymerization

NASA Astrophysics Data System (ADS)

Wu, Jiangtao; Zhao, Zeang; Hamel, Craig M.; Mu, Xiaoming; Kuang, Xiao; Guo, Zaoyang; Qi, H. Jerry

2018-03-01

Photopolymerization is a widely used polymerization method in many engineering applications such as coating, dental restoration, and 3D printing. It is a complex chemical and physical process, through which a liquid monomer solution is rapidly converted to a solid polymer. In the most common free-radical photopolymerization process, the photoinitiator in the solution is exposed to light and decomposes into active radicals, which attach to monomers to start the polymerization reaction. The activated monomers then attack Cdbnd C double bonds of unsaturated monomers, which leads to the growth of polymer chains. With increases in the polymer chain length and the average molecular weight, polymer chains start to connect and form a network structure, and the liquid polymer solution becomes a dense solid. During this process, the material properties of the cured polymer change dramatically. In this paper, experiments and theoretical modeling are used to investigate the free-radical photopolymerization reaction kinetics, material property evolution and mechanics during the photopolymerization process. The model employs the first order chemical reaction rate equations to calculate the variation of the species concentrations. The degree of monomer conversion is used as an internal variable that dictates the mechanical properties of the cured polymer at different curing states, including volume shrinkage, glass transition temperature, and nonlinear viscoelastic properties. To capture the nonlinear behavior of the cured polymer under low temperature and finite deformation, a multibranch nonlinear viscoelastic model is developed. A phase evolution model is used to describe the mechanics of the coupling between the crosslink network evolution and mechanical loading during the curing process. The comparison of the model and the experimental results indicates that the model can capture property changes during curing. The model is further applied to investigate the internal stress of a thick sample caused by volume shrinkage during photopolymerization. Changes in the conversion degree gradient and the internal stress during photopolymerization are determined using FEM simulation. The model can be extended to many photocuring processes, such as photopolymerization 3D printing, surface coating and automotive part curing processes.

Killing machines: three pore-forming proteins of the immune system

PubMed Central

McCormack, Ryan; de Armas, Lesley; Shiratsuchi, Motoaki

2014-01-01

The evolution of early multicellular eukaryotes 400–500 million years ago required a defensive strategy against microbial invasion. Pore-forming proteins containing the membrane-attack-complex-perforin (MACPF) domain were selected as the most efficient means to destroy bacteria or virally infected cells. The mechanism of pore formation by the MACPF domain is distinctive in that pore formation is purely physical and unspecific. The MACPF domain polymerizes, refolds, and inserts itself into bilayer membranes or bacterial outer cell walls. The displacement of surface lipid/carbohydrate molecules by the polymerizing MACPF domain creates clusters of large, water-filled holes that destabilize the barrier function and provide access for additional anti-bacterial or anti-viral effectors to sensitive sites that complete the destruction of the invader via enzymatic or chemical attack. The highly efficient mechanism of anti-microbial defense by a combined physical and chemical strategy using pore-forming MACPF-proteins has been retargeted during evolution of vertebrates and mammals for three purposes: (1) to kill extracellular bacteria C9/polyC9 evolved in conjunction with complement, (2) to kill virus infected and cancer cells perforin-1/polyperforin-1 CTL evolved targeted by NK and CTL, and (3) to kill intracellular bacteria transmembrane perforin-2/putative polyperforin-2 evolved targeted by phagocytic and nonphagocytic cells. Our laboratory has been involved in the discovery and description of each of the three pore-formers that will be reviewed here. PMID:24293008

Ultrasensitive and selective signal-on electrochemical DNA detection via exonuclease III catalysis and hybridization chain reaction amplification.

PubMed

Ren, Wang; Gao, Zhong Feng; Li, Nian Bing; Luo, Hong Qun

2015-01-15

This work reported a novel, ultrasensitive, and selective platform for electrochemical detection of DNA, employing an integration of exonuclease III (Exo-III) assisted target recycling and hybridization chain reaction (HCR) for the dual signal amplification strategy. The hairpin capture probe DNA (C-DNA) with an Exo-III 3' overhang end was self-assembled on a gold electrode. In the presence of target DNA (T-DNA), C-DNA hybridized with the T-DNA to form a duplex region, exposing its 5' complementary sequence (initiator). Exo-III was applied to selectively digest duplex region from its 3-hydroxyl termini until the duplex was fully consumed, leaving the remnant initiator. The intact T-DNA spontaneously dissociated from the structure and then initiated the next hybridization process as a result of catalysis of the Exo-III. HCR event was triggered by the initiator and two hairpin helper signal probes labeled with methylene blue, facilitating the polymerization of oligonucleotides into a long nicked dsDNA molecule. The numerous exposed remnant initiators can trigger more HCR events. Because of integration of dual signal amplification and the specific HCR process reaction, the resultant sensor showed a high sensitivity for the detection of the target DNA in a linear range from 1.0 fM to 1.0 nM, and a detection limit as low as 0.2 fM. The proposed dual signal amplification strategy provides a powerful tool for detecting different sequences of target DNA by changing the sequence of capture probe and signal probes, holding a great potential for early diagnosis in gene-related diseases. Copyright © 2014 Elsevier B.V. All rights reserved.

Convergent and divergent evolution in carnivorous pitcher plant traps.

PubMed

Thorogood, Chris J; Bauer, Ulrike; Hiscock, Simon J

2018-02-01

Contents Summary 1035 I. Introduction 1035 II. Evolution of the pitcher 1036 III. Convergent evolution 1036 IV. Divergent evolution 1038 V. Adaptive radiation and speciation 1040 VI. Conclusions and perspectives 1040 Acknowledgements 1040 References 1040 SUMMARY: The pitcher trap is a striking example of convergent evolution across unrelated carnivorous plant lineages. Convergent traits that have evolved across pitcher plant lineages are essential for trap function, suggesting that key selective pressures are in action. Recent studies have also revealed patterns of divergent evolution in functional pitcher morphology within genera. Adaptations to differences in local prey assemblages may drive such divergence and, ultimately, speciation. Here, we review recent research on convergent and divergent evolution in pitcher plant traps, with a focus on the genus Nepenthes, which we propose as a new model for research into adaptive radiation and speciation. © 2017 The Authors. New Phytologist © 2017 New Phytologist Trust.

On the theory of the type III burst exciter

NASA Technical Reports Server (NTRS)

Smith, R. A.; Goldstein, M. L.; Papadopoulos, K.

1976-01-01

In situ satellite observations of type III burst exciters at 1 AU show that the beam does not evolve into a plateau in velocity space, contrary to the prediction of quasilinear theory. The observations can be explained by a theory that includes mode coupling effects due to excitation of the parametric oscillating two-stream instability and its saturation by anomalous resistivity. The time evolution of the beam velocity distribution is included in the analysis.

Hydrogel based QCM aptasensor for detection of avian influenza virus.

PubMed

Wang, Ronghui; Li, Yanbin

2013-04-15

The objective of this study was to develop a quartz crystal microbalance (QCM) aptasensor based on ssDNA crosslinked polymeric hydrogel for rapid, sensitive and specific detection of avian influenza virus (AIV) H5N1. A selected aptamer with high affinity and specificity against AIV H5N1 surface protein was used, and hybridization between the aptamer and ssDNA formed the crosslinker in the polymer hydrogel. The aptamer hydrogel was immobilized on the gold surface of QCM sensor using a self-assembled monolayer method. The hydrogel remained in the state of shrink if no H5N1 virus was present in the sample because of the crosslinking between the aptamer and ssDNA in the polymer network. When it exposed to target virus, the binding reaction between the aptamer and H5N1 virus caused the dissolution of the linkage between the aptamer and ssDNA, resulting in the abrupt swelling of the hydrogel. The swollen hydrogel was monitored by the QCM sensor in terms of decreased frequency. Three polymeric hydrogels with different ratio (100:1 hydrogel I, 10:1 hydrogel II, 1:1 hydrogel III) of acrylamide and the aptamer monomer were synthesized, respectively, and then were used as the QCM sensor coating material. The results showed that the developed hydrogel QCM aptasensor was capable of detecting target H5N1 virus, and among the three developed aptamer hydrogels, hydrogel III coated QCM aptasensor achieved the highest sensitivity with the detection limit of 0.0128 HAU (HA unit). The total detection time from sampling to detection was only 30 min. In comparison with the anti-H5 antibody coated QCM immunosensor, the hydrogel QCM aptasensor lowered the detection limit and reduced the detection time. Copyright © 2012 Elsevier B.V. All rights reserved.

Effects of axions on Population III stars

NASA Astrophysics Data System (ADS)

Choplin, Arthur; Coc, Alain; Meynet, Georges; Olive, Keith A.; Uzan, Jean-Philippe; Vangioni, Elisabeth

2017-09-01

Aims: Following the renewed interest in axions as a dark matter component, we revisit the effects of energy loss by axion emission on the evolution of the first generation of stars. These stars with zero metallicity are assumed to be massive, more compact, and hotter than subsequent generations. It is hence important to extend previous studies, which were restricted to solar metallicity stars. Methods: Our analysis first compares the evolution of solar metallicity 8, 10, and 12 M⊙ stars to previous work. We then calculate the evolution of 8 zero-metallicity stars with and without axion losses and with masses ranging from 20 to 150 M⊙. Results: For the solar metallicity models, we confirm the disappearance of the blue-loop phase for a value of the axion-photon coupling of gaγ = 10-10 GeV-1. We show that for gaγ = 10-10 GeV-1, the evolution of Population III stars is not much affected by axion losses, except within the range of masses 80-130 M⊙. Such stars show significant differences in both their tracks within the Tc-ρc diagram and their central composition (in particular 20Ne and 24Mg). We discuss the origin of these modifications from the stellar physics point of view, and also their potential observational signatures.

Spectroscopic characterization of the coordination chemistry and hydrolysis of gallium(III) in the presence of aquatic organic matter

NASA Astrophysics Data System (ADS)

Hagvall, Kristoffer; Persson, Per; Karlsson, Torbjörn

2014-12-01

Interactions between metals and natural organic matter (NOM) are of great environmental importance and one of the key factors influencing hydrolysis, solubility, and speciation of the metals. However, studying geochemically relevant metals like Al, Fe, and Cu is sometimes associated with analytical problems; for example Fe and Cu are both redox active. Gallium (Ga) is a non-redox active metal that usually occurs at very low concentrations in environmental samples and therefore a wide concentration range of metal(III)-NOM species can be explored by adding Ga(III) to such samples. This makes Ga(III) a good probe and analogue for other metal ions, in particular Al. In addition, due to the increased usage of Ga in society, a better understanding of how Ga interacts with NOM is of importance but such studies are scarce. In this work, Ga(III) interactions with two different organic materials (Suwannee River natural organic matter and Suwannee River fulvic acid) were studied using infrared (IR) and extended X-ray absorption fine structure (EXAFS) spectroscopy in a large experimental range (101-84,076 μg Ga g-1 dry weight; pH 3-8). Our IR spectroscopic results showed that Ga(III) is bonded mainly to carboxylic functional groups and suggested that only a fraction of the total number of carboxylic sites in the samples was actively involved in the bonding. Modeling of the EXAFS data revealed that Ga(III) formed mononuclear chelate complexes with NOM that strongly suppressed the hydrolysis and polymerization of Ga(III). At low Ga(III) concentrations (1675-16,649 μg g-1) organic complexes, consisting of 1-3 chelate ring structures, were the dominating species in the entire pH range while at higher concentrations (67,673-84,076 μg g-1, pH 3.0-7.0) we detected mixtures of mononuclear organic Ga(III) complexes, Ga(III) (hydr)oxide, and free Ga(III) (here defined as the hydrated Ga(III) ion and its soluble hydrolysis products). Moreover, the EXAFS results showed significantly higher contribution from second-shell C atoms (9-11) for the Ga(III)-organic complexes at the lowest concentration (101-125 μg g-1, pH 4.9-5.1), indicating formation of cage-like structures similar to Ga(III)-EDTA. Our combined results showed that Ga(III)-NOM interactions can be of importance for the solubility and speciation of Ga in environmental systems. Furthermore, the similarities between Ga(III) and previous Fe(III) results demonstrate that Ga(III) can be utilized as a probe for metal(III)-NOM interactions over an extended experimental range (e.g., pH and metal concentration) and thereby improve our knowledge about these interactions in general.

The dawn of the RNA World: Toward functional complexity through ligation of random RNA oligomers

PubMed Central

Briones, Carlos; Stich, Michael; Manrubia, Susanna C.

2009-01-01

A main unsolved problem in the RNA World scenario for the origin of life is how a template-dependent RNA polymerase ribozyme emerged from short RNA oligomers obtained by random polymerization on mineral surfaces. A number of computational studies have shown that the structural repertoire yielded by that process is dominated by topologically simple structures, notably hairpin-like ones. A fraction of these could display RNA ligase activity and catalyze the assembly of larger, eventually functional RNA molecules retaining their previous modular structure: molecular complexity increases but template replication is absent. This allows us to build up a stepwise model of ligation-based, modular evolution that could pave the way to the emergence of a ribozyme with RNA replicase activity, step at which information-driven Darwinian evolution would be triggered. PMID:19318464

Chromium in rivers impacted by tannery wastes determined by high performance liquid chromatography - inductively coupled plasma mass spectrometry

NASA Astrophysics Data System (ADS)

Pereira de Abreu, M.-H.; Vignati, D.; Dominik, J.

2003-05-01

The total chromium concentrations by ICP-MS and HPLC-ICP-MS and the redox chromium species have been determined in rivers impacted by untreated wastes from tanneries at Fès (Morocco). The results obtained by two ICP-MS analysis methods showed significantly different chromium values at m/z 53. The higher values obtained with external calibration, can be attributed to matrix effects, especially ^{37}Cl ^{16}O at m/z 53. This is confirmed on the chromatograms by the presence of a peak at 100s with the anomalous ^{52}Cr/^{53}Cr isotopic ratio. The hexavalent chromium was not detected. Two trivalent chromium monomer species, Cr(OH)(H2O)5^{2+} and Cr(H2O)6^{3+}, were present in low concentrations. We suppose that the major part of chromium occurred as Cr(III) polymeric species which were not retained on the column. These Cr(III) forms are usually complexed with Cl^- or/and SO4^{2-}, used as tanning agents.

Effect of dissimilatory Fe(III) reducers on bio-reduction and nickel-cobalt recovery from Sukinda chromite-overburden.

PubMed

Esther, Jacintha; Panda, Sandeep; Behera, Sunil K; Sukla, Lala B; Pradhan, Nilotpala; Mishra, Barada K

2013-10-01

The effect of an adapted dissimilatory iron reducing bacterial consortium (DIRB) towards bio-reduction of Sukinda chromite overburden (COB) with enhanced recovery of nickel and cobalt is being reported for the first time. The remarkable ability of DIRB to utilize Fe(III) as terminal electron acceptor reducing it to Fe(II) proved beneficial for treatment of COB as compared to previous reports for nickel leaching. XRD studies showed goethite as the major iron-bearing phase in COB. Under facultative anaerobic conditions, goethite was reduced to hematite and magnetite with the exposure of nickel oxide. FESEM studies showed DIRB to be associated with COB through biofilm formation with secondary mineral precipitates of magnetite deposited as tiny globular clusters on the extra polymeric substances. The morphological and mineralogical changes in COB, post DIRB application, yielded a maximum of 68.5% nickel and 80.98% cobalt in 10 days using 8M H2SO4. Copyright © 2013 Elsevier Ltd. All rights reserved.

Bis(4-(3,4-dimethylenepyrrolidyl)-phenyl) methane

NASA Technical Reports Server (NTRS)

Ottenbrite, Raphael M. (Inventor)

1989-01-01

It is the primary object of the present invention to prepare high temperature polymeric materials, especially linear aromatic polyimides, which maintain their integrity and toughness during long exposure times at elevated temperatures. According to the present invention, this object is achieved, and the attending benefits are obtained, by first providing the bis(exocyclodiene) bis(4-(3,4-dinethylene pyrrolidyl) phenyl) methane, which is formed from the monomer N-phenyl 3,4-dimethylene pyrrolidine. This bis-(exocyclodiene) undergoes Diels-Alder reaction with a bismaleimide without the evolution of gaseous by-products, to form the aromatic polyimide.

[Cell-ELA-based determination of binding affinity of DNA aptamer against U87-EGFRvIII cell].

PubMed

Tan, Yan; Liang, Huiyu; Wu, Xidong; Gao, Yubo; Zhang, Xingmei

2013-05-01

A15, a DNA aptamer with binding specificity for U87 glioma cells stably overexpressing the epidermal growth factor receptor variant III (U87-EGFRvIII), was generated by cell systematic evolution of ligands by exponential enrichment (cell-SELEX) using a random nucleotide library. Subsequently, we established a cell enzyme-linked assay (cell-ELA) to detect the affinity of A15 compared to an EGFR antibody. We used A15 as a detection probe and cultured U87-EGFRvIII cells as targets. Our data indicate that the equilibrium dissociation constants (K(d)) for A15 were below 100 nmol/L and had similar affinity compared to an EGFR antibody for U87-EGFRvIII. We demonstrated that the cell-ELA was a useful method to determine the equilibrium dissociation constants (K(d)) of aptamers generated by cell-SELEX.

SDSS-III: Massive Spectroscopic Surveys of the Distant Universe, the Milky Way, and Extra-Solar Planetary Systems

NASA Astrophysics Data System (ADS)

Eisenstein, Daniel J.; Weinberg, David H.; Agol, Eric; Aihara, Hiroaki; Allende Prieto, Carlos; Anderson, Scott F.; Arns, James A.; Aubourg, Éric; Bailey, Stephen; Balbinot, Eduardo; Barkhouser, Robert; Beers, Timothy C.; Berlind, Andreas A.; Bickerton, Steven J.; Bizyaev, Dmitry; Blanton, Michael R.; Bochanski, John J.; Bolton, Adam S.; Bosman, Casey T.; Bovy, Jo; Brandt, W. N.; Breslauer, Ben; Brewington, Howard J.; Brinkmann, J.; Brown, Peter J.; Brownstein, Joel R.; Burger, Dan; Busca, Nicolas G.; Campbell, Heather; Cargile, Phillip A.; Carithers, William C.; Carlberg, Joleen K.; Carr, Michael A.; Chang, Liang; Chen, Yanmei; Chiappini, Cristina; Comparat, Johan; Connolly, Natalia; Cortes, Marina; Croft, Rupert A. C.; Cunha, Katia; da Costa, Luiz N.; Davenport, James R. A.; Dawson, Kyle; De Lee, Nathan; Porto de Mello, Gustavo F.; de Simoni, Fernando; Dean, Janice; Dhital, Saurav; Ealet, Anne; Ebelke, Garrett L.; Edmondson, Edward M.; Eiting, Jacob M.; Escoffier, Stephanie; Esposito, Massimiliano; Evans, Michael L.; Fan, Xiaohui; Femenía Castellá, Bruno; Dutra Ferreira, Leticia; Fitzgerald, Greg; Fleming, Scott W.; Font-Ribera, Andreu; Ford, Eric B.; Frinchaboy, Peter M.; García Pérez, Ana Elia; Gaudi, B. Scott; Ge, Jian; Ghezzi, Luan; Gillespie, Bruce A.; Gilmore, G.; Girardi, Léo; Gott, J. Richard; Gould, Andrew; Grebel, Eva K.; Gunn, James E.; Hamilton, Jean-Christophe; Harding, Paul; Harris, David W.; Hawley, Suzanne L.; Hearty, Frederick R.; Hennawi, Joseph F.; González Hernández, Jonay I.; Ho, Shirley; Hogg, David W.; Holtzman, Jon A.; Honscheid, Klaus; Inada, Naohisa; Ivans, Inese I.; Jiang, Linhua; Jiang, Peng; Johnson, Jennifer A.; Jordan, Cathy; Jordan, Wendell P.; Kauffmann, Guinevere; Kazin, Eyal; Kirkby, David; Klaene, Mark A.; Knapp, G. R.; Kneib, Jean-Paul; Kochanek, C. S.; Koesterke, Lars; Kollmeier, Juna A.; Kron, Richard G.; Lampeitl, Hubert; Lang, Dustin; Lawler, James E.; Le Goff, Jean-Marc; Lee, Brian L.; Lee, Young Sun; Leisenring, Jarron M.; Lin, Yen-Ting; Liu, Jian; Long, Daniel C.; Loomis, Craig P.; Lucatello, Sara; Lundgren, Britt; Lupton, Robert H.; Ma, Bo; Ma, Zhibo; MacDonald, Nicholas; Mack, Claude; Mahadevan, Suvrath; Maia, Marcio A. G.; Majewski, Steven R.; Makler, Martin; Malanushenko, Elena; Malanushenko, Viktor; Mandelbaum, Rachel; Maraston, Claudia; Margala, Daniel; Maseman, Paul; Masters, Karen L.; McBride, Cameron K.; McDonald, Patrick; McGreer, Ian D.; McMahon, Richard G.; Mena Requejo, Olga; Ménard, Brice; Miralda-Escudé, Jordi; Morrison, Heather L.; Mullally, Fergal; Muna, Demitri; Murayama, Hitoshi; Myers, Adam D.; Naugle, Tracy; Neto, Angelo Fausti; Nguyen, Duy Cuong; Nichol, Robert C.; Nidever, David L.; O'Connell, Robert W.; Ogando, Ricardo L. C.; Olmstead, Matthew D.; Oravetz, Daniel J.; Padmanabhan, Nikhil; Paegert, Martin; Palanque-Delabrouille, Nathalie; Pan, Kaike; Pandey, Parul; Parejko, John K.; Pâris, Isabelle; Pellegrini, Paulo; Pepper, Joshua; Percival, Will J.; Petitjean, Patrick; Pfaffenberger, Robert; Pforr, Janine; Phleps, Stefanie; Pichon, Christophe; Pieri, Matthew M.; Prada, Francisco; Price-Whelan, Adrian M.; Raddick, M. Jordan; Ramos, Beatriz H. F.; Reid, I. Neill; Reyle, Celine; Rich, James; Richards, Gordon T.; Rieke, George H.; Rieke, Marcia J.; Rix, Hans-Walter; Robin, Annie C.; Rocha-Pinto, Helio J.; Rockosi, Constance M.; Roe, Natalie A.; Rollinde, Emmanuel; Ross, Ashley J.; Ross, Nicholas P.; Rossetto, Bruno; Sánchez, Ariel G.; Santiago, Basilio; Sayres, Conor; Schiavon, Ricardo; Schlegel, David J.; Schlesinger, Katharine J.; Schmidt, Sarah J.; Schneider, Donald P.; Sellgren, Kris; Shelden, Alaina; Sheldon, Erin; Shetrone, Matthew; Shu, Yiping; Silverman, John D.; Simmerer, Jennifer; Simmons, Audrey E.; Sivarani, Thirupathi; Skrutskie, M. F.; Slosar, Anže; Smee, Stephen; Smith, Verne V.; Snedden, Stephanie A.; Stassun, Keivan G.; Steele, Oliver; Steinmetz, Matthias; Stockett, Mark H.; Stollberg, Todd; Strauss, Michael A.; Szalay, Alexander S.; Tanaka, Masayuki; Thakar, Aniruddha R.; Thomas, Daniel; Tinker, Jeremy L.; Tofflemire, Benjamin M.; Tojeiro, Rita; Tremonti, Christy A.; Vargas Magaña, Mariana; Verde, Licia; Vogt, Nicole P.; Wake, David A.; Wan, Xiaoke; Wang, Ji; Weaver, Benjamin A.; White, Martin; White, Simon D. M.; Wilson, John C.; Wisniewski, John P.; Wood-Vasey, W. Michael; Yanny, Brian; Yasuda, Naoki; Yèche, Christophe; York, Donald G.; Young, Erick; Zasowski, Gail; Zehavi, Idit; Zhao, Bo

2011-09-01

Building on the legacy of the Sloan Digital Sky Survey (SDSS-I and II), SDSS-III is a program of four spectroscopic surveys on three scientific themes: dark energy and cosmological parameters, the history and structure of the Milky Way, and the population of giant planets around other stars. In keeping with SDSS tradition, SDSS-III will provide regular public releases of all its data, beginning with SDSS Data Release 8 (DR8), which was made public in 2011 January and includes SDSS-I and SDSS-II images and spectra reprocessed with the latest pipelines and calibrations produced for the SDSS-III investigations. This paper presents an overview of the four surveys that comprise SDSS-III. The Baryon Oscillation Spectroscopic Survey will measure redshifts of 1.5 million massive galaxies and Lyα forest spectra of 150,000 quasars, using the baryon acoustic oscillation feature of large-scale structure to obtain percent-level determinations of the distance scale and Hubble expansion rate at z < 0.7 and at z ≈ 2.5. SEGUE-2, an already completed SDSS-III survey that is the continuation of the SDSS-II Sloan Extension for Galactic Understanding and Exploration (SEGUE), measured medium-resolution (R = λ/Δλ ≈ 1800) optical spectra of 118,000 stars in a variety of target categories, probing chemical evolution, stellar kinematics and substructure, and the mass profile of the dark matter halo from the solar neighborhood to distances of 100 kpc. APOGEE, the Apache Point Observatory Galactic Evolution Experiment, will obtain high-resolution (R ≈ 30,000), high signal-to-noise ratio (S/N >= 100 per resolution element), H-band (1.51 μm < λ < 1.70 μm) spectra of 105 evolved, late-type stars, measuring separate abundances for ~15 elements per star and creating the first high-precision spectroscopic survey of all Galactic stellar populations (bulge, bar, disks, halo) with a uniform set of stellar tracers and spectral diagnostics. The Multi-object APO Radial Velocity Exoplanet Large-area Survey (MARVELS) will monitor radial velocities of more than 8000 FGK stars with the sensitivity and cadence (10-40 m s-1, ~24 visits per star) needed to detect giant planets with periods up to two years, providing an unprecedented data set for understanding the formation and dynamical evolution of giant planet systems. As of 2011 January, SDSS-III has obtained spectra of more than 240,000 galaxies, 29,000 z >= 2.2 quasars, and 140,000 stars, including 74,000 velocity measurements of 2580 stars for MARVELS.

Evolution of corundum-structured III-oxide semiconductors: Growth, properties, and devices

NASA Astrophysics Data System (ADS)

Fujita, Shizuo; Oda, Masaya; Kaneko, Kentaro; Hitora, Toshimi

2016-12-01

The recent progress and development of corundum-structured III-oxide semiconductors are reviewed. They allow bandgap engineering from 3.7 to ∼9 eV and function engineering, leading to highly durable electronic devices and deep ultraviolet optical devices as well as multifunctional devices. Mist chemical vapor deposition can be a simple and safe growth technology and is advantageous for reducing energy and cost for the growth. This is favorable for the wide commercial use of devices at low cost. The III-oxide semiconductors are promising candidates for new devices contributing to sustainable social, economic, and technological development for the future.

BES-III distributed computing status

NASA Astrophysics Data System (ADS)

Belov, S. D.; Deng, Z. Y.; Korenkov, V. V.; Li, W. D.; Lin, T.; Ma, Z. T.; Nicholson, C.; Pelevanyuk, I. S.; Suo, B.; Trofimov, V. V.; Tsaregorodtsev, A. U.; Uzhinskiy, A. V.; Yan, T.; Yan, X. F.; Zhang, X. M.; Zhemchugov, A. S.

2016-09-01

The BES-III experiment at the Institute of High Energy Physics (Beijing, China) is aimed at the precision measurements in e+e- annihilation in the energy range from 2.0 till 4.6 GeV. The world's largest samples of J/psi and psi' events and unique samples of XYZ data have been already collected. The expected increase of the data volume in the coming years required a significant evolution of the computing model, namely shift from a centralized data processing to a distributed one. This report summarizes a current design of the BES-III distributed computing system, some of key decisions and experience gained during 2 years of operations.

Arsenic detoxification and evolution of trimethylarsine gas by a microbial arsenite S-adenosylmethionine methyltransferase

PubMed Central

Qin, Jie; Rosen, Barry P.; Zhang, Yang; Wang, Gejiao; Franke, Sylvia; Rensing, Christopher

2006-01-01

In this article, a mechanism of arsenite [As(III)]resistance through methylation and subsequent volatization is described. Heterologous expression of arsM from Rhodopseudomonas palustris was shown to confer As(III) resistance to an arsenic-sensitive strain of Escherichia coli. ArsM catalyzes the formation of a number of methylated intermediates from As(III), with trimethylarsine as the end product. The net result is loss of arsenic, from both the medium and the cells. Because ArsM homologues are widespread in nature, this microbial-mediated transformation is proposed to have an important impact on the global arsenic cycle. PMID:16452170

SENER molten salt tower technology. Ouarzazate NOOR III case

NASA Astrophysics Data System (ADS)

Relloso, Sergio; Gutiérrez, Yolanda

2017-06-01

NOOR III 150 MWe project is the evolution of Gemasolar (19.9 MWe) to large scale Molten Salt Tower plants. With more than 5 years of operational experience, Gemasolar lessons learned have been the starting point for the optimization of this technology, considered the leader of potential cost reduction in CSP. In addition, prototypes of plant key components (heliostat and receiver) were manufactured and thoroughly tested before project launch in order to prove the new engineering solutions adopted. The SENER proprietary technology of NOOR III will be applied in the next Molten Salt Tower plants that will follow in other countries, such as South Africa, Chile and Australia.

Towards a Computational Comparative Neuroprimatology: Framing the language-ready brain.

PubMed

Arbib, Michael A

2016-03-01

We make the case for developing a Computational Comparative Neuroprimatology to inform the analysis of the function and evolution of the human brain. First, we update the mirror system hypothesis on the evolution of the language-ready brain by (i) modeling action and action recognition and opportunistic scheduling of macaque brains to hypothesize the nature of the last common ancestor of macaque and human (LCA-m); and then we (ii) introduce dynamic brain modeling to show how apes could acquire gesture through ontogenetic ritualization, hypothesizing the nature of evolution from LCA-m to the last common ancestor of chimpanzee and human (LCA-c). We then (iii) hypothesize the role of imitation, pantomime, protosign and protospeech in biological and cultural evolution from LCA-c to Homo sapiens with a language-ready brain. Second, we suggest how cultural evolution in Homo sapiens led from protolanguages to full languages with grammar and compositional semantics. Third, we assess the similarities and differences between the dorsal and ventral streams in audition and vision as the basis for presenting and comparing two models of language processing in the human brain: A model of (i) the auditory dorsal and ventral streams in sentence comprehension; and (ii) the visual dorsal and ventral streams in defining "what language is about" in both production and perception of utterances related to visual scenes provide the basis for (iii) a first step towards a synthesis and a look at challenges for further research. Copyright © 2015 Elsevier B.V. All rights reserved.

Towards a Computational Comparative Neuroprimatology: Framing the language-ready brain

NASA Astrophysics Data System (ADS)

Arbib, Michael A.

2016-03-01

We make the case for developing a Computational Comparative Neuroprimatology to inform the analysis of the function and evolution of the human brain. First, we update the mirror system hypothesis on the evolution of the language-ready brain by (i) modeling action and action recognition and opportunistic scheduling of macaque brains to hypothesize the nature of the last common ancestor of macaque and human (LCA-m); and then we (ii) introduce dynamic brain modeling to show how apes could acquire gesture through ontogenetic ritualization, hypothesizing the nature of evolution from LCA-m to the last common ancestor of chimpanzee and human (LCA-c). We then (iii) hypothesize the role of imitation, pantomime, protosign and protospeech in biological and cultural evolution from LCA-c to Homo sapiens with a language-ready brain. Second, we suggest how cultural evolution in Homo sapiens led from protolanguages to full languages with grammar and compositional semantics. Third, we assess the similarities and differences between the dorsal and ventral streams in audition and vision as the basis for presenting and comparing two models of language processing in the human brain: A model of (i) the auditory dorsal and ventral streams in sentence comprehension; and (ii) the visual dorsal and ventral streams in defining ;what language is about; in both production and perception of utterances related to visual scenes provide the basis for (iii) a first step towards a synthesis and a look at challenges for further research.

How range shifts induced by climate change affect neutral evolution

PubMed Central

McInerny, G.J.; Turner, J.R.G.; Wong, H.Y.; Travis, J.M.J.; Benton, T.G.

2009-01-01

We investigate neutral evolution during range shifts in a strategic model of a metapopulation occupying a climate gradient. Using heritable, neutral markers, we track the spatio-temporal fate of lineages. Owing to iterated founder effects (‘mutation surfing’), survival of lineages derived from the leading range limit is enhanced. At trailing limits, where habitat suitability decreases, survival is reduced (mutations ‘wipe out’). These processes alter (i) the spatial spread of mutations, (ii) origins of persisting mutations and (iii) the generation of diversity. We show that large changes in neutral evolution can be a direct consequence of range shifting. PMID:19324824

How range shifts induced by climate change affect neutral evolution.

PubMed

McInerny, G J; Turner, J R G; Wong, H Y; Travis, J M J; Benton, T G

2009-04-22

We investigate neutral evolution during range shifts in a strategic model of a metapopulation occupying a climate gradient. Using heritable, neutral markers, we track the spatio-temporal fate of lineages. Owing to iterated founder effects ('mutation surfing'), survival of lineages derived from the leading range limit is enhanced. At trailing limits, where habitat suitability decreases, survival is reduced (mutations 'wipe out'). These processes alter (i) the spatial spread of mutations, (ii) origins of persisting mutations and (iii) the generation of diversity. We show that large changes in neutral evolution can be a direct consequence of range shifting.

Polymerization stress evolution of a bulk-fill flowable composite under different compliances.

PubMed

Guo, Yongwen; Landis, Forrest A; Wang, Zhengzhi; Bai, Ding; Jiang, Li; Chiang, Martin Y M

2016-04-01

To use a compliance-variable instrument to simultaneously measure and compare the polymerization stress (PS) evolution, degree of conversion (DC), and exotherm of a bulk-fill flowable composite to a packable composite. A bulk-fill flowable composite (Filtek Bulk-fill, FBF) and a conventional packable composite (Filtek Z250, Z250) purchased from 3M ESPE were investigated. The composites were studied using a cantilever-beam based instrument equipped with an in situ near infrared (NIR) spectrometer and a microprobe thermocouple. The measurements were carried out under various instrumental compliances (ranging from 0.3327μm/N to 12.3215μm/N) that are comparable to the compliances of clinically prepared tooth cavities. Correlations between the PS and temperature change as well as the DC were interpreted. The maximum PS of both composites at 10min after irradiation decreased with the increase in the compliance of the cantilever beam. The FBF composite generated a lower final stress than the Z250 sample under instrumental compliances less than ca. 4μm/N; however, both materials generated statistically similar PS values at higher compliances. The reaction exotherm and the DC of both materials were found to be independent of compliance. The DC of the FBF sample was slightly higher than that of the packable Z250 composite while the peak exotherm of FBF was almost double that of the Z250 composite. For FBF, a characteristic drop in the PS was observed during the early stage of polymerization for all compliances studied which was not observed in the Z250 sample. This drop was shown to relate to the greater exotherm of the less-filled FBF sample relative to the Z250 composite. While the composites with lower filler content (low viscosity) are generally considered to have lower PS than the conventional packable composites, a bulk-fill flowable composite was shown to produce lower PS under a lower compliance of constraint as would be experienced if the composite was used as the base material in clinical procedures. Published by Elsevier Ltd.

Application of SBA-15 in Adsorption-Fenton Oxidation Process for Simultaneous Remediation of Dehp and As(iii)

NASA Astrophysics Data System (ADS)

Latorre, I.; Hwang, S.

2013-12-01

Di-2-ethylhexyl phthalate (DEHP) has been widely used as plasticizer in the manufacturing of polymeric materials to enhance flexibility, transparency and softness, particularly, in polyvinyl chloride (PVC) production. Several studies elucidated that DEHP could be linked to hepatocellular tumors and pre-term birth and may be a developmental and reproductive toxicant. Arsenic (As) contamination has been widespread in the environment and because of its toxicity and prevalence in nature; it also has become a significant environmental health concern. Most solid waste materials containing DEHP and As(III) are disposed of in landfills and may migrate to groundwater and soil environments representing a threat to human receptors. Therefore, the application of adsorption-Fenton oxidation process with Fe adsorbed to SBA-15 matrix was assessed for simultaneous remediation of DEHP and As(III). Three sequences were run to assess the regeneration efficiency of the SBA-15. A response surface methodology was employed to optimize adsorption and Fenton regeneration. Adsorption optimization was evaluated with regard to SBA-15 doses and the extent of As(III) and Fe concentrations. Optimization of Fenton regeneration, in addition, assessed initial H2O2 concentration. Global optimization for maximum reduction of DEHP and As(III) was performed by D-Optimal. Highest adsorption of DEHP (90-95%) and As (40-95%) into the SBA-15 was predicted at 1.16 mM Fe, 18.74 mg SBA-15 and 3.71 mg/L As(III). Highest reduction of As (78-99%) and DEHP (90-97%) was predicted with 0.50 mM Fe, 22 mg SBA-15, 3.02 mg/L As(III) and 22.50 mM H2O2. Global optimal treatments were validated and SBA-15 regenerated material was characterized via SEM and XPS. The efficiency of DEHP and As(III) remediation by adsorption-Fenton oxidation process, applying optimal treatment combinations, was evaluated using leachate from a lab scale bioreactor monofill (i.e., filled with PVC materials). Capability of As(III) and DEHP adsorption into SBA-15 was affected by the preferentiality adsorption of Fe and other compounds present in the monofill leachate.

Capacity and recycling of polyoxometalate applied in As(III) oxidation by Fe(II)-Amended zero-valent aluminum.

PubMed

Hsu, Liang-Ching; Cho, Yen-Lin; Liu, Yu-Ting; Tzou, Yu-Min; Teah, Heng Yi

2018-06-01

Arsenic remediation is often initiated by oxidizing As(III) to As(V) to alleviate its toxicity and mobility. Due to the easy availability, zero-valent Al (ZVAl) like Al can was considered as potential alternatives to facilitate As(III) oxidation. This study determined the capability and recycling of polyoxometalate (POM) to catalyze As(III) oxidation in Fe(II)-amended ZVAl systems. POM acquired electrons from ZVAl more effectively at pH 1 than at pH 2. While 76% of the reduced POM [POM(e - )] reacted with O 2(g) to generate H 2 O 2 at pH 1, only 60% of POM(e - ) was used to produce H 2 O 2 at pH 2. The remaining POM(e - ) was oxidized by the generated H 2 O 2 . Such additional consumption of POM(e - ) and H 2 O 2 led to the incomplete As(III) oxidation in the system without residual ZVAl and emphasized the need for a continuous electron supply from ZVAl to compensate the depletion of POM(e - ). After the hydrolyzation at pH 6.0, the XANES data evidenced that not only As(V) but WO 4 released from the POM retained on surfaces of Al/Fe hydroxides. The competition for sorption sites on Al/Fe hydroxides between As(V) and WO 4 led to the incomplete As removal. Despite the loss of WO 4 , the POM re-polymerized at pH 1 still showed the comparable capability to catalyze As(III) oxidation with original POM. This study revealed electron transfer pathways from ZVAl to As(III) as catalyzed by POM and evidenced the effective POM recycling after As removal, which lowers the cost of POM application and turns the ZVAl/Fe(II)/POM/O 2 system into a practical strategy for As remediation. Copyright © 2018 Elsevier Ltd. All rights reserved.

Phylogenetics and evolution of Trx SET genes in fully sequenced land plants.

PubMed

Zhu, Xinyu; Chen, Caoyi; Wang, Baohua

2012-04-01

Plant Trx SET proteins are involved in H3K4 methylation and play a key role in plant floral development. Genes encoding Trx SET proteins constitute a multigene family in which the copy number varies among plant species and functional divergence appears to have occurred repeatedly. To investigate the evolutionary history of the Trx SET gene family, we made a comprehensive evolutionary analysis on this gene family from 13 major representatives of green plants. A novel clustering (here named as cpTrx clade), which included the III-1, III-2, and III-4 orthologous groups, previously resolved was identified. Our analysis showed that plant Trx proteins possessed a variety of domain organizations and gene structures among paralogs. Additional domains such as PHD, PWWP, and FYR were early integrated into primordial SET-PostSET domain organization of cpTrx clade. We suggested that the PostSET domain was lost in some members of III-4 orthologous group during the evolution of land plants. At least four classes of gene structures had been formed at the early evolutionary stage of land plants. Three intronless orphan Trx SET genes from the Physcomitrella patens (moss) were identified, and supposedly, their parental genes have been eliminated from the genome. The structural differences among evolutionary groups of plant Trx SET genes with different functions were described, contributing to the design of further experimental studies.

Real-time observation of rotational twin formation during molecular-beam epitaxial growth of GaAs on Si (111) by x-ray diffraction

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

Suzuki, Hidetoshi, E-mail: hsuzuki@cc.miyazaki-u.ac.jp; Nakata, Yuka; Takahasi, Masamitu

2016-03-15

The formation and evolution of rotational twin (TW) domains introduced by a stacking fault during molecular-beam epitaxial growth of GaAs on Si (111) substrates were studied by in situ x-ray diffraction. To modify the volume ratio of TW to total GaAs domains, GaAs was deposited under high and low group V/group III (V/III) flux ratios. For low V/III, there was less nucleation of TW than normal growth (NG) domains, although the NG and TW growth rates were similar. For high V/III, the NG and TW growth rates varied until a few GaAs monolayers were deposited; the mean TW domain sizemore » was smaller for all film thicknesses.« less

A self-assembled Ni(cyclam)-BTC network on ITO for an oxygen evolution catalyst in alkaline solution.

PubMed

Leem, Yun Jin; Cho, Keumnam; Oh, Kyung Hee; Han, Sung-Hwan; Nam, Ki Min; Chang, Jinho

2017-03-25

A self-assembled Ni(cyclam)-BTC film was formed on ITO in an acidic solution. Ni(cyclam)-BTC exhibited an enhanced electro-catalytic property for the oxygen evolution reaction (OER), which was strongly relevant to the Ni(iii)/Ni(iv) redox reaction activated by the potential dynamic process. A possible formation mechanism of Ni(cyclam)-BTC by self-assembly on ITO was also proposed.

Candidate Cell and Matrix Interaction Domains on the Collagen Fibril, the Predominant Protein of Vertebrates*S⃞

PubMed Central

Sweeney, Shawn M.; Orgel, Joseph P.; Fertala, Andrzej; McAuliffe, Jon D.; Turner, Kevin R.; Di Lullo, Gloria A.; Chen, Steven; Antipova, Olga; Perumal, Shiamalee; Ala-Kokko, Leena; Forlino, Antonella; Cabral, Wayne A.; Barnes, Aileen M.; Marini, Joan C.; Antonio, James D. San

2008-01-01

Type I collagen, the predominant protein of vertebrates, polymerizes with type III and V collagens and non-collagenous molecules into large cable-like fibrils, yet how the fibril interacts with cells and other binding partners remains poorly understood. To help reveal insights into the collagen structure-function relationship, a data base was assembled including hundreds of type I collagen ligand binding sites and mutations on a two-dimensional model of the fibril. Visual examination of the distribution of functional sites, and statistical analysis of mutation distributions on the fibril suggest it is organized into two domains. The “cell interaction domain” is proposed to regulate dynamic aspects of collagen biology, including integrin-mediated cell interactions and fibril remodeling. The “matrix interaction domain” may assume a structural role, mediating collagen cross-linking, proteoglycan interactions, and tissue mineralization. Molecular modeling was used to superimpose the positions of functional sites and mutations from the two-dimensional fibril map onto a three-dimensional x-ray diffraction structure of the collagen microfibril in situ, indicating the existence of domains in the native fibril. Sequence searches revealed that major fibril domain elements are conserved in type I collagens through evolution and in the type II/XI collagen fibril predominant in cartilage. Moreover, the fibril domain model provides potential insights into the genotype-phenotype relationship for several classes of human connective tissue diseases, mechanisms of integrin clustering by fibrils, the polarity of fibril assembly, heterotypic fibril function, and connective tissue pathology in diabetes and aging. PMID:18487200

Candidate Cell and Matrix Interaction Domains on the Collagen Fibril, the Predominant Protein of Vertebrates

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

Sweeney, Shawn M.; Orgel, Joseph P.; Fertala, Andrzej

Type I collagen, the predominant protein of vertebrates, polymerizes with type III and V collagens and non-collagenous molecules into large cable-like fibrils, yet how the fibril interacts with cells and other binding partners remains poorly understood. To help reveal insights into the collagen structure-function relationship, a data base was assembled including hundreds of type I collagen ligand binding sites and mutations on a two-dimensional model of the fibril. Visual examination of the distribution of functional sites, and statistical analysis of mutation distributions on the fibril suggest it is organized into two domains. The 'cell interaction domain' is proposed to regulatemore » dynamic aspects of collagen biology, including integrin-mediated cell interactions and fibril remodeling. The 'matrix interaction domain' may assume a structural role, mediating collagen cross-linking, proteoglycan interactions, and tissue mineralization. Molecular modeling was used to superimpose the positions of functional sites and mutations from the two-dimensional fibril map onto a three-dimensional x-ray diffraction structure of the collagen microfibril in situ, indicating the existence of domains in the native fibril. Sequence searches revealed that major fibril domain elements are conserved in type I collagens through evolution and in the type II/XI collagen fibril predominant in cartilage. Moreover, the fibril domain model provides potential insights into the genotype-phenotype relationship for several classes of human connective tissue diseases, mechanisms of integrin clustering by fibrils, the polarity of fibril assembly, heterotypic fibril function, and connective tissue pathology in diabetes and aging.« less

Biochemical evolution III: Polymerization on organophilic silica-rich surfaces, crystal–chemical modeling, formation of first cells, and geological clues

PubMed Central

Smith, Joseph V.; Arnold, Frederick P.; Parsons, Ian; Lee, Martin R.

1999-01-01

Catalysis at organophilic silica-rich surfaces of zeolites and feldspars might generate replicating biopolymers from simple chemicals supplied by meteorites, volcanic gases, and other geological sources. Crystal–chemical modeling yielded packings for amino acids neatly encapsulated in 10-ring channels of the molecular sieve silicalite-ZSM-5-(mutinaite). Calculation of binding and activation energies for catalytic assembly into polymers is progressing for a chemical composition with one catalytic Al–OH site per 25 neutral Si tetrahedral sites. Internal channel intersections and external terminations provide special stereochemical features suitable for complex organic species. Polymer migration along nano/micrometer channels of ancient weathered feldspars, plus exploitation of phosphorus and various transition metals in entrapped apatite and other microminerals, might have generated complexes of replicating catalytic biomolecules, leading to primitive cellular organisms. The first cell wall might have been an internal mineral surface, from which the cell developed a protective biological cap emerging into a nutrient-rich “soup.” Ultimately, the biological cap might have expanded into a complete cell wall, allowing mobility and colonization of energy-rich challenging environments. Electron microscopy of honeycomb channels inside weathered feldspars of the Shap granite (northwest England) has revealed modern bacteria, perhaps indicative of Archean ones. All known early rocks were metamorphosed too highly during geologic time to permit simple survival of large-pore zeolites, honeycombed feldspar, and encapsulated species. Possible microscopic clues to the proposed mineral adsorbents/catalysts are discussed for planning of systematic study of black cherts from weakly metamorphosed Archaean sediments. PMID:10097060

The evolution of lycopsid rooting structures: conservatism and disparity.

PubMed

Hetherington, Alexander J; Dolan, Liam

2017-07-01

Contents 538 I. 538 II. 539 III. 541 IV. 542 543 References 543 SUMMARY: The evolution of rooting structures was a crucial event in Earth's history, increasing the ability of plants to extract water, mine for nutrients and anchor above-ground shoot systems. Fossil evidence indicates that roots evolved at least twice among vascular plants, in the euphyllophytes and independently in the lycophytes. Here, we review the anatomy and evolution of lycopsid rooting structures. Highlighting recent discoveries made with fossils we suggest that the evolution of lycopsid rooting structures displays two contrasting patterns - conservatism and disparity. The structures termed roots have remained structurally similar despite hundreds of millions of years of evolution - an example of remarkable conservatism. By contrast, and over the same time period, the organs that give rise to roots have diversified, resulting in the evolution of numerous novel and disparate organs. © 2016 The Authors. New Phytologist © 2016 New Phytologist Trust.

49 CFR 171.16 - Detailed hazardous materials incident reports.

Code of Federal Regulations, 2010 CFR

2010-10-01

..., explosion or dangerous evolution of heat (i.e., an amount of heat sufficient to be dangerous to packaging or... seal, pump, compressor, or valve; or (iii) Connection or disconnection of loading or unloading lines...

Development of the chromatographic partitioning of cesium and strontium utilizing two macroporous silica-based calix[4]arene-crown and amide impregnated polymeric composites: PREC partitioning process.

PubMed

Zhang, Anyun; Kuraoka, Etsushu; Kumagai, Mikio

2007-07-20

To partition effectively Cs(I) and Sr(II), two harmful heat emitting nuclides, from a highly active liquid waste by extraction chromatography, two kinds of macroporous silica-based polymeric materials, Calix[4]arene-R14/SiO(2)-P and TODGA/SiO(2)-P, were synthesized. Two chelating agents, 1,3-[(2,4-diethyl-heptylethoxy)oxy]-2,4-crown-6-calix[4]arene (Calix[4]arene-R14), an excellent supramolecular compound having molecular recognition ability for Cs(I), and N,N,N',N'-tetraoctyl-3-oxapentane-1,5-diamide (TODGA) were impregnated and immobilized into the pores of SiO(2)-P particles support by a vacuum sucking technique. The loading and elution of 11 typical simulated fission and non-fission products from 4.0M or 2.0M HNO(3) were performed at 298K. It was found that in the first column packed with the Calix[4]arene-R14/SiO(2)-P, all of the simulated elements were separated effectively into two groups: (1) Na(I), K(I), Sr(II), Fe(III), Ba(II), Ru(III), Pd(II), Zr(IV), and Mo(VI) (noted as Sr-group); (2) Cs(I)-Rb(I) (Cs-group) by eluting with 4.0M HNO(3) and distilled water, respectively. The harmful element Cs(I) flowed into the second group along with Rb(I) because of their close sorption and elution properties towards Calix[4]arene-R14/SiO(2)-P, while Sr(II) showed no sorption and flowed into Sr-containing group. In the second column packed with TODGA/SiO(2)-P, the Sr-group was separated into (1) Ba(II), Ru(III), Na(I), K(I), Fe(III), and Mo(VI) (non-sorption group); (2) Sr(II); (3) Pd(II); and (4) Zr(IV) by eluting with 2.0M HNO(3), 0.01M HNO(3), 0.05M DTPA-pH 2.5, and 0.5M H(2)C(2)O(4), respectively. Sr(II) adsorbed towards TODGA/SiO(2)-P flowed into the second group and showed the excellent separation efficiency from others. Based on the elution behavior of the tested elements, an advanced PREC (Partitioning and Recovery of two heat generators from an acidic HLW (high activity liquid waste) by Extraction Chromatography) process was proposed.

Bioreducible Fluorinated Peptide Dendrimers Capable of Circumventing Various Physiological Barriers for Highly Efficient and Safe Gene Delivery.

PubMed

Cai, Xiaojun; Jin, Rongrong; Wang, Jiali; Yue, Dong; Jiang, Qian; Wu, Yao; Gu, Zhongwei

2016-03-09

Polymeric vectors have shown great promise in the development of safe and efficient gene delivery systems; however, only a few have been developed in clinical settings due to poor transport across multiple physiological barriers. To address this issue and promote clinical translocation of polymeric vectors, a new type of polymeric vector, bioreducible fluorinated peptide dendrimers (BFPDs), was designed and synthesized by reversible cross-linking of fluorinated low generation peptide dendrimers. Through masterly integration all of the features of reversible cross-linking, fluorination, and polyhedral oligomeric silsesquioxane (POSS) core-based peptide dendrimers, this novel vector exhibited lots of unique features, including (i) inactive surface to resist protein interactions; (ii) virus-mimicking surface topography to augment cellular uptake; (iii) fluorination-mediated efficient cellular uptake, endosome escape, cytoplasm trafficking, and nuclear entry, and (iv) disulfide-cleavage-mediated polyplex disassembly and DNA release that allows efficient DNA transcription. Noteworthy, all of these features are functionally important and can synergistically facilitate DNA transport from solution to the nucleus. As a consequences, BFPDs showed excellent gene transfection efficiency in several cell lines (∼95% in HEK293 cells) and superior biocompatibility compared with polyethylenimine (PEI). Meanwhile BFPDs provided excellent serum resistance in gene delivery. More importantly, BFPDs offer considerable in vivo gene transfection efficiency (in muscular tissues and in HepG2 tumor xenografts), which was approximately 77-fold higher than that of PEI in luciferase activity. These results suggest bioreducible fluorinated peptide dendrimers are a new class of highly efficient and safe gene delivery vectors and should be used in clinical settings.

Highly Efficient Photocatalytic H2 Evolution from Water using Visible Light and Structure-Controlled Graphitic Carbon Nitride**

PubMed Central

Martin, David James; Qiu, Kaipei; Shevlin, Stephen Andrew; Handoko, Albertus Denny; Chen, Xiaowei; Guo, Zhengxiao; Tang, Junwang

2014-01-01

The major challenge of photocatalytic water splitting, the prototypical reaction for the direct production of hydrogen by using solar energy, is to develop low-cost yet highly efficient and stable semiconductor photocatalysts. Herein, an effective strategy for synthesizing extremely active graphitic carbon nitride (g-C3N4) from a low-cost precursor, urea, is reported. The g-C3N4 exhibits an extraordinary hydrogen-evolution rate (ca. 20 000 μmol h−1 g−1 under full arc), which leads to a high turnover number (TON) of over 641 after 6 h. The reaction proceeds for more than 30 h without activity loss and results in an internal quantum yield of 26.5 % under visible light, which is nearly an order of magnitude higher than that observed for any other existing g-C3N4 photocatalysts. Furthermore, it was found by experimental analysis and DFT calculations that as the degree of polymerization increases and the proton concentration decreases, the hydrogen-evolution rate is significantly enhanced. PMID:25045013

Injection initiated fracture in soft solids

NASA Astrophysics Data System (ADS)

Hutchens, Shelby; Yang, Steven

Damage accumulation in soft materials under hydrostatic loading conditions is a primary injury mechanism in blast and blunt force trauma. A recently explored technique known as cavitation rheology (CR) provides a promising avenue for quickly and inexpensively approximating hydrostatic conditions via the reverse loading scenario, void pressurization. Past CR measurements of synthetic, polymeric materials at length scales from mm's to μm's have been found to correlate with both elastic modulus and fracture energy. The technique is performed via pressurization of fluid within a needle that is embedded within a material. This experimental setup allows crack evolution to be monitored, similar to traditional pre-notched failure samples. We observe a systematic evolution of crack morphology as a function of cross-link density in a soft elastomer. Crack shape is quantified using micro-computed tomography and shown to transition from being roughly penny-shaped to multi-lobed (predominately three) to spherical with decreasing crosslinking. Moduli are on the order of kPa. We describe this morphology evolution using a balance between the energetic costs of the strain energy in deforming the surrounding material and the intrinsic fracture energy necessary to form a new surface.

Observations of (S III) emission from Galactic radio sources - The detection of distant planetary nebulae and a search for supernova remnant emission

NASA Technical Reports Server (NTRS)

Kistiakowsky, V.; Helfand, D. J.

1993-01-01

Narrow-band near-infrared imaging observations at wavelengths corresponding to forbidden S III 9069,9532 A have been carried out at the MDM 1.3 m telescope for 23 radio sources near the Galactic plane in an attempt to detect emission associated with nebulae marking the endpoints of stellar evolution. While none of the known remnants or remnant candidates were detected, 10 of the 11 PN candidates from a new radio imaging survey of the Galactic plane were clearly seen in the forbidden S III 9532 A line. We present a calculation of the relative efficacy of searching for PNe in the forbidden O III and forbidden S III lines; for the majority of all PNe, the observed forbidden S III 9532 A line is predicted to be stronger than forbiden O III 5007 A whenever the visual extinction exceeds 3 magnitudes. This makes forbidden S III the superior tracer of PNe at distances exceeding a few kpc. We briefly comment on the significance of this approach to defining the spatial distribution of the PN population of the Galaxy.

Molecular architectures of benzoic acid-specific type III polyketide synthases

PubMed Central

Stewart, Charles; Woods, Kate; Macias, Greg; Allan, Andrew C.; Noel, Joseph P.

2017-01-01

Biphenyl synthase and benzophenone synthase constitute an evolutionarily distinct clade of type III polyketide synthases (PKSs) that use benzoic acid-derived substrates to produce defense metabolites in plants. The use of benzoyl-CoA as an endogenous substrate is unusual for type III PKSs. Moreover, sequence analyses indicate that the residues responsible for the functional diversification of type III PKSs are mutated in benzoic acid-specific type III PKSs. In order to gain a better understanding of structure–function relationships within the type III PKS family, the crystal structures of biphenyl synthase from Malus × domestica and benzophenone synthase from Hypericum androsaemum were compared with the structure of an archetypal type III PKS: chalcone synthase from Malus × domestica. Both biphenyl synthase and benzophenone synthase contain mutations that reshape their active-site cavities to prevent the binding of 4-coumaroyl-CoA and to favor the binding of small hydrophobic substrates. The active-site cavities of biphenyl synthase and benzophenone synthase also contain a novel pocket associated with their chain-elongation and cyclization reactions. Collectively, these results illuminate structural determinants of benzoic acid-specific type III PKSs and expand the understanding of the evolution of specialized metabolic pathways in plants. PMID:29199980

Formation of the first galaxies under Population III stellar feedback

NASA Astrophysics Data System (ADS)

Jeon, Myoungwon

2015-01-01

The first galaxies, which formed a few hundred million years after the big bang, are related to important cosmological questions. Given thatthey are thought to be the basic building blocks of large galaxies seen today, understanding their formation and properties is essentialto studying galaxy formation as a whole. In this dissertation talk, I will present the results of our highly-resolved cosmological ab-initio simulations to understand the assembly process of first galaxies under the feedback from the preceding generations of first stars, the so-called Population III (Pop III). The first stars formed at z≲30 in dark matter (DM) minihalos with M_{vir}=10^5-10^6Msun, predominately via molecular hydrogen (H_2) cooling. Radiation from Pop III stars dramatically altered the gas within their host minihalos, through photoionization, photoheating, and photoevaporation. Once a Pop III star explodes as a supernova (SN), heavy elements are dispersed, enriching the interstellar (ISM) and intergalactic medium (IGM), thus initiating the process of chemical evolution. I will begin by presenting how the SN explosion of the first stars influences early cosmic history, specifically assessing the time delay in further star formation and tracing the evolution of metal-enriched gas until the second episode star formation happens. These results will show the role of Pop III supernovae on the star formation transition from Pop III to Population II. Additionally, the more distant, diffuse IGM was heated by X-rays emitted by accreting black holes (BHs), or high-mass X-ray binaries (HMXBs), both remnants of Pop III stars. I will present results of a series of simulations where we study the impact of X-ray feedback from BHs and HMXBs on the star formation history in the early universe, and discuss the resulting implications on reionization. I will also present the role of X-rays on the early BH growth, providing constraints on models for supermassive black hole formation. Finally, I will discuss key physical quantities of the first galaxies derived from our simulations, such as their stellar population mix, star formation rates, metallicities, and resulting broad-band color and recombination spectra.

Formation of Light Absorbing Soluble Secondary Organics and Insoluble Polymeric Particles from the Dark Reaction of Catechol and Guaiacol with Fe(III).

PubMed

Slikboer, Samantha; Grandy, Lindsay; Blair, Sandra L; Nizkorodov, Sergey A; Smith, Richard W; Al-Abadleh, Hind A

2015-07-07

Transition metals such as iron are reactive components of environmentally relevant surfaces. Here, dark reaction of Fe(III) with catechol and guaiacol was investigated in an aqueous solution at pH 3 under experimental conditions that mimic reactions in the adsorbed phase of water. Using UV-vis spectroscopy, liquid chromatography, mass spectrometry, elemental analysis, dynamic light scattering, and electron microscopy techniques, we characterized the reactants, intermediates, and products as a function of reaction time. The reactions of Fe(III) with catechol and guaiacol produced significant changes in the optical spectra of the solutions due to the formation of light absorbing secondary organics and colloidal organic particles. The primary steps in the reaction mechanism were shown to include oxidation of catechol and guaiacol to hydroxy- and methoxy-quinones. The particles formed within a few minutes of reaction and grew to micron-size aggregates after half an hour reaction. The mass-normalized absorption coefficients of the particles were comparable to those of strongly absorbing brown carbon compounds produced by biomass burning. These results could account for new pathways that lead to atmospheric secondary organic aerosol formation and abiotic polymer formation on environmental surfaces mediated by transition metals.

Analyses and comparison of a novel, hybrid, multifunctional orthopedic composite and implant

NASA Astrophysics Data System (ADS)

Dicicco, Michael

In the orthopedic/medical device industry, 2, 2' -bis-(4-(2-hydroxy-3-methacryloxypropoxy)phenyl]propane (Bis-GMA)- and diurethanedimethacrylate (DUDMA)-based polymeric biomaterials have become well-known substitutes for polymethylmethacrylate (PMMA)- and ultra-high molecular weight polyethylene (UHMWPE)-based biomaterials, respectively. The development of these polymeric biomaterials cannot continue without direct comparison studies against currently marketed materials. The initiative for this research stems wholly from developing analytical methodologies that assist in qualifying novel biomaterials under development, by evaluating their chemical properties, performance, and safety. The goals of this research were: (i) Characterize the assay/quality of every resin component and quantify elution of extractable monomers from novel, DUDMA-based RHAKOSS(TM) implant, (ii) Determine degree of conversion (alpha) and rate of polymerization (Rp) for novel, Bis-GMA-based CORTOSS(TM) composite, (iii) Assess risk for radical-induced post-surgical cytotoxicity for CORTOSS, (iv) Determine if surface radical chemistries occur for sterilized RHAKOSS and assess its oxidative stability, and (v) Quantify antibiotic elution from antibiotic-impregnated CORTOSS and identify factors that control elution. The phenomena studied necessitated the utilization of several analytical spectroscopic techniques; fluorometry, differential scanning calorimetry (DSC), electron paramagnetic resonance (EPR), ultraviolet-visible (UV-VIS), attenuated total reflectance---Fourier-transform infrared (ATR-FTIR), and high performance liquid chromatography (HPLC). A battery of lateral chemical techniques were employed as well; including molecular derivatization/tagging, phase partitioning, spin-trapping, and thermal annealing. Results demonstrated that RHAKOSS monomer percent compositions were prepared according to formulations and monomer elution was virtually undetectable, serving as an empirical gauge to portend degree of polymerization (DOP). A high alpha was reported for CORTOSS and essentially all bifunctional monomers had at least one functional group polymerized, stressing low monomer elution potential. Regarding cytotoxicity, CORTOSS impeded further production of hydroxyl radicals (•OH), whereas RHAKOSS did not facilitate the Fenton reaction but displayed some chelating abilities. Residual radicals in RHAKOSS were easily terminated, thus not projected to form oxidative degradants. Additionally, significant antibiotic concentrations, over extended durations, eluted from CORTOSS in linear-type fashion, advocating a sustained therapeutic effect, and phase partitioning correlated antibiotic release to hydrophilicity. The incurred data comprehensively argues in favor of the excellent biocompatibility that CORTOSS and RHAKOSS inherently possess, and was definitive in rendering them as advanced biomaterials, possessing favorable chemical properties.

DETERMINING THE LARGE-SCALE ENVIRONMENTAL DEPENDENCE OF GAS-PHASE METALLICITY IN DWARF GALAXIES

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

Douglass, Kelly A.; Vogeley, Michael S., E-mail: kelly.a.douglass@drexel.edu

2017-01-10

We study how the cosmic environment affects galaxy evolution in the universe by comparing the metallicities of dwarf galaxies in voids with dwarf galaxies in more dense regions. Ratios of the fluxes of emission lines, particularly those of the forbidden [O iii] and [S ii] transitions, provide estimates of a region’s electron temperature and number density. From these two quantities and the emission line fluxes [O ii] λ 3727, [O iii] λ 4363, and [O iii] λλ 4959, 5007, we estimate the abundance of oxygen with the direct T{sub e}  method. We estimate the metallicity of 42 blue, star-forming voidmore » dwarf galaxies and 89 blue, star-forming dwarf galaxies in more dense regions using spectroscopic observations from the Sloan Digital Sky Survey Data Release 7, as reprocessed in the MPA-JHU value-added catalog. We find very little difference between the two sets of galaxies, indicating little influence from the large-scale environment on their chemical evolution. Of particular interest are a number of extremely metal-poor dwarf galaxies that are less prevalent in voids than in the denser regions.« less

Correlating Free-Volume Hole Distribution to the Glass Transition Temperature of Epoxy Polymers.

PubMed

Aramoon, Amin; Breitzman, Timothy D; Woodward, Christopher; El-Awady, Jaafar A

2017-09-07

A new algorithm is developed to quantify the free-volume hole distribution and its evolution in coarse-grained molecular dynamics simulations of polymeric networks. This is achieved by analyzing the geometry of the network rather than a voxelized image of the structure to accurately and efficiently find and quantify free-volume hole distributions within large scale simulations of polymer networks. The free-volume holes are quantified by fitting the largest ellipsoids and spheres in the free-volumes between polymer chains. The free-volume hole distributions calculated from this algorithm are shown to be in excellent agreement with those measured from positron annihilation lifetime spectroscopy (PALS) experiments at different temperature and pressures. Based on the results predicted using this algorithm, an evolution model is proposed for the thermal behavior of an individual free-volume hole. This model is calibrated such that the average radius of free-volumes holes mimics the one predicted from the simulations. The model is then employed to predict the glass-transition temperature of epoxy polymers with different degrees of cross-linking and lengths of prepolymers. Comparison between the predicted glass-transition temperatures and those measured from simulations or experiments implies that this model is capable of successfully predicting the glass-transition temperature of the material using only a PDF of the initial free-volume holes radii of each microstructure. This provides an effective approach for the optimized design of polymeric systems on the basis of the glass-transition temperature, degree of cross-linking, and average length of prepolymers.

Property evolution during vitrification of dimethacrylate photopolymer networks

PubMed Central

Abu-Elenain, Dalia; Lewis, Steven H.; Stansbury, Jeffrey W.

2013-01-01

Objectives This study seeks to correlate the interrelated properties of conversion, shrinkage, modulus and stress as dimethacrylate networks transition from rubbery to glassy states during photopolymerization. Methods An unfilled BisGMA/TEGDMA resin was photocured for various irradiation intervals (7–600 s) to provide controlled levels of immediate conversion, which was monitored continuously for 10 min. Fiber optic near-infrared spectroscopy permitted coupling of real-time conversion measurement with dynamic polymerization shrinkage (linometer), modulus (dynamic mechanical analyzer) and stress (tensometer) development profiles. Results The varied irradiation conditions produced final conversion ranging from 6 % to more than 60 %. Post-irradiation conversion (dark cure) was quite limited when photopolymerization was interrupted either at very low or very high levels of conversion while significant dark cure contributions were possible for photocuring reactions suspended within the post-gel, rubbery regime. Analysis of conversion-based property evolution during and subsequent to photocuring demonstrated that the shrinkage rate increased significantly at about 40 % conversion followed by late-stage suppression in the conversion-dependent shrinkage rate that begins at about 45–50 % conversion. The gradual vitrification process over this conversion range is evident based on the broad but well-defined inflection in the modulus versus conversion data. As limiting conversion is approached, modulus and, to a somewhat lesser extent, stress rise precipitously as a result of vitrification with the stress profile showing little if any late-stage suppression as seen with shrinkage. Significance Near the limiting conversion for this model resin, the volumetric polymerization shrinkage rate slows while an exponential rise in modulus promotes the vitrification process that appears to largely dictate stress development. PMID:24080378

Composite nanofibers prepared from metallic iron nanoparticles and polyaniline: high performance for water treatment applications.

PubMed

Bhaumik, Madhumita; Choi, Hyoung J; McCrindle, Rob I; Maity, Arjun

2014-07-01

Presented here is a simple preparation of metallic iron nanoparticles, supported on polyaniline nanofibers at room temperature. The preparation is based on polymerization of interconnected nanofibers by rapid mixing of the aniline monomer with Fe(III) chloride as the oxidant, followed by reductive deposition of Fe(0) nanoparticles, using the polymerization by-products as the Fe precursor. The morphology and other physico-chemical properties of the resulting composite were characterized by scanning and transmission electron microscopy, Brunauer-Emmett-Teller method, X-ray diffraction, Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy, and vibrating-sample magnetometry. The composite fibers were 80-150 nm in diameter and exhibited the expected ferromagnetic behavior. The composite rapidly and efficiently removed As(V), Cr(VI), and also Congo red dye, from aqueous solutions suggesting their usefulness for removal of toxic materials from wastewater. The composite fibers have high capacity for toxin removal: 42.37 mg/g of As(V), 434.78 mg/g of Cr(VI), and 243.9 mg/g of Congo red. The fibers are easily recovered from fluids by exploiting their ferromagnetic properties. Copyright © 2014 Elsevier Inc. All rights reserved.

Covalent immobilization of metal–organic frameworks onto the surface of nylon—a new approach to the functionalization and coloration of textiles

PubMed Central

Yu, Ming; Li, Wanxin; Wang, Ziqiang; Zhang, Bowu; Ma, Hongjuan; Li, Linfan; Li, Jingye

2016-01-01

The prevention of refractory organic pollution caused by conventional dyeing and the development of new fabrics with various functions are two issues to be solved urgently in the field of textile fabrication. Here, we report a new environmentally friendly route for the simultaneous coloration and functionalization of textiles by the covalent immobilization of a metal–organic framework, Cr-based MIL-101(Cr), onto the surfaces of nylon fabrics by co-graft polymerization with 2-hydroxyethyl acrylate initiated by γ-ray irradiation. The Cr(III) clusters color the nylon fabric, and the color intensity varies with the MIL-101 content, providing a “green” textile coloration method that is different from conventional dyeing processes. An X-ray diffraction (XRD) analysis shows that the nanoporous structure of the original MIL-101 particles is retained during radiation-induced graft polymerization. Numerous nanopores are introduced onto the surface of the nylon fabric, which demonstrated better sustained-release-of-aroma performance versus pristine nylon fabric in tests. The modified fabrics exhibit laundering durability, with MIL-101 nanoparticles intact on the nylon surface after 30 h of dry cleaning. PMID:26948405

Graphene Quantum Dot-Aerogel: From Nanoscopic to Macroscopic Fluorescent Materials. Sensing Polyaromatic Compounds in Water.

PubMed

Martín-Pacheco, Ana; Del Río Castillo, Antonio Esaú; Martín, Cristina; Herrero, María Antonia; Merino, Sonia; García Fierro, José Luis; Díez-Barra, Enrique; Vázquez, Ester

2018-05-30

Fluorescence based on quantum confinement is a property restricted to the nanoscopic range. The incorporation of nanoparticles in a three-dimensional polymeric network could afford macroscopic scaffolds that show nanoscopic properties. Moreover, if these scaffolds are based on strong bonds, the stability of the resulting materials can be preserved, thus enhancing their final applications. We report for the first time the preparation of a graphene quantum dot (GQD) composite based on a cationic covalent network. This new material has unusual features: (i) the final composite remains stable after several swelling-deswelling cycles, thus demonstrating strong interactions between GQDs and the polymeric material, and therefore it could be used as a portable system. (ii) Fluorescence emission in the composite and in solution is quasi-independent to the excitation wavelength. (iii) However, and in contrast to the behavior observed in GQD solutions, the fluorescence of the composite remains unaltered over a wide pH range and in the presence of different ions commonly found in tap water. (iv) Fluorescence quenching is only observed as a consequence of molecules that bear aromatic systems, and this could be applied to the preparation of in situ water sensors.

Influence of carboxylic acid type on microstructure and magnetic properties of polymeric complex sol-gel driven NiFe2O4

NASA Astrophysics Data System (ADS)

Hessien, M. M.; Mostafa, Nasser Y.; Abd-Elkader, Omar H.

2016-01-01

Citric, oxalic and tartaric acids were used for synthesis of NiFe2O4 using polymeric complex precursor route. The dry precursor gels were calcined at various temperatures (400-1100 °C) for 2 h. All carboxylic acids produce iron-deficient NiFe2O4 with considerable amount of α-Fe2O3 at 400 °C. Increase in the annealing temperature caused reaction of α-Fe2O3 with iron-deficient ferrite phase. The amount of initially formed α-Fe2O3 is directly correlated with stability constant and inversely correlated with the decomposition temperature of Fe(III) carboxylate precursors. In case of tartaric acid precursor, single phase of the ferrite was obtained at 450 °C. However, in case of oxalic acid and citric acid precursors, single phase ferrite was obtained at 550 °C and 700 °C, respectively. The lattice parameters were increased with increasing annealing temperature and with decreasing the amount of α-Fe2O3. Maximum saturation magnetization (55 emu/g) was achieved using tartaric acid precursor annealed at 1100 °C.

Experimental use of new absorbable tracheal stent.

PubMed

Schopf, Luciano F; Fraga, José Carlos; Porto, Rodrigo; Santos, Luis A; Marques, Douglas R; Sanchez, Paulo R; Meyer, Fabíola S; Ulbrich, Jane M

2017-11-16

Silicone and metallic stents are not effective in children with tracheobronchial stenosis or tracheomalacia. Herein, we aimed to evaluate the clinical manifestations and histological reaction of rabbit trachea to the presence of a new poly(lactic-co-glycolic acid) with polyisoprene (PLGA/PI) polymer absorbable stent. Fourteen adult white rabbits (weight, 3.0-3.5kg) were randomly assigned to three groups: Group I (n=6): PLGA/PI spiral stent; Group II (n=6): PLGA/PI fragment; and Group III (n=2): controls. After a longitudinal incision on three cervical tracheal rings, the stents and fragments were inserted into the trachea and fixed onto the lateral wall with nonabsorbable sutures. The stented group showed significantly more stridor at rest (p=0.0041), agitation (p=0.014), and use of accessory muscles (p=0.0002) and required more emergency endoscopies than the fragment group. Further, it showed significantly more remarkable histological inflammatory damage than the fragment and control groups (p=0.002). The new PLGA/PI polymeric stent implanted into the trachea of rabbits caused more clinical manifestations and histologically verified inflammatory reaction than the PLGA/PI polymeric fragment. Future studies should be aimed at reducing the stent-wall thickness. Copyright © 2017 Elsevier Inc. All rights reserved.

Atomically Thin Mesoporous Nanomesh of Graphitic C₃N₄ for High-Efficiency Photocatalytic Hydrogen Evolution.

PubMed

Han, Qing; Wang, Bing; Gao, Jian; Cheng, Zhihua; Zhao, Yang; Zhang, Zhipan; Qu, Liangti

2016-02-23

Delamination of layer materials into two-dimensional single-atom sheets has induced exceptional physical properties, including large surface area, ultrahigh intrinsic carrier mobility, pronounced changes in the energy band structure, and other properties. Here, atomically thin mesoporous nanomesh of graphitic carbon nitride (g-C3N4) is fabricated by solvothermal exfoliation of mesoporous g-C3N4 bulk made from thermal polymerization of freeze-drying assembled Dicyandiamide nanostructure precursor. With the unique structural advantages for aligned energy levels, electron transfer, light harvesting, and the richly available reaction sites, the as-prepared monolayer of mesoporous g-C3N4 nanomesh exhibits a superior photocatalytic hydrogen evolution rate of 8510 μmol h(-1) g(-1) under λ > 420 nm and an apparent quantum efficiency of 5.1% at 420 nm, the highest of all the metal-free g-C3N4 nanosheets photocatalysts.

49 CFR 171.16 - Detailed hazardous materials incident reports.

Code of Federal Regulations, 2011 CFR

2011-10-01

..., explosion or dangerous evolution of heat (i.e., an amount of heat sufficient to be dangerous to packaging or...; (ii) The routine operation of a seal, pump, compressor, or valve; or (iii) Connection or disconnection...

Conserved Proteins of the RNA Interference System in the Arbuscular Mycorrhizal Fungus Rhizoglomus irregulare Provide New Insight into the Evolutionary History of Glomeromycota.

PubMed

Lee, Soon-Jae; Kong, Mengxuan; Harrison, Paul; Hijri, Mohamed

2018-01-01

Horizontal gene transfer (HGT) is an important mechanism in the evolution of many living organisms particularly in Prokaryotes where genes are frequently dispersed between taxa. Although, HGT has been reported in Eukaryotes, its accumulative effect and its frequency has been questioned. Arbuscular mycorrhizal fungi (AMF) are an early diverged fungal lineage belonging to phylum Glomeromycota, whose phylogenetic position is still under debate. The history of AMF and land plant symbiosis dates back to at least 460 Ma. However, Glomeromycota are estimated to have emerged much earlier than land plants. In this study, we surveyed genomic and transcriptomic data of the model arbuscular mycorrhizal fungus Rhizoglomus irregulare (synonym Rhizophagus irregularis) and its relatives to search for evidence of HGT that occurred during AMF evolution. Surprisingly, we found a signature of putative HGT of class I ribonuclease III protein-coding genes that occurred from autotrophic cyanobacteria genomes to R. irregulare. At least one of two HGTs was conserved among AMF species with high levels of sequence similarity. Previously, an example of intimate symbiosis between AM fungus and cyanobacteria was reported in the literature. Ribonuclease III family enzymes are important in small RNA regulation in Fungi together with two additional core proteins (Argonaute/piwi and RdRP). The eukaryotic RNA interference system found in AMF was conserved and showed homology with high sequence similarity in Mucoromycotina, a group of fungi closely related to Glomeromycota. Prior to this analysis, class I ribonuclease III has not been identified in any eukaryotes. Our results indicate that a unique acquisition of class I ribonuclease III in AMF is due to a HGT event that occurred from cyanobacteria to Glomeromycota, at the latest before the divergence of the two Glomeromycota orders Diversisporales and Glomerales. © The Author(s) 2018. Published by Oxford University Press on behalf of the Society for Molecular Biology and Evolution.

Formation of Complex Amino Acid Precursors in Simulated Primitive Atmosphere and Their Alteration under Simulated Submarine Hydrothermal Conditions

NASA Astrophysics Data System (ADS)

Kobayashi, Kensei; Kurihara, Hironari; Hirako, Tomoaki; Obayashi, Yumiko; Kaneko, Takeo; Takano, Yoshinori; Yoshimura, Yoshitaka

Since late 1970's a great number of submarine hydrothermal systems (SHSs) has been dis-covered, and they are considered possible sites of chemical evolution and generation of life on the Earth since their discovery in late 1970s. A number of experiments simulating the con-ditions of SHSs were conducted, and abiotic production and polymerization of amino acids were reported. Free amino acids were frequently used as starting materials to examine possible organic reactions in the simulation experiments. In our early studies, not free amino acids but complex amino acids precursors with large molecular weights were formed abiotically from simulated primitive Earth atmosphere (a mixture of CO, N2 and H2 O) (Takano et al., 2004). Such complex organics (hereafter referred as to CNWs) should have been delivered to SHSs in Primitive Ocean, where they were subjected to further alteration. We examined possible alteration of the complex organics in high-temperature high-pressure environments by the su-percritical water flow reactor (SCWFR) (Islam et al.. 2003) and an autoclave. CNWs were quite hydrophilic compounds whose molecular weights were ca. 3000. After heating 573 K for 2 min in the SCWFR, aggregates of organics were formed, which were separated from aque-ous solution with a Nucleopore filter (pore size: 200 nm). We propose the following scenario of chemical evolution: (1) Complex organics including amino acid precursors were formed in primitive atmosphere and/or extraterrestrial environments, (ii) they were delivered to primor-dial SHSs, (iii) hydrothermal alteration occurred in SHSs to give organic aggregates, (iv) quite primitive molecular systems with subtle biological functions were generated in the competition among such aggregates. References: Islam, Md. N., Kaneko, T., and Kobayashi, K (2003). Reactions of Amino Acids with a Newly ConstructedSupercritical Water Flow Reactor Simulating Submarine Hydrothermal Systems. Bull. Chem. Soc. Jpn., 76, 1171. Takano, Y., Marumo, K., Yabashi, S., Kaneko, T., and Kobayashi, K., (2004). Curie-Point Pyrolysis of Complex Organics Simulated by Cosmic Rays Irradiation of Simple Inorganic Gas Mixture. Appl Phys. Lett., 85, 1633.

Crack initiation and potential hot-spot formation around a cylindrical defect under dynamic compression

NASA Astrophysics Data System (ADS)

Ma, Xiao; Li, Xinguo; Zheng, Xianxu; Li, Kewu; Hu, Qiushi; Li, Jianling

2017-11-01

In recent decades, the hot-spot theory of condensed-phase explosives has been a compelling focus of scientific investigation attracting many researchers. The defect in the polymeric binder of the polymer-bonded explosive is called the intergranular defect. In this study, the real polymeric binder was substituted by poly(methyl methacrylate) (PMMA) as it is transparent and has similar thermodynamic properties to some binders. A set of modified split Hopkinson pressure bars equipped with a time-resolved shadowgraph was used to study the process of crack initiation and potential hot-spot formation around a cylindrical defect in PMMA. The new and significant phenomenon that the opening-mode crack emerged earlier than the shearing-mode crack from the cylindrical defect has been published for the first time in this paper. Furthermore, a two-dimensional numerical simulation was performed to show the evolution of both the stress field and the temperature field. The simulation results were in good agreement with the experiment. Finally, the law of potential hot-spot formation is discussed in detail.

Investigation of the Evolution of Crystal Size and Shape during Temperature Cycling and in the Presence of a Polymeric Additive Using Combined Process Analytical Technologies

PubMed Central

2017-01-01

Crystal size and shape can be manipulated to enhance the qualities of the final product. In this work the steady-state shape and size of succinic acid crystals, with and without a polymeric additive (Pluronic P123) at 350 mL, scale is reported. The effect of the amplitude of cycles as well as the heating/cooling rates is described, and convergent cycling (direct nucleation control) is compared to static cycling. The results show that the shape of succinic acid crystals changes from plate- to diamond-like after multiple cycling steps, and that the time required for this morphology change to occur is strongly related to the type of cycling. Addition of the polymer is shown to affect both the final shape of the crystals and the time needed to reach size and shape steady-state conditions. It is shown how this phenomenon can be used to improve the design of the crystallization step in order to achieve more efficient downstream operations and, in general, to help optimize the whole manufacturing process. PMID:28867966

Red cell substitutes.

PubMed

Winslow, Robert M

2007-01-01

Oxygen-carrying plasma expanders (blood substitutes) have been sought for over a century. Development of current products is a result of evolution in the understanding of proteins in general, of hemoglobin in particular, and of how cell-free hemoglobin interacts with the control of local blood flow to ensure adequate tissue oxygenation. Hemoglobin-based products are considered in four "generations" corresponding to major improvements. First-generation products consisted of hemoglobin, freed of red cell membranes (stroma-free hemoglobin [SFH]), which was renal toxic and vasoactive. Second-generation products were polymerized with aldehyde reagents to reduce or eliminate the renal toxicity, but the products were heterogeneous and still vasoactive. Third-generation products employed more specific intramolecular crosslinking to eliminate polymerization and promote homogeneity, but they also remained vasoactive. Fourth-generation products are based on a new understanding of the way in which microvascular blood flow is controlled and the influence of O(2) delivery to vascular walls. After more than a century of research, one of these new solutions should find use as an alternative to red cells for transfusion in certain clinical settings.

Coherent photoluminescence excitation spectroscopy of semicrystalline polymeric semiconductors

NASA Astrophysics Data System (ADS)

Silva, Carlos; Grégoire, Pascal; Thouin, Félix

In polymeric semiconductors, the competition between through-bond (intrachain) and through-space (interchain) electronic coupling determines two-dimensional spatial coherence of excitons. The balance of intra- and interchain excitonic coupling depends very sensitively on solid-state microstructure of the polymer film (polycrystalline, semicrystalline with amorphous domains, etc.). Regioregular poly(3-hexylthiophene) has emerged as a model material because its photoluminescence (PL) spectral lineshape reveals intricate information on the magnitude of excitonic coupling, the extent of energetic disorder, and on the extent to which the disordered energy landscape is correlated. I discuss implementation of coherent two-dimensional electronic spectroscopy. We identify cross peaks between 0-0 and 0-1 excitation peaks, and we measure their time evolution, which we interpret within the context of a hybrid HJ aggregate model. By measurement of the homogeneous linewidth in diverse polymer microstructures, we address the nature of optical transitions within such hynbrid aggregate model. These depend strongly on sample processing, and I discuss the relationship between microstructure, steady-state absorption and PL spectral lineshape, and 2D coherent PL excitation spectral lineshapes.

Theoretical Model for Cellular Shapes Driven by Protrusive and Adhesive Forces

PubMed Central

Kabaso, Doron; Shlomovitz, Roie; Schloen, Kathrin; Stradal, Theresia; Gov, Nir S.

2011-01-01

The forces that arise from the actin cytoskeleton play a crucial role in determining the cell shape. These include protrusive forces due to actin polymerization and adhesion to the external matrix. We present here a theoretical model for the cellular shapes resulting from the feedback between the membrane shape and the forces acting on the membrane, mediated by curvature-sensitive membrane complexes of a convex shape. In previous theoretical studies we have investigated the regimes of linear instability where spontaneous formation of cellular protrusions is initiated. Here we calculate the evolution of a two dimensional cell contour beyond the linear regime and determine the final steady-state shapes arising within the model. We find that shapes driven by adhesion or by actin polymerization (lamellipodia) have very different morphologies, as observed in cells. Furthermore, we find that as the strength of the protrusive forces diminish, the system approaches a stabilization of a periodic pattern of protrusions. This result can provide an explanation for a number of puzzling experimental observations regarding cellular shape dependence on the properties of the extra-cellular matrix. PMID:21573201

Super-enhanced particle nucleation in styrene emulsion polymerization in the presence of sodium styrene sulfonate.

PubMed

Farias-Cepeda, Lorena; Herrera-Ordonez, Jorge; Hernandez-Martinez, Angel R; Estevez, Miriam; Rosales-Marines, Lucero

2017-08-15

The styrene (St) emulsion polymerization using Aerosol MA80 as surfactant and in the presence of sodium styrene sulfonate (NaSS) was studied. The effect of NaSS content was assessed using MA80 concentrations below and at the critical micellar concentration. It was found that at the higher NaSS and MA80 contents, the number of particles (N) reaches a maximum of the order of 10 17 particles/cm 3 water, a huge value that has never been reported. In this work an explanation for this super-enhanced particle nucleation phenomenon is proposed. Such hypothesis is based on the role of St-NaSS oligomers formed in the aqueous phase and their synergy with MA80 molecules to provide colloidal stability to the system. The proposal seems to be consistent with the experimental data obtained for the evolution of monomer conversion, N, particles size distribution and the wideness of this latter as well as with a theoretical estimation of the N. Copyright © 2017 Elsevier Inc. All rights reserved.

Polymerization and Structure of Bio-Based Plastics: A Computer Simulation

NASA Astrophysics Data System (ADS)

Khot, Shrikant N.; Wool, Richard P.

2001-03-01

We recently examined several hundred chemical pathways to convert chemically functionalized plant oil triglycerides, monoglycerides and reactive diluents into high performance plastics with a broad range of properties (US Patent No. 6,121,398). The resulting polymers had linear, branched, light- and highly-crosslinked chain architectures and could be used as pressure sensitive adhesives, elastomers and high performance rigid thermoset composite resins. To optimize the molecular design and minimize the number of chemical trials in this system with excess degrees of freedom, we developed a computer simulation of the free radical polymerization process. The triglyceride structure, degree of chemical substitution, mole fractions, fatty acid distribution function, and reaction kinetic parameters were used as initial inputs on a 3d lattice simulation. The evolution of the network fractal structure was computed and used to measure crosslink density, dangling ends, degree of reaction and defects in the lattice. The molecular connectivity was used to determine strength via a vector percolation model of fracture. The simulation permitted the optimal design of new bio-based materials with respect to monomer selection, cure reaction conditions and desired properties. Supported by the National Science Foundation

Plant-bacterial pathogen interactions mediated by type III effectors.

PubMed

Feng, Feng; Zhou, Jian-Min

2012-08-01

Effectors secreted by the bacterial type III system play a central role in the interaction between Gram-negative bacterial pathogens and their host plants. Recent advances in the effector studies have helped cementing several key concepts concerning bacterial pathogenesis, plant immunity, and plant-pathogen co-evolution. Type III effectors use a variety of biochemical mechanisms to target specific host proteins or DNA for pathogenesis. The identifications of their host targets led to the identification of novel components of plant innate immune system. Key modules of plant immune signaling pathways such as immune receptor complexes and MAPK cascades have emerged as a major battle ground for host-pathogen adaptation. These modules are attacked by multiple type III effectors, and some components of these modules have evolved to actively sense the effectors and trigger immunity. Copyright © 2012 Elsevier Ltd. All rights reserved.

Studying the evolution of a type III radio from the Sun up to 1 AU

NASA Astrophysics Data System (ADS)

Mann, Gottfried; Breitling, Frank; Vocks, Christian; Fallows, Richard; Melnik, Valentin; Konovalenko, Alexander

2017-04-01

On March 16, 2016, a type III burst was observed with the ground-based radio telescopes LOFAR and URAN-2 as well as with the radiospectrometer aboard the spacecraft WIND.It started at 80 MHz at 06:37 UT and reached 50 kHz after 23 minutes. A type III burst are considered as the radio signature of an electron beam travelling from the corona into the interplanetary space. The energetic electrons carrying the beam excites Langmuir waves, which convert into radio waves by wave-particle interaction. The relationship between the drift rate and the frequency as derived from the dynamic radio spectra reveals that the velocity of the electrons generating the radio waves of the type III burst is increasing with increasing distance from the center of the Sun.

Clinical factors that affect perceived quality of life in arthroscopic reconstruction for acromioclavicular joint dislocation.

PubMed

Abat, F; Gich, I; Natera, L; Besalduch, M; Sarasquete, J

To analyse the results of arthroscopic repair of acromioclavicular dislocation in terms of health-related quality of life. Prospective study of patients with acromioclavicular dislocation Rockwood grade iii-v, treated arthroscopically with a mean follow up of 25.4 months. The demographics of the series were recorded and evaluations were performed preoperatively, at 3 months and 2 years with validated questionnaires as Short Form-36 Health Survey (SF-36), visual analogue scale (VAS), The Disabilities of the Arm, Shoulder and Hand (DASH), Constant-Murley Shoulder Outcome Score (Constant) and Walch-Duplay Score (WD). Twenty patients, 17 men and 3 women with a mean age of 36.1 years, were analysed. According to the classification of Rockwood, 3 patients were grade iii, 3 grade iv and 14 grade v. Functional and clinical improvement was detected in all clinical tests (SF-36, VAS and DASH) at 3 months and 2 years follow up (P<.001). The final Constant score was 95.3±2.4 and the WD was 1.8±0.62. It was not found that the health-related quality of life was affected by any variable studied except the evolution of DASH. The health-related quality of life (assessed by SF-36) in patients undergoing arthroscopic repair of acromioclavicular joint dislocation grades iii-v was not influenced by gender, age, grade, displacement, handedness, evolution of the VAS, scoring of the Constant or by the WD. However, it is correlated with the evolution in the DASH score. Copyright © 2017 SECOT. Publicado por Elsevier España, S.L.U. All rights reserved.

Evolution of the Cannabinoid and Terpene Content during the Growth of Cannabis sativa Plants from Different Chemotypes.

PubMed

Aizpurua-Olaizola, Oier; Soydaner, Umut; Öztürk, Ekin; Schibano, Daniele; Simsir, Yilmaz; Navarro, Patricia; Etxebarria, Nestor; Usobiaga, Aresatz

2016-02-26

The evolution of major cannabinoids and terpenes during the growth of Cannabis sativa plants was studied. In this work, seven different plants were selected: three each from chemotypes I and III and one from chemotype II. Fifty clones of each mother plant were grown indoors under controlled conditions. Every week, three plants from each variety were cut and dried, and the leaves and flowers were analyzed separately. Eight major cannabinoids were analyzed via HPLC-DAD, and 28 terpenes were quantified using GC-FID and verified via GC-MS. The chemotypes of the plants, as defined by the tetrahydrocannabinolic acid/cannabidiolic acid (THCA/CBDA) ratio, were clear from the beginning and stable during growth. The concentrations of the major cannabinoids and terpenes were determined, and different patterns were found among the chemotypes. In particular, the plants from chemotypes II and III needed more time to reach peak production of THCA, CBDA, and monoterpenes. Differences in the cannabigerolic acid development among the different chemotypes and between monoterpene and sesquiterpene evolution patterns were also observed. Plants of different chemotypes were clearly differentiated by their terpene content, and characteristic terpenes of each chemotype were identified.

The Luminosity Function and Star Formation Rate between Redshifts of 0.07 and 1.47 for Narrowband Emitters in the Subaru Deep Field

NASA Astrophysics Data System (ADS)

Ly, Chun; Malkan, Matt A.; Kashikawa, Nobunari; Shimasaku, Kazuhiro; Doi, Mamoru; Nagao, Tohru; Iye, Masanori; Kodama, Tadayuki; Morokuma, Tomoki; Motohara, Kentaro

2007-03-01

SDF line-emitting galaxies in four narrowband filters at low and intermediate redshifts are presented. Broadband colors, follow-up optical spectroscopy, and multiple NB filters are used to distinguish Hα, [O II], and [O III] emitters at z=0.07-1.47 to construct their LFs. These LFs are derived down to faint magnitudes, allowing for an accurate determination of the faint-end slope. With a large (N~200-900) sample for each redshift interval, a Schechter profile is fitted to each LF. Prior to dust extinction corrections, the [O III] and [O II] LFs agree reasonably well with those of Hippelein et al. The z=0.08 Hα LF, which reaches 2 orders of magnitude fainter than Gallego et al., is steeper by 25%. This indicates that there are more low-luminosity star-forming galaxies for z<0.1. The faint-end slope α and φ* show a strong redshift evolution, while L* shows little evolution. The evolution in α indicates that low-luminosity galaxies have a stronger evolution compared to brighter ones. Integrated SFR densities are derived via Hα, [O III], and [O II] for 0.071, the SFR densities are similar. The latter is consistent with previous UV and [O II] measurements. Below z<0.4, the SFR densities are consistent with several Hα, [O II], and UV measurements, but others are a factor of 2 higher. For example, the z=0.066-0.092 LF agrees with Jones & Bland-Hawthorn, but at z=0.24 and 0.40, their number densities are twice as high. This discrepancy can be explained by cosmic variance. Based in part on data collected at Subaru Telescope, which is operated by the National Astronomical Observatory of Japan.

History of the Diet History Questionnaire (DHQ) | EGRP/DCCPS/NCI/NIH

Cancer.gov

Learn about the evolution of the Diet History Questionnaire (DHQ), developed by the National Cancer Institute (NCI) initially in 2001, to the DHQ II in 2010, up to the present version, DHQ III, launched in 2018.

Following the Cosmic Evolution of Pristine Gas. I. Implications for Milky Way Halo Stars

NASA Astrophysics Data System (ADS)

Sarmento, Richard; Scannapieco, Evan; Pan, Liubin

2017-01-01

We make use of a new subgrid model of turbulent mixing to accurately follow the cosmological evolution of the first stars, the mixing of their supernova (SN) ejecta, and the impact on the chemical composition of the Galactic Halo. Using the cosmological adaptive mesh refinement code ramses, we implement a model for the pollution of pristine gas as described in Pan et al. Tracking the metallicity of Pop III stars with metallicities below a critical value allows us to account for the fraction of Z< {Z}{crit} stars formed even in regions in which the gas’s average metallicity is well above {Z}{crit}. We demonstrate that such partially mixed regions account for 0.5 to 0.7 of all Pop III stars formed up to z = 5. Additionally, we track the creation and transport of “primordial metals” (PM) generated by Pop III SNe. These neutron-capture deficient metals are taken up by second-generation stars and likely lead to unique abundance signatures characteristic of carbon-enhanced, metal-poor (CEMP-no) stars. As an illustrative example, we associate primordial metals with abundance ratios used by Keller et al. to explain the source of metals in the star SMSS J031300.36-670839.3, finding good agreement with the observed [Fe/H], [C/H], [O/H], and [Mg/Ca] ratios in CEMP-no Milky Way halo stars. Similar future simulations will aid in further constraining the properties of Pop III stars using CEMP observations, as well as improve predictions of the spatial distribution of Pop III stars, as will be explored by the next generation of ground- and space-based telescopes.

The Eleventh and Twelfth Data Releases of the Sloan Digital Sky Survey: Final Data from SDSS-III

NASA Astrophysics Data System (ADS)

Alam, Shadab; Albareti, Franco D.; Allende Prieto, Carlos; Anders, F.; Anderson, Scott F.; Anderton, Timothy; Andrews, Brett H.; Armengaud, Eric; Aubourg, Éric; Bailey, Stephen; Basu, Sarbani; Bautista, Julian E.; Beaton, Rachael L.; Beers, Timothy C.; Bender, Chad F.; Berlind, Andreas A.; Beutler, Florian; Bhardwaj, Vaishali; Bird, Jonathan C.; Bizyaev, Dmitry; Blake, Cullen H.; Blanton, Michael R.; Blomqvist, Michael; Bochanski, John J.; Bolton, Adam S.; Bovy, Jo; Shelden Bradley, A.; Brandt, W. N.; Brauer, D. E.; Brinkmann, J.; Brown, Peter J.; Brownstein, Joel R.; Burden, Angela; Burtin, Etienne; Busca, Nicolás G.; Cai, Zheng; Capozzi, Diego; Carnero Rosell, Aurelio; Carr, Michael A.; Carrera, Ricardo; Chambers, K. C.; Chaplin, William James; Chen, Yen-Chi; Chiappini, Cristina; Chojnowski, S. Drew; Chuang, Chia-Hsun; Clerc, Nicolas; Comparat, Johan; Covey, Kevin; Croft, Rupert A. C.; Cuesta, Antonio J.; Cunha, Katia; da Costa, Luiz N.; Da Rio, Nicola; Davenport, James R. A.; Dawson, Kyle S.; De Lee, Nathan; Delubac, Timothée; Deshpande, Rohit; Dhital, Saurav; Dutra-Ferreira, Letícia; Dwelly, Tom; Ealet, Anne; Ebelke, Garrett L.; Edmondson, Edward M.; Eisenstein, Daniel J.; Ellsworth, Tristan; Elsworth, Yvonne; Epstein, Courtney R.; Eracleous, Michael; Escoffier, Stephanie; Esposito, Massimiliano; Evans, Michael L.; Fan, Xiaohui; Fernández-Alvar, Emma; Feuillet, Diane; Filiz Ak, Nurten; Finley, Hayley; Finoguenov, Alexis; Flaherty, Kevin; Fleming, Scott W.; Font-Ribera, Andreu; Foster, Jonathan; Frinchaboy, Peter M.; Galbraith-Frew, J. G.; García, Rafael A.; García-Hernández, D. A.; García Pérez, Ana E.; Gaulme, Patrick; Ge, Jian; Génova-Santos, R.; Georgakakis, A.; Ghezzi, Luan; Gillespie, Bruce A.; Girardi, Léo; Goddard, Daniel; Gontcho, Satya Gontcho A.; González Hernández, Jonay I.; Grebel, Eva K.; Green, Paul J.; Grieb, Jan Niklas; Grieves, Nolan; Gunn, James E.; Guo, Hong; Harding, Paul; Hasselquist, Sten; Hawley, Suzanne L.; Hayden, Michael; Hearty, Fred R.; Hekker, Saskia; Ho, Shirley; Hogg, David W.; Holley-Bockelmann, Kelly; Holtzman, Jon A.; Honscheid, Klaus; Huber, Daniel; Huehnerhoff, Joseph; Ivans, Inese I.; Jiang, Linhua; Johnson, Jennifer A.; Kinemuchi, Karen; Kirkby, David; Kitaura, Francisco; Klaene, Mark A.; Knapp, Gillian R.; Kneib, Jean-Paul; Koenig, Xavier P.; Lam, Charles R.; Lan, Ting-Wen; Lang, Dustin; Laurent, Pierre; Le Goff, Jean-Marc; Leauthaud, Alexie; Lee, Khee-Gan; Lee, Young Sun; Licquia, Timothy C.; Liu, Jian; Long, Daniel C.; López-Corredoira, Martín; Lorenzo-Oliveira, Diego; Lucatello, Sara; Lundgren, Britt; Lupton, Robert H.; Mack, Claude E., III; Mahadevan, Suvrath; Maia, Marcio A. G.; Majewski, Steven R.; Malanushenko, Elena; Malanushenko, Viktor; Manchado, A.; Manera, Marc; Mao, Qingqing; Maraston, Claudia; Marchwinski, Robert C.; Margala, Daniel; Martell, Sarah L.; Martig, Marie; Masters, Karen L.; Mathur, Savita; McBride, Cameron K.; McGehee, Peregrine M.; McGreer, Ian D.; McMahon, Richard G.; Ménard, Brice; Menzel, Marie-Luise; Merloni, Andrea; Mészáros, Szabolcs; Miller, Adam A.; Miralda-Escudé, Jordi; Miyatake, Hironao; Montero-Dorta, Antonio D.; More, Surhud; Morganson, Eric; Morice-Atkinson, Xan; Morrison, Heather L.; Mosser, Benôit; Muna, Demitri; Myers, Adam D.; Nandra, Kirpal; Newman, Jeffrey A.; Neyrinck, Mark; Nguyen, Duy Cuong; Nichol, Robert C.; Nidever, David L.; Noterdaeme, Pasquier; Nuza, Sebastián E.; O'Connell, Julia E.; O'Connell, Robert W.; O'Connell, Ross; Ogando, Ricardo L. C.; Olmstead, Matthew D.; Oravetz, Audrey E.; Oravetz, Daniel J.; Osumi, Keisuke; Owen, Russell; Padgett, Deborah L.; Padmanabhan, Nikhil; Paegert, Martin; Palanque-Delabrouille, Nathalie; Pan, Kaike; Parejko, John K.; Pâris, Isabelle; Park, Changbom; Pattarakijwanich, Petchara; Pellejero-Ibanez, M.; Pepper, Joshua; Percival, Will J.; Pérez-Fournon, Ismael; P´rez-Ra`fols, Ignasi; Petitjean, Patrick; Pieri, Matthew M.; Pinsonneault, Marc H.; Porto de Mello, Gustavo F.; Prada, Francisco; Prakash, Abhishek; Price-Whelan, Adrian M.; Protopapas, Pavlos; Raddick, M. Jordan; Rahman, Mubdi; Reid, Beth A.; Rich, James; Rix, Hans-Walter; Robin, Annie C.; Rockosi, Constance M.; Rodrigues, Thaíse S.; Rodríguez-Torres, Sergio; Roe, Natalie A.; Ross, Ashley J.; Ross, Nicholas P.; Rossi, Graziano; Ruan, John J.; Rubiño-Martín, J. A.; Rykoff, Eli S.; Salazar-Albornoz, Salvador; Salvato, Mara; Samushia, Lado; Sánchez, Ariel G.; Santiago, Basílio; Sayres, Conor; Schiavon, Ricardo P.; Schlegel, David J.; Schmidt, Sarah J.; Schneider, Donald P.; Schultheis, Mathias; Schwope, Axel D.; Scóccola, C. G.; Scott, Caroline; Sellgren, Kris; Seo, Hee-Jong; Serenelli, Aldo; Shane, Neville; Shen, Yue; Shetrone, Matthew; Shu, Yiping; Silva Aguirre, V.; Sivarani, Thirupathi; Skrutskie, M. F.; Slosar, Anže; Smith, Verne V.; Sobreira, Flávia; Souto, Diogo; Stassun, Keivan G.; Steinmetz, Matthias; Stello, Dennis; Strauss, Michael A.; Streblyanska, Alina; Suzuki, Nao; Swanson, Molly E. C.; Tan, Jonathan C.; Tayar, Jamie; Terrien, Ryan C.; Thakar, Aniruddha R.; Thomas, Daniel; Thomas, Neil; Thompson, Benjamin A.; Tinker, Jeremy L.; Tojeiro, Rita; Troup, Nicholas W.; Vargas-Magaña, Mariana; Vazquez, Jose A.; Verde, Licia; Viel, Matteo; Vogt, Nicole P.; Wake, David A.; Wang, Ji; Weaver, Benjamin A.; Weinberg, David H.; Weiner, Benjamin J.; White, Martin; Wilson, John C.; Wisniewski, John P.; Wood-Vasey, W. M.; Ye`che, Christophe; York, Donald G.; Zakamska, Nadia L.; Zamora, O.; Zasowski, Gail; Zehavi, Idit; Zhao, Gong-Bo; Zheng, Zheng; Zhou, Xu; Zhou, Zhimin; Zou, Hu; Zhu, Guangtun

2015-07-01

The third generation of the Sloan Digital Sky Survey (SDSS-III) took data from 2008 to 2014 using the original SDSS wide-field imager, the original and an upgraded multi-object fiber-fed optical spectrograph, a new near-infrared high-resolution spectrograph, and a novel optical interferometer. All of the data from SDSS-III are now made public. In particular, this paper describes Data Release 11 (DR11) including all data acquired through 2013 July, and Data Release 12 (DR12) adding data acquired through 2014 July (including all data included in previous data releases), marking the end of SDSS-III observing. Relative to our previous public release (DR10), DR12 adds one million new spectra of galaxies and quasars from the Baryon Oscillation Spectroscopic Survey (BOSS) over an additional 3000 deg2 of sky, more than triples the number of H-band spectra of stars as part of the Apache Point Observatory (APO) Galactic Evolution Experiment (APOGEE), and includes repeated accurate radial velocity measurements of 5500 stars from the Multi-object APO Radial Velocity Exoplanet Large-area Survey (MARVELS). The APOGEE outputs now include the measured abundances of 15 different elements for each star. In total, SDSS-III added 5200 deg2 of ugriz imaging; 155,520 spectra of 138,099 stars as part of the Sloan Exploration of Galactic Understanding and Evolution 2 (SEGUE-2) survey; 2,497,484 BOSS spectra of 1,372,737 galaxies, 294,512 quasars, and 247,216 stars over 9376 deg2; 618,080 APOGEE spectra of 156,593 stars; and 197,040 MARVELS spectra of 5513 stars. Since its first light in 1998, SDSS has imaged over 1/3 of the Celestial sphere in five bands and obtained over five million astronomical spectra.

Ion transfer through solvent polymeric membranes driven by an exponential current flux.

PubMed

Molina, A; Torralba, E; González, J; Serna, C; Ortuño, J A

2011-03-21

General analytical equations which govern ion transfer through liquid membranes with one and two polarized interfaces driven by an exponential current flux are derived. Expressions for the transient and stationary E-t, dt/dE-E and dI/dE-E curves are obtained, and the evolution from transient to steady behaviour has been analyzed in depth. We have also shown mathematically that the voltammetric and stationary chronopotentiometric I(N)-E curves are identical (with E being the applied potential for voltammetric techniques and the measured potential for chronopotentiometric techniques), and hence, their derivatives provide identical information.

Organic compounds in the Murchison meteorite.

NASA Technical Reports Server (NTRS)

Ponnamperuma, C.

1972-01-01

Impressive supporting evidence for the concept of the chemical evolution of life has appeared in the discovery of biologically important compounds in extraterrestrial samples. The approaches pursued to detect extraterrestrial organic compounds include the study of interstellar space by radioastronomy, the evaluation of the Apollo lunar samples, and the analysis of meteorites, both ancient and recent. It has been found that the clouds of gas in the interstellar medium contain a wide variety of molecules, most of which are organic in nature. The carbonaceous chondrites contain polymeric organic matter. Amino acids have been detected in the Murchison meteorite.

Polymerization of amino acids under primitive earth conditions.

NASA Technical Reports Server (NTRS)

Flores, J. J.; Ponnamperuma, C.

1972-01-01

Small amounts of peptides were obtained when equal amounts of methane and ammonia were reacted with vaporized aqueous solutions of C14-labeled glycine, L-alanine, L-aspartic acid, L-glutamic acid and L-threonine in the presence of a continuous spark discharge in a 24-hr cyclic process. The experiment was designed to demonstrate the possibility of peptide synthesis under simulated primeval earth conditions. It is theorized that some dehydration-condensation processes may have taken place, with ammonium cyanide, the hydrogencyanide tetramer or aminonitriles as intermediate products, during the early chemical evolution of the earth.

Symposium on Rechargeable Lithium Batteries, Hollywood, FL, Oct. 19-24, 1989, Proceedings

NASA Technical Reports Server (NTRS)

Subbarao, S. (Editor); Koch, V. R. (Editor); Owens, B. B. (Editor); Smyrl, W. H. (Editor)

1990-01-01

Recent advances in the technology and applications of rechargeable Li cells are discussed in reviews and reports. A general overview of the field is provided, and sections are devoted to organic electrolyte systems, polymeric electrolyte systems, inorganic electrolytes systems, and molten-salt electrolytes. Particular attention is given to electrolyte stabilization, the effects of organic additives on electrolyte performance, a cycle-life sensor, consumer-product applications, in situ measurements of gas evolution in Li secondary cells, ultrathin polymer cathodes, electrochemical growth of conducting polymers, and sealing Li/FeS(x) cells for a bipolar battery.

The role of metal ions in chemical evolution - Polymerization of alanine and glycine in a cation-exchanged clay environment

NASA Technical Reports Server (NTRS)

Lawless, J. G.; Levi, N.

1979-01-01

The effect of the exchangeable cation on the condensation of glycine and alanine was investigated using a series of homoionic bentonites. A cycling procedure of drying, warming and wetting was employed. Peptide bond formation was observed, and the effectiveness of metal ions to catalyze the condensation was Cu(2+) greater than Ni(2) approximately equals Zn(2+) greater than Na(+). Glycine showed 6% of the monomer incorporated into oligomers with the largest detected being the pentamer. Alanine showed less peptide bond formation (a maximum of 2%) and only the dimer was observed.

The controlled preparation of polypyrrole nanostructures via tuning the concentration of acrylic acid.

PubMed

Wang, Yujie; Zhong, Wenbin; Ning, Xutao; Li, Yuntao; Chen, Xiaohua; Wang, Yongxin; Yang, Wantai

2013-03-01

Two types of nanostructures, nanowires and nanoribbons were prepared with polypyrrole (PPy) by controlling the concentration of acrylic acid (AA) in systems containing cationic surfactant, cetyltrimethylammonium bromide (CTAB) at about 12 degrees C. The effect of reaction conditions involving the concentration of AA, CTAB, pyrrole as well as the reaction temperature was systematically studied on the final structures of prepared PPy. The results revealed that the polymerization of AA, resulting in PAA, played a key role in the evolution of PPy nanostructures. A possible mechanism was briefly discussed on the formation of these two nanostructures, nanowires and nanoribbons.

Interaction between a recombinant prion protein and organo-mineral complexes as evidenced by CPMAS 13C-NMR

NASA Astrophysics Data System (ADS)

Russo, F.; Scotti, R.; Gianfreda, L.; Conte, P.; Rao, M. A.

2009-04-01

Prion proteins (PrP) are the main responsible for Transmissible Spongiform Encephalopathies (TSE). The TSE etiological agent is a misfolded form of the normal cellular prion protein. The amyloidal aggregates accumulated in the brain of infected animals and mainly composed of PrPSc exhibit resistance to protease attack and many conventional inactivating procedures. The prion protein diseases cause an environmental issue because the environment and in particular the soil compartment can be contaminated and then become a potential reservoir and diffuser of TSEs infectivity as a consequence of (i) accidental dispersion from storage plants of meat and bone meal, (ii) incorporation of contaminated material in fertilizers, (iii) possible natural contamination of pasture soils by grazing herds, and (v) burial of carcasses. The environmental problem can be even more relevant because very low amounts of PrPSc are able to propagate the disease. Several studies evidenced that infectious prion protein remains active in soils for years. Contaminated soils result, thus, a possible critical route of TSE transmission in wild animals. Soil can also protect prion protein toward degradation processes due to the presence of humic substances and inorganic components such as clays. Mineral and organic colloids and the more common association between clay minerals and humic substances can contribute to the adsorption/entrapment of molecules and macromolecules. The polymerization of organic monomeric humic precursors occurring in soil in the presence of oxidative enzymes or manganese and iron oxides, is considered one of the most important processes contributing to the formation of humic substances. The process is very fast and produces a population of polymeric products of different molecular structures, sizes, shapes and complexity. Other molecules and possibly biomacromolecules such as proteins may be involved. The aim of the present work was to study by CPMAS 13C-NMR the interactions between a non pathogenic ovine recombinant prion protein and a model soil system represented by a manganese oxide in the form of birnessite (δ-MnO2), coated with a polymerized catechol. To better understand the effect of the polymerization process, PrP was added to the birnessite-cathecol system either before or after the polymerization processes. The NMR spectra of the prion protein interacting directly with birnessite revealed disappearance of the signals due to the paramagnetic nature of manganese oxide or abiotic degradation. Conversely, the signal pattern of the protein re-appeared as it is mixed to the soil-like system either during or after the catechol polymerization process. Results suggested that the possible interactions of the prion protein on soil systems can be mediated by natural organic matter. However, deeper studies on more complex real soil systems are needed to definitely confirm such hypothesis.

Identification of sucrose synthase as an actin-binding protein

NASA Technical Reports Server (NTRS)

Winter, H.; Huber, J. L.; Huber, S. C.; Davies, E. (Principal Investigator)

1998-01-01

Several lines of evidence indicate that sucrose synthase (SuSy) binds both G- and F-actin: (i) presence of SuSy in the Triton X-100-insoluble fraction of microsomal membranes (i.e. crude cytoskeleton fraction); (ii) co-immunoprecipitation of actin with anti-SuSy monoclonal antibodies; (iii) association of SuSy with in situ phalloidin-stabilized F-actin filaments; and (iv) direct binding to F-actin, polymerized in vitro. Aldolase, well known to interact with F-actin, interfered with binding of SuSy, suggesting that a common or overlapping binding site may be involved. We postulate that some of the soluble SuSy in the cytosol may be associated with the actin cytoskeleton in vivo.

Impact of Na- and K-C pi-interactions on the structure and binding of M3(sol)n(BINOLate)3Ln catalysts.

PubMed

Wooten, Alfred J; Carroll, Patrick J; Walsh, Patrick J

2007-08-16

Shibasaki's heterobimetallic complexes M3(THF)n(BINOLate)3Ln [M = Li, Na, K; Ln = lanthanide(III)] are among the most successful asymmetric Lewis acid catalysts. Why does M3(THF)n(BINOLate)3Ln readily bind substrates when M = Li but not when M = Na or K? Structural studies herein indicate Na- and K-C cation-pi interactions and alkali metal radius may be more important than even lanthanide radius. Also reported is a novel polymeric [K3(THF)2(BINOLate)3Yb]n structure that provides the first evidence of interactions between M3(THF)n(BINOLate)3Ln complexes.

Synthesis and Adsorption Properties of 4-Vinylpyridine and Styrene Copolymer In Situ Immobilized on Silica Surface

NASA Astrophysics Data System (ADS)

Yanovska, E. S.; Vretik, L. O.; Nikolaeva, O. A.; Polonska, Y.; Sternik, D.; Kichkiruk, O. Yu.

2017-03-01

Copolymer of 4-vinylpyridine with styrene was in situ immobilized on silica gel surface via the heterogeneous radical polymerization. Anchorage of the copolymer on the surface layer was confirmed by IR spectroscopy. The quantity of copolymer on the silica gel surface was evaluated as 25.73 wt.% by TG and DSC-MS analysis. "Islet" location of polymer layer on the silica surface was confirmed by the scanning electron microscopy. A high adsorption activity of silica gel with immobilized copolymer towards microquantitatives of Cu(II), Cd(II), Pb(II), Fe(III), and Ni(II) ions in steady state conditions as well as of Ni(II) ions in dynamic regime was found.

Synthesis and Adsorption Properties of 4-Vinylpyridine and Styrene Copolymer In Situ Immobilized on Silica Surface.

PubMed

Yanovska, E S; Vretik, L O; Nikolaeva, O A; Polonska, Y; Sternik, D; Kichkiruk, O Yu

2017-12-01

Copolymer of 4-vinylpyridine with styrene was in situ immobilized on silica gel surface via the heterogeneous radical polymerization. Anchorage of the copolymer on the surface layer was confirmed by IR spectroscopy. The quantity of copolymer on the silica gel surface was evaluated as 25.73 wt.% by TG and DSC-MS analysis. "Islet" location of polymer layer on the silica surface was confirmed by the scanning electron microscopy. A high adsorption activity of silica gel with immobilized copolymer towards microquantitatives of Cu(II), Cd(II), Pb(II), Fe(III), and Ni(II) ions in steady state conditions as well as of Ni(II) ions in dynamic regime was found.

Impact of Na- and K-C π-Interactions on the Structure and Binding of M3(sol)n(BINOLate)3Ln Catalysts

PubMed Central

Wooten, Alfred J.; Carroll, Patrick J.; Walsh, Patrick J.

2008-01-01

Shibasaki’s heterobimetallic complexes M3(THF)n(BINOLate)3Ln [M = Li, Na, K, Ln = lanthanide(III)] are among the most successful asymmetric Lewis acid catalysts. Why does M3(THF)n(BINOLate)3Ln readily bind substrates when M = Li but not when M = Na or K? Structural studies herein indicate Na- and K-C cation-π interactions and alkali metal radius may be more important than even lanthanide radius. Also reported is a novel polymeric [K3(THF)2(BINOLate)3Yb]n structure that provides the first evidence of interactions between M3(THF)n(BINOLate)3Ln complexes. PMID:17658838

The mass distribution of Population III stars

NASA Astrophysics Data System (ADS)

Fraser, M.; Casey, A. R.; Gilmore, G.; Heger, A.; Chan, C.

2017-06-01

Extremely metal-poor (EMP) stars are uniquely informative on the nature of massive Population III stars. Modulo a few elements that vary with stellar evolution, the present-day photospheric abundances observed in EMP stars are representative of their natal gas cloud composition. For this reason, the chemistry of EMP stars closely reflects the nucleosynthetic yields of supernovae from massive Population III stars. Here we collate detailed abundances of 53 EMP stars from the literature and infer the masses of their Population III progenitors. We fit a simple initial mass function (IMF) to a subset of 29 of the inferred Population III star masses, and find that the mass distribution is well represented by a power-law IMF with exponent α = 2.35^{+0.29}_{-0.24}. The inferred maximum progenitor mass for supernovae from massive Population III stars is M_{max} = 87^{+13}_{-33} M⊙, and we find no evidence in our sample for a contribution from stars with masses above ˜120 M⊙. The minimum mass is strongly consistent with the theoretical lower mass limit for Population III supernovae. We conclude that the IMF for massive Population III stars is consistent with the IMF of present-day massive stars and there may well have formed stars much below the supernova mass limit that could have survived to the present day.

The Formation of Supermassive Black Holes from Population III.1 Seeds. I. Cosmic Formation Histories and Clustering Properties

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

Banik, Nilanjan; Tan, Jonathan C.; Monaco, Pierluigi

We calculate the cosmic distributions in space and time of the formation sites of the first, "Pop III.1" stars, exploring a model in which these are the progenitors of all supermassive black holes (SMBHs). Pop III.1 stars are defined to form from primordial composition gas in dark matter minihalos withmore » $$\\sim10^6\\:M_\\odot$$ that are isolated from neighboring astrophysical sources by a given isolation distance, $$d_{\\rm{iso}}$$. We assume Pop III.1 sources are seeds of SMBHs, based on protostellar support by dark matter annihilation heating that allows them to accrete a large fraction of their minihalo gas, i.e., $$\\sim 10^5\\:M_\\odot$$. Exploring $$d_{\\rm{iso}}$$ from 10--$$100\\:\\rm{kpc}$$ (proper distances), we predict the redshift evolution of Pop III.1 source and SMBH remnant number densities. The local, $z=0$ density of SMBHs constrains $$d_{\\rm{iso}}\\lesssim 100\\:\\rm{kpc}$$ (i.e., $$3\\:\\rm{Mpc}$$ comoving distance at $$z\\simeq30$$). In our simulated ($$\\sim60\\:\\rm{Mpc}$$)$^3$ comoving volume, Pop III.1 stars start forming just after $z=40$. Their formation is largely complete by $$z\\simeq25$$ to 20 for $$d_{\\rm{iso}}=100$$ to $$50\\:\\rm{kpc}$$. We follow source evolution to $z=10$, by which point most SMBHs reside in halos with $$\\gtrsim10^8\\:M_\\odot$$. Over this period, there is relatively limited merging of SMBHs for these values of $$d_{\\rm{iso}}$$. We also predict SMBH clustering properties at $z=10$$: feedback suppression of neighboring sources leads to relatively flat angular correlation functions. Finally, we consider a simple "Str\\"omgren" model for $$d_{\\rm iso}$, based on ionizing feedback from zero age main sequence supermassive Pop III.1 stars that may be the direct progenitors of SMBHs in this scenario. Such models naturally produce feedback effects on scales of $$\\sim100\\:$$kpc and thus self-consistently generate a SMBH number density similar to the observed value.« less

Membrane-based technologies for biogas separations.

PubMed

Basu, Subhankar; Khan, Asim L; Cano-Odena, Angels; Liu, Chunqing; Vankelecom, Ivo F J

2010-02-01

Over the past two decades, membrane processes have gained a lot of attention for the separation of gases. They have been found to be very suitable for wide scale applications owing to their reasonable cost, good selectivity and easily engineered modules. This critical review primarily focuses on the various aspects of membrane processes related to the separation of biogas, more in specific CO(2) and H(2)S removal from CH(4) and H(2) streams. Considering the limitations of inorganic materials for membranes, the present review will only focus on work done with polymeric materials. An overview on the performance of commercial membranes and lab-made membranes highlighting the problems associated with their applications will be given first. The development studies carried out to enhance the performance of membranes for gas separation will be discussed in the subsequent section. This review has been broadly divided into three sections (i) performance of commercial polymeric membranes (ii) performance of lab-made polymeric membranes and (iii) performance of mixed matrix membranes (MMMs) for gas separations. It will include structural modifications at polymer level, polymer blending, as well as synthesis of mixed matrix membranes, for which addition of silane-coupling agents and selection of suitable fillers will receive special attention. Apart from an overview of the different membrane materials, the study will also highlight the effects of different operating conditions that eventually decide the performance and longevity of membrane applications in gas separations. The discussion will be largely restricted to the studies carried out on polyimide (PI), cellulose acetate (CA), polysulfone (PSf) and polydimethyl siloxane (PDMS) membranes, as these membrane materials have been most widely used for commercial applications. Finally, the most important strategies that would ensure new commercial applications will be discussed (156 references).

Synthesis of Fe3O4 poly(styrene-glycidyl methacrylate) magnetic porous microspheres and application in the immobilization of Klebsiella sp. FD-3 to reduce Fe(III)EDTA in a NO(x) scrubbing solution.

PubMed

Wang, Xiaoyan; Zhou, Zuoming; Jing, Guohua

2013-02-01

Magnetic poly(styrene-glycidyl methacrylate) porous microspheres (MPPM) with high magnetic contents were prepared by surfactant reverse micelles and emulsion polymerization of monomers, in which the well-dispersed Fe(3)O(4) nanoparticles were modified by polyethylene glycol (PEG) and oleic acid (OA) respectively. The characterizations showed that both of the OA-MPPM and the PEG-MPPM were ferromagnetic, however, the OA-MPPM was used to immobilize the bacteria for more advantages. Therefore, the effects of monomer ratio, surfactant, crosslinker and amount of Fe(3)O(4) on the structure, morphology and magnetic contents of the OA-MPPM were investigated. Then, the OA-MPPM was utilized to immobilize Klebsiella sp. FD-3, an iron-reducing bacterium for Fe(III)EDTA reduction applied in NO(x) removal. Compared with free bacteria, the immobilized FD-3 showed a better tolerance to the unbeneficial pH and temperature conditions. Copyright © 2012 Elsevier Ltd. All rights reserved.

Photo-cured PMMA/PEI core/shell nanoparticles surface-modified with Gd-DTPA for T1 MR imaging.

PubMed

Ratanajanchai, Montri; Lee, Don Haeng; Sunintaboon, Panya; Yang, Su-Geun

2014-02-01

Herein, we introduced amine-functionalized core-shell nanoparticles (Polymethyl methacrylate/Polyethyleneimine; PMMA/PEI) with surface primary amines (3.15×10(5) groups/particle) and uniform size distribution (150-200nm) that were prepared by one-step photo-induced emulsion polymerization. Further PEI-surface was modified with diethylenetriamine pentaacetic acid (DTPA) and introduced with Gd(III). The modified particles possessing DTPA can entrap a high content of Gd(III) ions of over 5.5×10(4)Gd/particle with stable chelation (no release of free Gd) at least 7h. The Gd-DTPA-conjugated core-shell nanoparticles (PMMA/PEI-DTPA-Gd NPs) enhanced the MRI intensity more than Primovist (a commercial hepatic contrast agent). Moreover, the PMMA/PEI-DTPA-Gd NPs showed non-cytotoxicity up to 250μM in normal liver cells. Thus, in vitro data suggested the PMMA/PEI-DTPA-Gd NPs is promising delivery system as a superior MRI contrast agent, especially for hepatic lesion targeted MR imaging. Copyright © 2013 Elsevier Inc. All rights reserved.

An immuno-wall microdevice exhibits rapid and sensitive detection of IDH1-R132H mutation specific to grade II and III gliomas

NASA Astrophysics Data System (ADS)

Yamamichi, Akane; Kasama, Toshihiro; Ohka, Fumiharu; Suzuki, Hiromichi; Kato, Akira; Motomura, Kazuya; Hirano, Masaki; Ranjit, Melissa; Chalise, Lushun; Kurimoto, Michihiro; Kondo, Goro; Aoki, Kosuke; Kaji, Noritada; Tokeshi, Manabu; Matsubara, Toshio; Senga, Takeshi; Kaneko, Mika K.; Suzuki, Hidenori; Hara, Masahito; Wakabayashi, Toshihiko; Baba, Yoshinobu; Kato, Yukinari; Natsume, Atsushi

2016-01-01

World Health Organization grade II and III gliomas most frequently occur in the central nervous system (CNS) in adults. Gliomas are not circumscribed; tumor edges are irregular and consist of tumor cells, normal brain tissue, and hyperplastic reactive glial cells. Therefore, the tumors are not fully resectable, resulting in recurrence, malignant progression, and eventual death. Approximately 69-80% of grade II and III gliomas harbor mutations in the isocitrate dehydrogenase 1 gene (IDH1), of which 83-90% are found to be the IDH1-R132H mutation. Detection of the IDH1-R132H mutation should help in the differential diagnosis of grade II and III gliomas from other types of CNS tumors and help determine the boundary between the tumor and normal brain tissue. In this study, we established a highly sensitive antibody-based device, referred to as the immuno-wall, to detect the IDH1-R132H mutation in gliomas. The immuno-wall causes an immunoreaction in microchannels fabricated using a photo-polymerizing polymer. This microdevice enables the analysis of the IDH1 status with a small sample within 15 min with substantially high sensitivity. Our results suggested that 10% content of the IDH1-R132H mutation in a sample of 0.33 μl volume, with 500 ng protein, or from 500 cells is theoretically sufficient for the analysis. The immuno-wall device will enable the rapid and highly sensitive detection of the IDH1-R132H mutation in routine clinical practice.

An immuno-wall microdevice exhibits rapid and sensitive detection of IDH1-R132H mutation specific to grade II and III gliomas.

PubMed

Yamamichi, Akane; Kasama, Toshihiro; Ohka, Fumiharu; Suzuki, Hiromichi; Kato, Akira; Motomura, Kazuya; Hirano, Masaki; Ranjit, Melissa; Chalise, Lushun; Kurimoto, Michihiro; Kondo, Goro; Aoki, Kosuke; Kaji, Noritada; Tokeshi, Manabu; Matsubara, Toshio; Senga, Takeshi; Kaneko, Mika K; Suzuki, Hidenori; Hara, Masahito; Wakabayashi, Toshihiko; Baba, Yoshinobu; Kato, Yukinari; Natsume, Atsushi

2016-01-01

World Health Organization grade II and III gliomas most frequently occur in the central nervous system (CNS) in adults. Gliomas are not circumscribed; tumor edges are irregular and consist of tumor cells, normal brain tissue, and hyperplastic reactive glial cells. Therefore, the tumors are not fully resectable, resulting in recurrence, malignant progression, and eventual death. Approximately 69-80% of grade II and III gliomas harbor mutations in the isocitrate dehydrogenase 1 gene ( IDH1 ), of which 83-90% are found to be the IDH1-R132H mutation. Detection of the IDH1-R132H mutation should help in the differential diagnosis of grade II and III gliomas from other types of CNS tumors and help determine the boundary between the tumor and normal brain tissue. In this study, we established a highly sensitive antibody-based device, referred to as the immuno-wall, to detect the IDH1-R132H mutation in gliomas. The immuno-wall causes an immunoreaction in microchannels fabricated using a photo-polymerizing polymer. This microdevice enables the analysis of the IDH1 status with a small sample within 15 min with substantially high sensitivity. Our results suggested that 10% content of the IDH1-R132H mutation in a sample of 0.33 μl volume, with 500 ng protein, or from 500 cells is theoretically sufficient for the analysis. The immuno-wall device will enable the rapid and highly sensitive detection of the IDH1-R132H mutation in routine clinical practice.

A comprehensive bibliography on vacation homes and recreational lands in the United States

Treesearch

Richard L. Ragatz; H. Ken Cordell

1980-01-01

This bibliography contains 619 references on vacation homes and recreational lands. It is divided into five major parts: I-evolution of the markets. II-analyzing the markets. III-the consumer, IV-impacts from recreational properties, and V-miscellaneous.

Addressing the [O III] / Hβ offset in metal poor star forming galaxies found in the RESOLVE survey and ECO catalog

NASA Astrophysics Data System (ADS)

Richardson, Chris T.; Kannappan, Sheila; Moffett, Amanda J.; RESOLVE survey team

2018-06-01

Metal poor star forming galaxies sit on the far left wing of the BPT diagram just below traditional demarcation lines. The basic approach to reproducing their emission lines by coupling photoionization models to stellar population synthesis models underestimates the observed [O III] / Hβ ratio by a factor 0.3-0.5 dex. We classified galaxies as metal poor in the REsolved Spectroscopy of a Local VolumE (RESOLVE) survey and the Environmental COntext (ECO) catalog by using the IZI code based off of Bayesian inference. We used a variety of stellar population synthesis codes to generate SEDs covering a range of starburst ages and metallicities including both secular and binary stellar evolution. Here, we show that multiple SPS codes can produce SEDs hard enough to reduce the offset assuming that simple, and perhaps unjustified, nebular conditions hold. Adopting more realistic nebular conditions shows that, despite the recent emphasis placed on binary evolution to fit high O III ratios, none of our SEDs can reduce the offset. We propose several new solutions including using ensembles of nebular clouds and improved microphysics to address this issue. This work is supported by National Science Foundation awards OCI-1053575, though XSEDE award TG-AST140040, and NSF awards AST-0955368 and CISE/ACI-1156614.

Genome-wide identification, expansion, and evolution analysis of homeobox genes and their expression profiles during root development in carrot.

PubMed

Que, Feng; Wang, Guang-Long; Li, Tong; Wang, Ya-Hui; Xu, Zhi-Sheng; Xiong, Ai-Sheng

2018-06-16

The homeobox gene family, a large family represented by transcription factors, has been implicated in secondary growth, early embryo patterning, and hormone response pathways in plants. However, reports about the information and evolutionary history of the homeobox gene family in carrot are limited. In the present study, a total of 130 homeobox family genes were identified in the carrot genome. Specific codomain and phylogenetic analyses revealed that the genes were classified into 14 subgroups. Whole genome and proximal duplication participated in the homeobox gene family expansion in carrot. Purifying selection also contributed to the evolution of carrot homeobox genes. In Gene Ontology (GO) analysis, most members of the HD-ZIP III and IV subfamilies were found to have a lipid binding (GO:0008289) term. Most HD-ZIP III and IV genes also harbored a steroidogenic acute regulatory protein-related lipid transfer (START) domain. These results suggested that the HD-ZIP III and IV subfamilies might be related to lipid transfer. Transcriptome and quantitative real-time PCR (RT-qPCR) data indicated that members of the WOX and KNOX subfamilies were likely implicated in carrot root development. Our study provided a useful basis for further studies on the complexity and function of the homeobox gene family in carrot.

The continuity of bacterial and physicochemical evolution: theory and experiments.

PubMed

Spitzer, Jan

2014-01-01

The continuity of chemical and biological evolution, incorporating life's emergence, can be explored experimentally by energizing 'dead' bacterial biomacromolecules with nutrients under cycling physicochemical gradients. This approach arises from three evolutionary principles rooted in physical chemistry: (i) broken bacterial cells cannot spontaneously self-assemble into a living state without the supply of external energy - 2nd law of thermodynamics, (ii) the energy delivery must be cycling - the primary mechanism of chemical evolution at rotating planetary surfaces under solar irradiation, (iii) the cycling energy must act on chemical mixtures of high molecular diversity and crowding - provided by dead bacterial populations. Copyright © 2014 Institut Pasteur. Published by Elsevier Masson SAS. All rights reserved.

Experimental study of cyclic creep and high-cycle fatigue of welded joints of St3 steel by the DIC technique

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

Kibitkin, Vladimir V., E-mail: vvk@ispms.tsc.ru; Solodushkin, Andrey I., E-mail: s.ai@sibmail.com; Pleshanov, Vasily S., E-mail: vsp@ispms.tsc.ru

In the paper the mechanisms of plastic deformation and fracture of welded joints of steel St3 were investigated at high-cycle fatigue and cyclic creep by the digital image correlation (DIC) technique. The evolution of strain rate is studied for the following regions: base metal, HAZ, and fusion zone. This strain rate evolution can be considered as a mechanical response of material. Three stages of deformation evolution are shown: deformation hardening (I), fatigue crack initiation (II), and the last stage is related to main crack (III). Two criteria are offered to evaluate the current mechanical state of welded joints.

Directionality theory and the evolution of body size.

PubMed

Demetrius, L

2000-12-07

Directionality theory, a dynamic theory of evolution that integrates population genetics with demography, is based on the concept of evolutionary entropy, a measure of the variability in the age of reproducing individuals in a population. The main tenets of the theory are three principles relating the response to the ecological constraints a population experiences, with trends in entropy as the population evolves under mutation and natural selection. (i) Stationary size or fluctuations around a stationary size (bounded growth): a unidirectional increase in entropy; (ii) prolonged episodes of exponential growth (unbounded growth), large population size: a unidirectional decrease in entropy; and (iii) prolonged episodes of exponential growth (unbounded growth), small population size: random, non-directional change in entropy. We invoke these principles, together with an allometric relationship between entropy, and the morphometric variable body size, to provide evolutionary explanations of three empirical patterns pertaining to trends in body size, namely (i) Cope's rule, the tendency towards size increase within phyletic lineages; (ii) the island rule, which pertains to changes in body size that occur as species migrate from mainland populations to colonize island habitats; and (iii) Bergmann's rule, the tendency towards size increase with increasing latitude. The observation that these ecotypic patterns can be explained in terms of the directionality principles for entropy underscores the significance of evolutionary entropy as a unifying concept in forging a link between micro-evolution, the dynamics of gene frequency change, and macro-evolution, dynamic changes in morphometric variables.

Property evolution during vitrification of dimethacrylate photopolymer networks.

PubMed

Abu-elenain, Dalia A; Lewis, Steven H; Stansbury, Jeffrey W

2013-11-01

This study seeks to correlate the interrelated properties of conversion, shrinkage, modulus and stress as dimethacrylate networks transition from rubbery to glassy states during photopolymerization. An unfilled BisGMA/TEGDMA resin was photocured for various irradiation intervals (7-600 s) to provide controlled levels of immediate conversion, which was monitored continuously for 10 min. Fiber optic near-infrared spectroscopy permitted coupling of real-time conversion measurement with dynamic polymerization shrinkage (linometer), modulus (dynamic mechanical analyzer) and stress (tensometer) development profiles. The varied irradiation conditions produced final conversion ranging from 6% to more than 60%. Post-irradiation conversion (dark cure) was quite limited when photopolymerization was interrupted either at very low or very high levels of conversion while significant dark cure contributions were possible for photocuring reactions suspended within the post-gel, rubbery regime. Analysis of conversion-based property evolution during and subsequent to photocuring demonstrated that the shrinkage rate increased significantly at about 40% conversion followed by late-stage suppression in the conversion-dependent shrinkage rate that begins at about 45-50% conversion. The gradual vitrification process over this conversion range is evident based on the broad but well-defined inflection in the modulus versus conversion data. As limiting conversion is approached, modulus and, to a somewhat lesser extent, stress rise precipitously as a result of vitrification with the stress profile showing little if any late-stage suppression as seen with shrinkage. Near the limiting conversion for this model resin, the volumetric polymerization shrinkage rate slows while an exponential rise in modulus promotes the vitrification process that appears to largely dictate stress development. Copyright © 2013 Academy of Dental Materials. Published by Elsevier Ltd. All rights reserved.

Formation of ferric oxides from aqueous solutions: A polyhedral approach by X-ray absorption spectroscopy. I. Hydrolysis and formation of ferric gels

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

Combes, J.M.; Manceau, A.; Calas, G.

1989-03-01

X-ray absorption spectroscopy (XAS) was used to follow the evolution of local structural environments around ferric ions during the formation of ferric hydrous oxide gels from 1 M chloride and 0.1 M nitrate solutions. Fe K-XANES and EXAFS confirm that ferric ions remain 6-fold coordinated during this evolution. With increasing OH availability in the solution, Cl{sup {minus}} anions tend gradually to be exchanged for (O, OH, OH{sub 2}) ligands. Below OH/Fe = 1, no structural order is detected beyond the first coordination sphere. Above this ratio, two Fe-Fe distances at 3.05 {angstrom} and 3.44 {angstrom} are observed and correspond tomore » the presence of edge- and vertex-sharing Fe-octahedra. XAS results show that ferric gels and highly polymerized aqueous species are short-range ordered. The main contribution to disorder in the gels arises from the small size of coherently scattering domains also responsible for their X-ray amorphous character. From the initial to the final stage of hydrolysis, particles possess a nearly spherical shape with a minimum average diameter ranging from 10-30 {angstrom} for polymers formed from chloride and nitrate solutions. As polymerization proceeds, the local order extends to several tens of angstroms and the particle structures becomes progressively closer to that of akaganeite ({beta}-FeOOH) or goethite ({alpha}-FeOOH). This local structure is distinct from that of the lepidocrocite ({gamma}-FeOOH)-like structure of ferric gels precipitated after oxidation of divalent Fe solutions. The growth of the crystalline Fe-oxyhydroxides from gels takes place by the progressive long-range ordering in the ferric polymers without modifying the short-range order around Fe.« less

Desiccation tolerance of iron bacteria biofilms on Mars regolith simulants

NASA Astrophysics Data System (ADS)

Feyh, Nina; Szewzyk, Ulrich

2010-05-01

Iron oxidizing bacteria play an important role in the geological redox cycling of iron on earth. The redox change between Fe(II) and Fe(III) can be used for biological energy production [1]. Therefore iron oxidation in the iron rich martian soils may be or may have been microbially mediated. The microbial conversion of iron is considered to be an ancient form of metabolism [2], so it might have evolved on Mars as well. However, to exist in recent martian soils, bacteria must be able to endure dry and cold conditions. Neutrophilic iron oxidizers can be found in various iron rich aquatic environments, where they lead to the precipitation of insoluble ferric hydroxides. Some of these environments fall temporarily dry, what could have led to an adaptation to desiccation by bacteria, existing there. One strategy of iron bacteria to endure drought stress might be the formation of biofilms by excreting Extracellular Polymeric Substances (EPS). The deposition of iron hydroxides could enable them to endure dry conditions as well. For our experiments, neutrophilic iron oxidizing bacteria have been isolated from a creek in Bad Salzhausen/Hesse and temporarily drying out pools in Tierra del Fuego. Strains from aquatic environments in the national park "Unteres Odertal" and from water wells in Berlin/Brandenburg are included in the tests as well. In desiccation experiments, the capability of iron bacteria to tolerate dry conditions are investigated. The aim of our first experiment is the adaptation to dry conditions. Biofilms of 15 strains are grown on ceramic beads in liquid medium containing complexed Fe(II), established biofilms contain Fe(III) precipitates. The cultures are desiccated in a sterile airflow until the weight of the cultures remained constant. After a desiccation period of 9 h up to 7 d, the beads are transferred to fresh liquid medium. Adapted strains are used in further desiccation experiments, where biofilms are grown on two martian regolith simulants. These mineral mixtures were developed and produced by the Naturkundemuseum Berlin according to recent data of Mars research missions [3, 4, 5, 6, 7]. The minerals are attached to object slides with potassium silicate and biofilms are grown on the mineral surface. The biofilms are quantified by cell counting and the structure is evaluated by epifluorescence microscopy. After desiccation in a sterile airflow, the survival of cells is determined by fluorescence staining. Acknowledgements This research was supported by the Helmholtz Association through the research alliance "Planetary Evolution and Life". References [1] Weber, K. A. et al. (2006). Microorganisms pumping iron: anaerobic microbial iron oxidation and reduction. Nature Reviews Microbiology 4: 752-764. [2] Vargas, M. et al. (1998). Microbiological evidence for Fe(III) reduction on early Earth. Nature 395: 65-67. [3] Bibring, J.-P., Y. Langevin, et al. (2005). Mars surface diversity as revealed by the OMEGA/Mars express observations. Science 307(5715): 1576-1581. [4] Bibring, J.-P., S. W. Squyres, et al. (2006). Merging Views on Mars. Science 313(5795): 1899-1901. [5] Chevrier, V. and P. E. Mathé (2007). Mineralogy and evolution of the surface of Mars: A review. Planetary and Space Science 55(3): 289-314. [6] McCollom, T. M. and B. M. Hynek (2005). A volcanic environment for bedrock diagenesis at Meridiani Planum on Mars. Nature 438(7071): 1129-1131. [7] Poulet, F., J. P. Bibring, et al. (2005). Phyllosilicates on Mars and implications for early martian climate. Nature 438(7068): 623-627.

The Cytophaga hutchinsonii ChTPSP: First characterized bifunctional TPS-TPP protein as putative ancestor of all eukaryotic trehalose biosynthesis proteins.

PubMed

Avonce, Nelson; Wuyts, Jan; Verschooten, Katrien; Vandesteene, Lies; Van Dijck, Patrick

2010-02-01

The most widely distributed pathway to synthesize trehalose in nature consists of two consecutive enzymatic reactions with a trehalose-6-P (T6P)-synthase (TPS) enzyme, producing the intermediate T6P, and a T6P-phosphatase (TPP) enzyme, which dephosphorylates T6P to produce trehalose and inorganic phosphate. In plants, these enzymes are called Class I and Class II proteins, respectively, with some Class I proteins being active enzymes. The Class II proteins possess both TPS and TPP consensus regions but appear to have lost enzymatic activity during evolution. Plants also contain an extra group of enzymes of small protein size, of which some members have been characterized as functional TPPs. These Class III proteins have less sequence similarity with the Class I and Class II proteins. Here, we characterize for the first time, by using biochemical analysis and yeast growth complementation assays, the existence of a natural TPS-TPP bifunctional enzyme found in the bacterial species Cytophaga hutchinsonii. Through phylogenetic analysis, we show that prokaryotic genes such as ChTPSP might be the ancestor of the eukaryotic trehalose biosynthesis genes. Second, we show that plants have recruited during evolution, possibly by horizontal transfer from bacteria such as Rhodoferax ferrireducens, a new type of small protein, encoding TPP activity, which have been named Class III proteins. RfTPP has very high TPP activity upon expression in yeast. Finally, we demonstrate that TPS gene duplication, the recruitment of the Class III enzymes, and recruitment of an N-terminal regulatory element, which regulates the Class I enzyme activity in higher plants, were initiated very early in eukaryan evolution as the three classes of trehalose biosynthesis genes are already present in the alga Ostreococcus tauri.

Structural relaxation processes in polyethylene glycol/CCl4 solutions by Brillouin scattering.

PubMed

Pochylski, M; Aliotta, F; Błaszczak, Z; Gapiński, J

2005-03-10

We present results of a Brillouin scattering experiment on solutions of poly(ethylene glycol) of mean molecular mass 600 g/mol (PEG600) in CCl4. The relaxation process detected has been assigned to conformational rearrangements of the polymeric chains, triggered by reorientation of the side groups. The concentration dependencies of the hypersound velocity and normalized absorption are compared against the indications from several models proposed in the literature. The concentration evolution of the system is described in terms of two distinct regimes. At high polymer content, the system is dominated by the structure of the dense polymer, where polymer-polymer interactions, together with excluded volume effects, induce the existence of a preferred local arrangement resulting in a narrow distribution of the relaxation times, with the average value of the relaxation time following a simple Arrhenius temperature dependence. As the concentration decreases, the original structure of the hydrogen bonded polymer network is destroyed, and a number of different local configuration coexist, giving rise to a wider distribution of relaxation times or to a multiple relaxation. At low concentrations, the experimental data are well fitted assuming a Vogel-Fulker-Tammon behavior for the average relaxation time. In addition, the observed deviation from the ideal behavior for the refractive index and the density suggests that CCl4 does not behave as an inert solvent, and due to polarization effects, it can develop local hetero-associated structures via electrostatic interaction with the O-H end groups of the polymeric chains. The hypothesis has been successfully tested by fitting the concentration behavior of the hypersonic velocity to a recent three-component model, suitable to describe the concentration dependence of sound velocity in moderately interacting fluids. The indication of the model furnishes a very high value for the association constant of the PEG600, confirming the literature indication that, in polymeric systems capable of developing long liner aggregates via hydrogen bonding interaction, the Brillouin probe is insensitive to the true length of the polymeric chains. The Brillouin scattering experiment just sees an effective hydrogen bonded aggregate that is huge relative to the length of the single polymeric chain and becomes sensitive only to the density fluctuations of the local segmental motions.

Combined cosmological tests of a bivalent tachyonic dark energy scalar field model

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

Keresztes, Zoltán; Gergely, László Á., E-mail: zkeresztes@titan.physx.u-szeged.hu, E-mail: gergely@physx.u-szeged.hu

A recently investigated tachyonic scalar field dark energy dominated universe exhibits a bivalent future: depending on initial parameters can run either into a de Sitter exponential expansion or into a traversable future soft singularity followed by a contraction phase. We also include in the model (i) a tiny amount of radiation, (ii) baryonic matter (Ω{sub b}h{sup 2} = 0.022161, where the Hubble constant is fixed as h = 0.706) and (iii) cold dark matter (CDM). Out of a variety of six types of evolutions arising in a more subtle classification, we identify two in which in the past the scalar field effectively degenerates intomore » a dust (its pressure drops to an insignificantly low negative value). These are the evolutions of type IIb converging to de Sitter and type III hitting the future soft singularity. We confront these background evolutions with various cosmological tests, including the supernova type Ia Union 2.1 data, baryon acoustic oscillation distance ratios, Hubble parameter-redshift relation and the cosmic microwave background (CMB) acoustic scale. We determine a subset of the evolutions of both types which at 1σ confidence level are consistent with all of these cosmological tests. At perturbative level we derive the CMB temperature power spectrum to find the best agreement with the Planck data for Ω{sub CDM} = 0.22. The fit is as good as for the ΛCDM model at high multipoles, but the power remains slightly overestimated at low multipoles, for both types of evolutions. The rest of the CDM is effectively generated by the tachyonic field, which in this sense acts as a combined dark energy and dark matter model.« less

Microengineered embryonic stem cells niche to induce neural differentiation.

PubMed

Joshi, Ramila; Tavana, Hossein

2015-08-01

A major challenge in therapeutic use of embryonic stem cells (ESCs) for treating neurodegenerative diseases is creating a niche in vitro for controlled neural-specific differentiation of ESCs. We employ a niche microengineering approach to derive neural cells from ESCs by mimicking embryonic development in terms of direct intercellular interactions. Using a polymeric aqueous two-phase system (ATPS) microprinting technology, murine ESCs (mESCs) are precisely localized over a monolayer of supporting stromal cells to allow formation of individual mESC colonies. Polyethylene glycol (PEG) and dextran (DEX) are dissolved in culture media to form two immiscible aqueous solutions. A robotic liquid handler is used to print a nanoliter-volume drop of the denser DEX phase solution containing mESCs onto a confluent layer of supporting PA6 stromal cells submerged in the aqueous PEG phase. mESCs proliferate into isolated colonies of uniform size. For the first time, a comprehensive protein expression analysis of individual mESC colonies is performed over a two-week culture period to track temporal progression of cells from a pluripotent stage to specific neural cells. Starting from day 4, the expression of nestin, neural cell adhesion molecule (NCAM), and beta-III tubulin shows a significant increase but then levels off after the first week of culture. The expression of specific neural cell markers glial fibrillary acidic protein (GFAP), 2',3'-cyclic-nucleotide 3'-phosphodiesterase (CNPase), and tyrosine hydroxylase (TH) is elevated during the second week of culture. This microengineering approach to control ESCs differentiation niche combined with the time-course protein expression analysis of individual differentiating colonies facilitates understanding of evolution of specific neural cells from ESCs and identifying underlying molecular markers.

Method development for speciation analysis of nanoparticle and ionic forms of gold in biological samples by high performance liquid chromatography hyphenated to inductively coupled plasma mass spectrometry

NASA Astrophysics Data System (ADS)

Malejko, Julita; Świerżewska, Natalia; Bajguz, Andrzej; Godlewska-Żyłkiewicz, Beata

2018-04-01

A new method based on coupling high performance liquid chromatography (HPLC) to inductively coupled plasma mass spectrometry (ICP MS) has been developed for the speciation analysis of gold nanoparticles (AuNPs) and dissolved gold species (Au(III)) in biological samples. The column type, the composition and the flow rate of the mobile phase were carefully investigated in order to optimize the separation conditions. The usefulness of two polymeric reversed phase columns (PLRP-S with 100 nm and 400 nm pore size) to separate gold species were investigated for the first time. Under the optimal conditions (PLRP-S400 column, 10 mmol L-1 SDS and 5% methanol as the mobile phase, 0.5 mL min-1 flow rate), detection limits of 2.2 ng L-1 for Au(III), 2.8 ng L-1 for 10 nm AuNPs and 3.7 ng L-1 for 40 nm AuNPs were achieved. The accuracy of the method was proved by analysis of reference material RM 8011 (NIST) of gold nanoparticles of nominal diameter of 10 nm. The HPLC-ICP MS method has been successfully applied to the detection and size characterization of gold species in lysates of green algae Acutodesmus obliquus, typical representative of phytoplankton flora, incubated with 10 nm AuNPs or Au(III).

As(III) Removal from Drinking Water by Carbon Nanotube Membranes with Magnetron-Sputtered Copper: Performance and Mechanisms.

PubMed

Luan, Hongyan; Zhang, Quan; Cheng, Guo-An; Huang, Haiou

2018-06-20

Current approaches for functionalizing carbon nanotubes (CNTs) often utilize harsh chemical conditions, and the resulting harmful wastes can cause various environmental and health concerns. In this study, magnetron sputtering technique is facilely employed to functionalize CNT membranes by depositing Cu onto premade CNT membranes without using any chemical treatment. A comparative evaluation of the substrate polymeric membrane (mixed cellulose ester (MCE)), MCE sputtered with copper (Cu/MCE), the pristine CNT membrane (CNT), and CNT membrane sputtered with Cu (Cu/CNT) shows that Cu/CNT possesses mechanically stable structures and similar membrane permeability as MCE. More importantly, Cu/CNT outperforms other membranes with high As(III) removal efficiency of above 90%, as compared to less than 10% by MCE and CNT, and 75% by Cu/MCE from water. The performance of Cu/CNT membranes for As(III) removal is also investigated as a function of ionic strength, sputtering time, co-existing ions, solution pH, and the reusability. Further characterizations of As speciation in the filtrate and on Cu/CNT reveal that arsenite removal by Cu/CNT possibly began with Cu-catalyzed oxidation of arsenite to arsenate, followed by adsorptive filtration of arsenate by the membrane. Overall, this study demonstrates that magnetron sputtering is a promising greener technology for the productions of metal-CNT composite membranes for environmental applications.

Model compounds of iron gall inks - a Mössbauer study

NASA Astrophysics Data System (ADS)

Lerf, A.; Wagner, F. E.

2016-12-01

Ferrogallic inks were used for at least two millennia before they became obsolete in the 20th century. The chemistry of such inks is, however, still largely unclear. Today it is of particular interest for the conservation of old manuscripts. 57Fe Mössbauer spectra of the ink on historical documents showed the presence of Fe(II) oxalate and of Fe(III) sites presumably representing iron oxihydroxides. To obtain more information on the behaviour of ink on paper we have performed Mössbauer studies at 300 and 4.2 K on iron gall inks prepared from FeSO4ṡ7H2O and tannin. These inks were either written on paper or isolated as a precipitate by centrifugation. In the dried precipitate there is still a strong contribution of the FeSO4ṡ7H2O which is absent in the same ink written on paper, for which a broad ferrous component with a quadrupole splitting (QS) of about 2.5 mm/s was found. The dominant Fe(III) site present in all inks on paper with QS ≈ 0.82 mm/s is not Fe(III) gallate and different from the precipitates. We propose that nanoparticulate oxidic clusters or molecular composites covered by a shell of polymerized oxidation products of the phenols are formed on the paper.

A cyclometalated iridium(III) complex used as a conductor for the electrochemical sensing of IFN-γ

NASA Astrophysics Data System (ADS)

Miao, Xiangmin; Ko, Chung-Nga; Vellaisamy, Kasipandi; Li, Zongbing; Yang, Guanjun; Leung, Chung-Hang; Ma, Dik-Lung

2017-02-01

A novel iridium(III) complex was prepared and used as a conductor for sensitive and enzyme-free electrochemical detection of interferon gamma (IFN-γ). This assay is based on a dual signal amplification mechanism involving positively charged gold nanoparticles ((+)AuNPs) and hybridization chain reaction (HCR). To construct the sensor, nafion (Nf) and (+)AuNPs composite membrane was first immobilized onto the electrode surface. Subsequently, a loop-stem structured capture probe (CP) containing a special IFN-γ interact strand was modified onto the (+)AuNP surface via the formation of Au-S bonds. Upon addition of IFN-γ, the loop-stem structure of CP was opened, and the newly exposed “sticky” region of CP then hybridized with DNA hairpin-1 (H1), which in turn opened its hairpin structure for hybridizing with DNA hairpin-2 (H2). Happen of HCR between H1 and H2 thus generated a polymeric duplex DNA (dsDNA) chain. Meanwhile, the iridium(III) complex could interact with the grooves of the dsDNA polymer, producing a strong current signal that was proportional to IFN-γ concentration. Thus, sensitive detection of IFN-γ could be realized with a detection limit down to 16.3 fM. Moreover, satisfied results were achieved by using this method for the detection of IFN-γ in human serum samples.

K 3 Fe(CN) 6 under External Pressure: Dimerization of CN – Coupled with Electron Transfer to Fe(III)

DOE PAGES

Li, Kuo; Zheng, Haiyan; Wang, Lijuan; ...

2015-09-14

The addition polymerization of charged monomers like C≡C 2– and C≡N– is scarcely seen at ambient conditions but can progress under external pressure with their conductivity significantly enhanced, which expands the research field of polymer science to inorganic salts. Moreover, the reaction pressures of transition metal cyanides like Prussian blue and K 3Fe(CN) 6 are much lower than that of alkali cyanides. To figure out the effect of the transition metal on the reaction, the crystal structure and electronic structure of K 3Fe(CN) 6 under external pressure are investigated by in situ neutron diffraction, in situ X-ray absorption fine structuremore » (XAFS), and neutron pair distribution functions (PDF) up to ~15 GPa. The cyanide anions react following a sequence of approaching–bonding–stabilizing. The Fe(III) brings the cyanides closer which makes the bonding progress at a low pressure (2–4 GPa). At ~8 GPa, an electron transfers from the CN to Fe(III), reduces the charge density on cyanide ions, and stabilizes the reaction product of cyanide. Finally, from this study we can conclude that bringing the monomers closer and reducing their charge density are two effective routes to decrease the reaction pressure, which is important for designing novel pressure induced conductor and excellent electrode materials.« less

A Modified Edge Crack Torsion Test for Measurement of Mode III Fracture Toughness of Laminated Tape Composites

NASA Technical Reports Server (NTRS)

Czabaj, Michael W.; Davidson, Barry D.; Ratcliffe, James G.

2016-01-01

Modifications to the edge crack torsion (ECT) test are studied to improve the reliability of this test for measuring the mode-III fracture toughness, G (sub IIIc), of laminated tape fiber-reinforced polymeric (FRP) composites. First, the data reduction methods currently used in the ECT test are evaluated and deficiencies in their accuracy are discussed. An alternative data reduction technique, which uses a polynomial form to represent ECT specimen compliance solution, is evaluated and compared to FEA (finite element analysis) results. Second, seven batches of ECT specimens are tested, each batch containing specimens with a preimplanted midplane edge delamination and midplane plies with orientations of plus theta divided by minus theta, with theta ranging from 0 degrees to 90 degrees in 15-degree increments. Tests on these specimens show that intralaminar cracking occurs in specimens from all batches except for which theta = 15 degrees and 30 degrees. Tests on specimens of these two batches are shown to result in mode-III delamination growth at the intended ply interface. The findings from this study are encouraging steps towards the use of the ECT test as a standardized method for measuring G (sub IIIc), although further modification to the data reduction method is required to make it suitable for use as part of a standardized test method.

An Open-Label, Randomized, Parallel, Phase III Trial Evaluating the Efficacy and Safety of Polymeric Micelle-Formulated Paclitaxel Compared to Conventional Cremophor EL-Based Paclitaxel for Recurrent or Metastatic HER2-Negative Breast Cancer.

PubMed

Park, In Hae; Sohn, Joo Hyuk; Kim, Sung Bae; Lee, Keun Seok; Chung, Joo Seop; Lee, Soo Hyeon; Kim, Tae You; Jung, Kyung Hae; Cho, Eun Kyung; Kim, Yang Soo; Song, Hong Suk; Seo, Jae Hong; Ryoo, Hun Mo; Lee, Sun Ah; Yoon, So Young; Kim, Chul Soo; Kim, Yong Tai; Kim, Si Young; Jin, Mi Ryung; Ro, Jungsil

2017-07-01

Genexol-PM is a Cremophor EL-free formulation of low-molecular-weight, non-toxic, and biodegradable polymeric micelle-bound paclitaxel. We conducted a phase III study comparing the clinical efficacy and toxicity of Genexol-PM with conventional paclitaxel (Genexol). Patients were randomly assigned (1:1) to receive Genexol-PM 260 mg/m 2 or Genexol 175 mg/m 2 intravenously every 3 weeks. The primary outcome was the objective response rate (ORR). The study enrolled 212 patients, of whom 105 were allocated to receive Genexol-PM. The mean received dose intensity of Genexol-PM was 246.8±21.3 mg/m 2 (95.0%), and that of Genexol was 168.3±10.6 mg/m 2 (96.2%). After a median follow-up of 24.5 months (range, 0.0 to 48.7 months), the ORR of Genexol-PM was 39.1% (95% confidence interval [CI], 31.2 to 46.9) and the ORR of Genexol was 24.3% (95% CI, 17.5 to 31.1) (p non-inferiority =0.021, p superiority =0.016). The two groups did not differ significantly in overall survival (28.8 months for Genexol-PM vs. 23.8 months for Genexol; p=0.52) or progression-free survival (8.0 months for Genexol-PM vs. 6.7 months for Genexol; p=0.26). In both groups, the most common toxicities were neutropenia, with 68.6% occurrence in the Genexol-PM group versus 40.2% in the Genexol group (p < 0.01). The incidences of peripheral neuropathy of greater than grade 2 did not differ significantly between study treatments. Compared with standard paclitaxel, Genexol-PM demonstrated non-inferior and even superior clinical efficacy with a manageable safety profile in patients with metastatic breast cancer.

Structural characterization of the Yersinia pestis type III secretion system needle protein YscF in complex with its heterodimeric chaperone YscE/YscG

PubMed Central

Sun, Ping; Tropea, Joseph E.; Austin, Brian P.; Cherry, Scott; Waugh, David S.

2008-01-01

Summary The plague-causing bacterium Yersinia pestis utilizes a Type III Secretion System (T3SS) to deliver effector proteins into mammalian cells where they interfere with signal transduction pathways that mediate phagocytosis and the inflammatory response. Effector proteins are injected through a hollow needle structure composed of the protein YscF. YscG and YscE act as "chaperones" to prevent premature polymerization of YscF in the cytosol of the bacterium prior to assembly of the needle. Here, we report the crystal structure of the YscEFG protein complex at 1.8 Å resolution. Overall, the structure is similar to that of the analogous PscEFG complex from the Pseudomonas aeruginosa T3SS, but there are noteworthy differences. The structure confirms that, like PscG, YscG is a member of the tetratricopeptide repeat (TPR) family of proteins. YscG binds tightly to the C-terminal half of YscF, implying that it is this region of YscF that controls its polymerization into the needle structure. YscE interacts with the N-terminal TPR motif of YscG but makes very little direct contact with YscF. Its function may be to stabilize the structure of YscG and/or to participate in recruiting the complex to the secretion apparatus. No electron density could be observed for the N-terminal 49 residues of YscF. This and additional evidence suggest that the N-terminus of YscF is disordered in the complex with YscE and YscG. As expected, conserved residues in the C-terminal half of YscF mediate important intra- and intermolecular interactions in the complex. Moreover, the phenotypes of some previously characterized mutations in the C-terminal half of YscF can be rationalized in terms of the structure of the heterotrimeric YscEFG complex. PMID:18281060

Assessing the transport potential of polymeric nanocapsules developed for crop protection.

PubMed

Petosa, Adamo Riccardo; Rajput, Faraz; Selvam, Olivia; Öhl, Carolin; Tufenkji, Nathalie

2017-03-15

Nanotechnology is increasingly important in the agricultural sector, with novel products being developed to heighten crop yields and increase pesticide efficacy. Herein, the transport potential of different polymeric nanocapsules (nCAPs) developed as pesticide delivery vehicles was assessed in model soil systems. The nCAPs examined are (i) poly(acrylic acid)-based (nCAP1), (ii) poly(methacrylic acid)-ran-poly(ethyl acrylate) copolymer-based (nCAP2), (iii) poly(methacrylic acid-ran-styrene) copolymer-based (nCAP3), and (iv) poly(methacrylic acid-ran-butylmethacrylate)-based (nCAP4). nCAP mobility was examined in columns packed with agricultural loamy sand saturated with artificial porewater containing Ca 2+ and Mg 2+ cations (10 mM ionic strength, pH 6 and 8). Furthermore, the impact of (i) cation species, (ii) sand type, and (iii) ammonium polyphosphate fertilizer on the transport potential of a nanoformulation combining nCAP4 capsules and the pyrethroid bifenthrin (nCAP4-BIF) was examined and compared to a commercial bifenthrin formulation (Capture ® LFR). Although nCAP4-BIF and Capture ® LFR formulations were highly mobile in quartz sand saturated with 10 mM NaNO 3 (≥95% elution), they were virtually immobile in the presence of 10% ammonium polyphosphate fertilizer. The presence of Ca 2+ and Mg 2+ did not hinder nCAP4-BIF elution in quartz sand saturated with 10 mM standard CIPAC D synthetic porewater; however, limited Capture ® LFR transport (<10% elution) was observed under the same conditions. Capture ® LFR also exhibited limited mobility in the presence or absence of fertilizer in loamy sand saturated with divalent salt solutions, whereas nCAP4-BIF exhibited increased elution with time and enhanced transport upon the addition of fertilizer. Overall, nCAP4 is a promising delivery vehicle in pyrethroid nanoformulations such as nCAP4-BIF. Copyright © 2016 Elsevier Ltd. All rights reserved.

Conducting polymer actuators: From basic concepts to proprioceptive systems

NASA Astrophysics Data System (ADS)

Martinez Gil, Jose Gabriel

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

Micro-fluidic partitioning between polymeric sheets for chemical amplification and processing

DOEpatents

Anderson, Brian L.

2017-01-24

A system for fluid partitioning for chemical amplification or other chemical processing or separations of a sample, comprising a first dispenser of a first polymeric sheet, wherein the first polymeric sheet contains chambers; a second dispenser of a second polymeric sheet wherein the first dispenser and the second dispenser are positioned so that the first polymeric sheet and the second polymeric sheet become parallel; a dispenser of the fluid positioned to dispense the fluid between the first polymeric sheet and the second polymeric sheet; and a seal unit that seals the first polymeric sheet and the second polymeric sheet together thereby sealing the sample between the first polymeric sheet and the second polymeric sheet and partitioning the fluid for chemical amplification or other chemical processing or separations.

Micro-fluidic partitioning between polymeric sheets for chemical amplification and processing

DOEpatents

Anderson, Brian L.

2015-05-26

A system for fluid partitioning for chemical amplification or other chemical processing or separations of a sample, comprising a first dispenser of a first polymeric sheet, wherein the first polymeric sheet contains chambers; a second dispenser of a second polymeric sheet wherein the first dispenser and the second dispenser are positioned so that the first polymeric sheet and the second polymeric sheet become parallel; a dispenser of the fluid positioned to dispense the fluid between the first polymeric sheet and the second polymeric sheet; and a seal unit that seals the first polymeric sheet and the second polymeric sheet together thereby sealing the sample between the first polymeric sheet and the second polymeric sheet and partitioning the fluid for chemical amplification or other chemical processing or separations.

Preparation of novel polyamine-type chelating resin with hyperbranched structures and its adsorption performance

NASA Astrophysics Data System (ADS)

Chen, Youning; Zhao, Wei; Wang, Huan; Li, Yuhong; Li, Chenxi

2018-02-01

This paper explored the method of combining atom transfer radical polymerization (ATRP) technology and hyperbranched polymer principle to prepare the high capacity chelating resin. First, surface-initiated atom transfer radical polymerization (SI-ATRP) method was used to graft glycidyl methacrylate (GMA) on chloromethylated cross-linked styrene-divinylbenzene resin, and then the novel polyamine chelating resin with a kind of hyperbranched structure was prepared through the amination reaction between amino group of (2-aminoethyl) triamine and epoxy group in GMA. This resin had a selective effect on As(V) and Cr(VI) at a relatively low pH and can be used for the disposal of waste water containing As(V) and Cr(VI). It had a relatively strong adsorption effect on Cu(II), Pb(II), Cd(II) and Cr(III) and can be used for the disposal of heavy metal ion waste water. The finding was that, the adsorption capacity of resin on the studied heavy metal ions was higher than that of the chelating resin synthesized by traditional technology and also higher than that of the resin modified by ATRP technology and bifunctional chelator, indicating that the combination of ATRP and hyperbranched polymer concept is an effective method to prepare chelating resin with high capacity.

Fluorescence-tagged amphiphilic brush copolymer encapsulated Gd2O3 core-shell nanostructures for enhanced T 1 contrast effect and fluorescent imaging

NASA Astrophysics Data System (ADS)

Wang, Fenghe; Peng, Erwin; Liu, Feng; Li, Pingjing; Fong Yau Li, Sam; Xue, Jun Min

2016-10-01

To obtain suitable T 1 contrast agents for magnetic resonance imaging (MRI) application, aqueous Gd2O3 nanoparticles (NPs) with high longitudinal relativity (r 1) are demanded. High quality Gd2O3 NPs are usually synthesized through a non-hydrolytic route which requires post-synthetic modification to render the NPs water soluble. The current challenge is to obtain aqueous Gd2O3 NPs with high colloidal stability and enhanced r 1 relaxivity. To overcome this challenge, fluorescence-tagged amphiphilic brush copolymer (AFCP) encapsulated Gd2O3 NPs were proposed as suitable T 1 contrast agents. Such a coating layer provided (i) superior aqueous stability, (ii) biocompatibility, as well as (iii) multi-modality (conjugation with fluorescence dye). The polymeric coating layer thickness was simply adjusted by varying the phase-transfer parameters. By reducing the coating thickness, i.e. the distance between the paramagnetic centre and surrounding water protons, the r 1 relaxivity could be enhanced. In contrast, a thicker polymeric layer coating prevents Gd3+ ions leakage, thus improving its biocompatibility. Therefore, it is important to strike a balance between the biocompatibility and the r 1 relaxivity behaviour. Lastly, by conjugating fluorescence moiety, an additional imaging modality was enabled, as demonstrated from the cell-labelling experiment.

Bioinspired Ultratough Hydrogel with Fast Recovery, Self-Healing, Injectability and Cytocompatibility.

PubMed

Azevedo, Sara; Costa, Ana M S; Andersen, Amanda; Choi, Insung S; Birkedal, Henrik; Mano, João F

2017-07-01

Inspired by the mussel byssus adhesiveness, a highly hydrated polymeric structure is designed to combine, for the first time, a set of interesting features for load-bearing purposes. These characteristics include: i) a compressive strength and stiffness in the MPa range, ii) toughness and the ability to recover it upon successive cyclic loading, iii) the ability to quickly self-heal upon rupture, iv) the possibility of administration through minimally invasive techniques, such as by injection, v) the swelling ratio being adjusted to space-filling applications, and vi) cytocompatibility. Owing to these characteristics and the mild conditions employed, the encapsulation of very unstable and sensitive cargoes is possible, highlighting their potential to researchers in the biomedical field for the repair of load-bearing soft tissues, or to be used as an encapsulation platform for a variety of biological applications such as disease models for drug screening and therapies in a more realistic mechanical environment. Moreover, given the simplicity of this methodology and the enhanced mechanical performance, this strategy can be expanded to applications in other fields, such as agriculture and electronics. As such, it is anticipated that the proposed strategy will constitute a new, versatile, and cost-effective tool to produce engineered polymeric structures for both science and technology. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Preparation of novel polyamine-type chelating resin with hyperbranched structures and its adsorption performance

PubMed Central

Zhao, Wei; Wang, Huan; Li, Yuhong; Li, Chenxi

2018-01-01

This paper explored the method of combining atom transfer radical polymerization (ATRP) technology and hyperbranched polymer principle to prepare the high capacity chelating resin. First, surface-initiated atom transfer radical polymerization (SI-ATRP) method was used to graft glycidyl methacrylate (GMA) on chloromethylated cross-linked styrene-divinylbenzene resin, and then the novel polyamine chelating resin with a kind of hyperbranched structure was prepared through the amination reaction between amino group of (2-aminoethyl) triamine and epoxy group in GMA. This resin had a selective effect on As(V) and Cr(VI) at a relatively low pH and can be used for the disposal of waste water containing As(V) and Cr(VI). It had a relatively strong adsorption effect on Cu(II), Pb(II), Cd(II) and Cr(III) and can be used for the disposal of heavy metal ion waste water. The finding was that, the adsorption capacity of resin on the studied heavy metal ions was higher than that of the chelating resin synthesized by traditional technology and also higher than that of the resin modified by ATRP technology and bifunctional chelator, indicating that the combination of ATRP and hyperbranched polymer concept is an effective method to prepare chelating resin with high capacity. PMID:29515875

Macroporous polyacrylamide monolithic gels with immobilized metal affinity ligands: the effect of porous structure and ligand coupling chemistry on protein binding.

PubMed

Plieva, Fatima; Bober, Beata; Dainiak, Maria; Galaev, Igor Yu; Mattiasson, Bo

2006-01-01

Macroporous polyacrylamide gels (MPAAG) with iminodiacetic acid (IDA) functionality were prepared by (i) chemical modification of polyacrylamide gel, (ii) co-polymerization of acrylamide with allyl glycidyl ether (AGE) and N,N'metylene-bis(acrylamide) (MBAAm) followed by coupling IDA ligand or (iii) by copolymerization of acrylamide and MBAAm with functional monomer carrying IDA-functionality (1-(N,N-bis(carboxymethyl)amino-3-allylglycerol). Screening for optimized conditions for the production of the MPAAG with required porous properties was performed in a 96-well chromatographic format that allowed parallel production and analysis of the MPAAG prepared from reaction mixtures with different compositions. Scanning electron microscopy of the fabricated MPAAG revealed two different types of the porous structures: monomodal macroporous structure with large interconnected pores separated by dense non-porous pore walls in case of plain gels or gels produced via copolymerization with AGE. The other type of the MPAAG (gel produced via co-polymerization with functional monomer carrying IDA-functionality) had bimodal pore structure with large interconnected pores separated by the pore walls pierced through with micropores. The effect of different modifications of MPAAG monoliths and of porous structure of the MPAAG (monomodal and bimodal porous structure) on protein binding has been evaluated. Copyright 2006 John Wiley & Sons, Ltd.

Use of lectins to in situ visualize glycoconjugates of extracellular polymeric substances in acidophilic archaeal biofilms

PubMed Central

Zhang, R Y; Neu, T R; Bellenberg, S; Kuhlicke, U; Sand, W; Vera, M

2015-01-01

Biofilm formation and the production of extracellular polymeric substances (EPS) by meso- and thermoacidophilic metal-oxidizing archaea on relevant substrates have been studied to a limited extent. In order to investigate glycoconjugates, a major part of the EPS, during biofilm formation/bioleaching by archaea on pyrite, a screening with 75 commercially available lectins by fluorescence lectin-binding analysis (FLBA) has been performed. Three representative archaeal species, Ferroplasma acidiphilum DSM 28986, Sulfolobus metallicus DSM 6482T and a novel isolate Acidianus sp. DSM 29099 were used. In addition, Acidianus sp. DSM 29099 biofilms on elemental sulfur were studied. The results of FLBA indicate (i) 22 lectins bound to archaeal biofilms on pyrite and 21 lectins were binding to Acidianus sp. DSM 29099 biofilms on elemental sulfur; (ii) major binding patterns, e.g. tightly bound EPS and loosely bound EPS, were detected on both substrates; (iii) the three archaeal species produced various EPS glycoconjugates on pyrite surfaces. Additionally, the substratum induced different EPS glycoconjugates and biofilm structures of cells of Acidianus sp. DSM 29099. Our data provide new insights into interactions between acidophilic archaea on relevant surfaces and also indicate that FLBA is a valuable tool for in situ investigations on archaeal biofilms. PMID:25488256

Urinary tract infection in small children: the evolution of renal damage over time.

PubMed

Swerkersson, Svante; Jodal, Ulf; Sixt, Rune; Stokland, Eira; Hansson, Sverker

2017-10-01

Our objective was to analyze the evolution of kidney damage over time in small children with urinary tract infection (UTI) and factors associated with progression of renal damage. From a cohort of 1003 children <2 years of age with first-time UTI, a retrospective analysis of 103 children was done. Children were selected because of renal damage at index 99m Tc-dimercaptosuccinic acid (DMSA) scintigraphy at least 3 months after UTI, and a late DMSA scan was performed after at least 2 years. Damage was classified as progression when there was a decline in differential renal function (DRF) by ≥4%, as regression when there was complete or partial resolution of uptake defects. Of 103 children, 20 showed progression, 20 regression, and 63 remained unchanged. There were no differences between groups regarding gender or age. In the progression group, 16/20 (80%) children had vesicoureteral reflux (VUR) grade III-V and 13 (65%) had recurrent UTI. In multivariable regression analysis, both VUR grade III-V and recurrent UTI were associated with progression. In the regression group, 16/20 (80%) had no VUR or grade I-II, and two (10%) had recurrent UTI. Most small children with febrile UTI do not develop renal damage and if they do the majority remain unchanged or regress over time. However, up to one-fifth of children with renal damage diagnosed after UTI are at risk of renal deterioration. These children are characterized by the presence of VUR grades III-V and recurrent febrile UTI and may benefit from follow-up.

Directed evolution of an endoinulinase from Talaromyces purpureogenus toward efficient production of inulooligosaccharides.

PubMed

Afriat-Jurnou, Livnat; Cohen, Rami; Paluy, Irina; Ben-Adiva, Ran; Yadid, Itamar

2018-02-01

Inulinases are fructofuranosyl hydrolases that target the β-2,1 linkage of inulin and hydrolyze it into fructose, glucose and inulooligosaccharides (IOS), the latter are of growing interest as dietary fibers. Inulinases from various microorganisms have been purified, characterized and produced for industrial applications. However, there remains a need for inulinases with increased catalytic activity and better production yields to improve the hydrolysis process and fulfill the growing industrial demands for specific fibers. In this study, we used directed enzyme evolution to increase the yield and activity of an endoinulinase enzyme originated from the filamentous fungus Talaromyces purpureogenus (Penicillium purpureogenum ATCC4713). Our directed evolution approach yielded variants showing up to fivefold improvements in soluble enzyme production compared to the starting point which enabled high-yield production of highly purified recombinant enzyme. The distribution of the enzymatic reaction products demonstrated that after 24 h of incubation, the main product (57%) had a degree of polymerization of 3 (DP3). To the best of our knowledge, this is the first application of directed enzyme evolution to improve inulooligosaccharide production. The approach enabled the screening of large genetic libraries within short time frames and facilitated screening for improved enzymatic activities and properties, such as substrate specificity, product range, thermostability and pH optimum. © 2018 American Institute of Chemical Engineers Biotechnol. Prog., 2018. © 2018 American Institute of Chemical Engineers.

The early evolution of giant H II regions formed by supernova explosions

NASA Technical Reports Server (NTRS)

Kafatos, M. C.

1971-01-01

The evolution of a giant H II region, which cools after an initial ionization, is discussed. The discussion is applied to the Vela X and Tycho supernovae. Other giant H II regions might not be as easily detectable as the Vela X region. The Tycho region may be just detectable in the O(II) or O(III) optical lines or as a hole in the 21-cm emission line profiles, as is suggested in the data. These giant H II regions last appreciably longer than the continuum radio sources within them.

Click polymerization for the synthesis of reduction-responsive polymeric prodrug

NASA Astrophysics Data System (ADS)

Zhang, Xiaojin; Wang, Hongquan; Dai, Yu

2018-05-01

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

Chain Reaction Polymerization.

ERIC Educational Resources Information Center

McGrath, James E.

1981-01-01

The salient features and importance of chain-reaction polymerization are discussed, including such topics as the thermodynamics of polymerization, free-radical polymerization kinetics, radical polymerization processes, copolymers, and free-radical chain, anionic, cationic, coordination, and ring-opening polymerizations. (JN)

Chromosomal structures and repetitive sequences divergence in Cucumis species revealed by comparative cytogenetic mapping.

PubMed

Zhang, Yunxia; Cheng, Chunyan; Li, Ji; Yang, Shuqiong; Wang, Yunzhu; Li, Ziang; Chen, Jinfeng; Lou, Qunfeng

2015-09-25

Differentiation and copy number of repetitive sequences affect directly chromosome structure which contributes to reproductive isolation and speciation. Comparative cytogenetic mapping has been verified an efficient tool to elucidate the differentiation and distribution of repetitive sequences in genome. In present study, the distinct chromosomal structures of five Cucumis species were revealed through genomic in situ hybridization (GISH) technique and comparative cytogenetic mapping of major satellite repeats. Chromosome structures of five Cucumis species were investigated using GISH and comparative mapping of specific satellites. Southern hybridization was employed to study the proliferation of satellites, whose structural characteristics were helpful for analyzing chromosome evolution. Preferential distribution of repetitive DNAs at the subtelomeric regions was found in C. sativus, C hystrix and C. metuliferus, while majority was positioned at the pericentromeric heterochromatin regions in C. melo and C. anguria. Further, comparative GISH (cGISH) through using genomic DNA of other species as probes revealed high homology of repeats between C. sativus and C. hystrix. Specific satellites including 45S rDNA, Type I/II, Type III, Type IV, CentM and telomeric repeat were then comparatively mapped in these species. Type I/II and Type IV produced bright signals at the subtelomeric regions of C. sativus and C. hystrix simultaneously, which might explain the significance of their amplification in the divergence of Cucumis subgenus from the ancient ancestor. Unique positioning of Type III and CentM only at the centromeric domains of C. sativus and C. melo, respectively, combining with unique southern bands, revealed rapid evolutionary patterns of centromeric DNA in Cucumis. Obvious interstitial telomeric repeats were observed in chromosomes 1 and 2 of C. sativus, which might provide evidence of the fusion hypothesis of chromosome evolution from x = 12 to x = 7 in Cucumis species. Besides, the significant correlation was found between gene density along chromosome and GISH band intensity in C. sativus and C. melo. In summary, comparative cytogenetic mapping of major satellites and GISH revealed the distinct differentiation of chromosome structure during species formation. The evolution of repetitive sequences was the main force for the divergence of Cucumis species from common ancestor.

Directional growth of Ag nanorod from polymeric silver cyanide: A potential substrate for concentration dependent SERS signal enhancement leading to melamine detection

NASA Astrophysics Data System (ADS)

Roy, Anindita; Sahoo, Ramkrishna; Chowdhury, Joydeep; Bhattacharya, Tara Shankar; Agarwal, Ratnesh; Pal, Tarasankar

2017-08-01

Attention has been directed to prepare exclusive one-dimensional silver nanostructure from the linear inorganic polymer AgCN. Successive color change from yellow to orange, to red and finally to green reflects the evolution of high yielding Ag nanorods (NRs) from well-known -[Ag-CN]- chains of polymeric AgCN at room temperature. The parental 1D morphology of AgCN is retained within the as-synthesized Ag NRs. So we could successfully exploit the Ag NR for surface-enhanced Raman scattering (SERS) studies for sensing a popular milk adulterant melamine down to picomolar level. We observed interesting concentration dependent selective SERS band enhancement of melamine. The enhanced 1327 cm- 1 SERS signal intensity at lower concentration (10- 9 and 10- 12 M) of melamine speaks for the preferential participation of -C-N of melamine molecule with Ag surface. On the other hand, '-NH2' group together with ring 'N' participation of melamine molecule onto Ag surface suggested an adsorptive stance at higher (10- 3-10- 7 M) concentration range. Thus the binding modes of the molecule at the Ag surface justify its fluxional behavior.

Structure, viscoelasticity, and interfacial dynamics of a model polymeric bicontinuous microemulsion

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

Hickey, Robert J.; Gillard, Timothy M.; Irwin, Matthew T.

2016-01-01

We have systematically studied the equilibrium structure and dynamics of a polymeric bicontinuous microemulsion (BμE) composed of poly(cyclohexylethylene) (PCHE), poly(ethylene) (PE), and a volumetrically symmetric PCHE–PE diblock copolymer, using dynamic mechanical spectroscopy, small angle X-ray and neutron scattering, and transmission electron microscopy. The BμE was investigated over an 80 °C temperature range, revealing a structural evolution and a rheological response not previously recognized in such systems. As the temperature is reduced below the point associated with the lamellar-disorder transition at compositions adjacent to the microemulsion channel, the interfacial area per chain of the BμE approaches that of the neat (undiluted)more » lamellar diblock copolymer. With increasing temperature, the diblock-rich interface swells through homopolymer infiltration. Time–temperature-superposed linear dynamic data obtained as a function of frequency show that the viscoelastic response of the BμE is strikingly similar to that of the fluctuating pure diblock copolymer in the disordered state, which we associate with membrane undulations and the breaking and reforming of interfaces. This work provides new insights into the structure and dynamics that characterize thermodynamically stable BμEs in the limits of relatively weak and strong segregation.« less

Quantum dynamics of the Einstein-Rosen wormhole throat

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

Kunstatter, Gabor; Peltola, Ari; Louko, Jorma

2011-02-15

We consider the polymer quantization of the Einstein wormhole throat theory for an eternal Schwarzschild black hole. We numerically solve the difference equation describing the quantum evolution of an initially Gaussian, semiclassical wave packet. As expected from previous work on loop quantum cosmology, the wave packet remains semiclassical until it nears the classical singularity at which point it enters a quantum regime in which the fluctuations become large. The expectation value of the radius reaches a minimum as the wave packet is reflected from the origin and emerges to form a near-Gaussian but asymmetrical semiclassical state at late times. Themore » value of the minimum depends in a nontrivial way on the initial mass/energy of the pulse, its width, and the polymerization scale. For wave packets that are sufficiently narrow near the bounce, the semiclassical bounce radius is obtained. Although the numerics become difficult to control in this limit, we argue that for pulses of finite width the bounce persists as the polymerization scale goes to zero, suggesting that in this model the loop quantum gravity effects mimicked by polymer quantization do not play a crucial role in the quantum bounce.« less

Enhancing the mechanical and in vitro performance of robocast bioglass scaffolds by polymeric coatings: Effect of polymer composition.

PubMed

Motealleh, Azadeh; Eqtesadi, Siamak; Pajares, Antonia; Miranda, Pedro

2018-08-01

The effect of different polymeric coatings, including natural and synthetic compositions, on the mechanical performance of 45S5 bioglass robocast scaffolds is systematically analyzed in this work. Fully amorphous 45S5 bioglass robocast scaffolds sintered at 550 °C were impregnated with natural (gelatin, alginate, and chitosan) and synthetic (polycaprolactone, PCL and poly-lactic acid, PLA) polymers through a dip-coating process. Mechanical enhancement provided by these coatings in terms of both compressive strength and strain energy density was evaluated. Natural polymers, in general, and chitosan, in particular, were found to produce the greater reinforcement. The effect of these coatings on the in vitro bioactivity and degradation behavior of 45S5 bioglass robocast scaffolds was also investigated through immersion tests in simulated body fluid (SBF). Coatings from natural polymers, especially chitosan, are shown to have a positive effect on the bioactivity of 45S5 bioglass, accelerating the formation of an apatite-like layer. Besides, most coating compositions reduced the degradation (weight loss) rate of the scaffold, which has a positive impact on the evolution of their mechanical properties. Copyright © 2018 Elsevier Ltd. All rights reserved.

Facile synthesis of main-chain degradable block copolymers for performance enhanced dismantlable adhesion.

PubMed

Sato, Eriko; Hagihara, Takashi; Matsumoto, Akikazu

2012-04-01

Block copolymers consisting of readily degradable polyperoxides and non-degradable vinyl polymers as the block segments were successfully synthesized by reversible chain transfer catalyzed polymerization, which is one of living radical polymerization techniques. The block copolymers showed characteristic morphology and wettability being different from the polymer blends. When block copolymers containing polyperoxide and polymethacrylate blocks were heated below 150 °C, the polyperoxide blocks were completely degraded and the polymethacrylate blocks were recovered without degradation. Block copolymers containing a poly(2-ethylhexyl methacrylate) block were then investigated as a dismantlable adhesion material, which requires adequate bonding strength during use and easy debonding on demand. Among the several block copolymers, the one consisting of poly(2-ethylhexyl methacrylate) and polyperoxide from methyl sorbate (PPMS) (M(n) = 4900) exhibited good performance as a pressure-sensitive adhesive (PSA). After heating the test specimens in a temperature range from 60 to 100 °C, PSA performance, which was evaluated by 180° peel strength and shear holding power measurements, was significantly diminished. Especially, after heating at 100 °C for 1 h, spontaneous debonding of some test specimens was observed because of the evolution of volatile acetaldehyde from PPMS.

Interplanetary density models as inferred from solar Type III bursts

NASA Astrophysics Data System (ADS)

Oppeneiger, Lucas; Boudjada, Mohammed Y.; Lammer, Helmut; Lichtenegger, Herbert

2016-04-01

We report on the density models derived from spectral features of solar Type III bursts. They are generated by beams of electrons travelling outward from the Sun along open magnetic field lines. Electrons generate Langmuir waves at the plasma frequency along their ray paths through the corona and the interplanetary medium. A large frequency band is covered by the Type III bursts from several MHz down to few kHz. In this analysis, we consider the previous empirical density models proposed to describe the electron density in the interplanetary medium. We show that those models are mainly based on the analysis of Type III bursts generated in the interplanetary medium and observed by satellites (e.g. RAE, HELIOS, VOYAGER, ULYSSES,WIND). Those models are confronted to stereoscopic observations of Type III bursts recorded by WIND, ULYSSES and CASSINI spacecraft. We discuss the spatial evolution of the electron beam along the interplanetary medium where the trajectory is an Archimedean spiral. We show that the electron beams and the source locations are depending on the choose of the empirical density models.

Bipartite Structure of the 5s Ribosomal Gene Family in a Drosophila Melanogaster Strain, and Its Evolutionary Implications

PubMed Central

Samson, M. L.; Wegnez, M.

1988-01-01

Knowledge of multigenic family organization should provide insight into their mode of evolution. Accordingly, we characterized the 5S ribosomal gene family in the Drosophila melanogaster strain ry(506). The 5S genes in this strain display a striking HindIII restriction difference compared to the ``standard'' D. melanogaster 5S genes. The sequence of three ry(506) 5S genes was determined. We show that the HindIII restriction site heterogeneity within the ry(506) 5S family most probably results from the same point mutation, suggesting that a single 5S variant was propagated into the 5S cluster of this strain. Furthermore, we demonstrate that the structural organization of the 5S genes in ry(506) is a bipartite structure, i.e., that about 40% of the 5S genes constitute a HindIII(+)/HindIII(-) mixed cluster, while those remaining constitute an homogeneous HindIII(-) cluster. The events which might lead to such an heterogeneous pattern are discussed from an evolutionary point of view. PMID:2835290

Structure, Evolution, and Functions of Bacterial Type III Toxin-Antitoxin Systems.

PubMed

Goeders, Nathalie; Chai, Ray; Chen, Bihe; Day, Andrew; Salmond, George P C

2016-09-28

Toxin-antitoxin (TA) systems are small genetic modules that encode a toxin (that targets an essential cellular process) and an antitoxin that neutralises or suppresses the deleterious effect of the toxin. Based on the molecular nature of the toxin and antitoxin components, TA systems are categorised into different types. Type III TA systems, the focus of this review, are composed of a toxic endoribonuclease neutralised by a non-coding RNA antitoxin in a pseudoknotted configuration. Bioinformatic analysis shows that the Type III systems can be classified into subtypes. These TA systems were originally discovered through a phage resistance phenotype arising due to a process akin to an altruistic suicide; the phenomenon of abortive infection. Some Type III TA systems are bifunctional and can stabilise plasmids during vegetative growth and sporulation. Features particular to Type III systems are explored here, emphasising some of the characteristics of the RNA antitoxin and how these may affect the co-evolutionary relationship between toxins and cognate antitoxins in their quaternary structures. Finally, an updated analysis of the distribution and diversity of these systems are presented and discussed.

Structure, Evolution, and Functions of Bacterial Type III Toxin-Antitoxin Systems

PubMed Central

Goeders, Nathalie; Chai, Ray; Chen, Bihe; Day, Andrew; Salmond, George P. C.

2016-01-01

Toxin-antitoxin (TA) systems are small genetic modules that encode a toxin (that targets an essential cellular process) and an antitoxin that neutralises or suppresses the deleterious effect of the toxin. Based on the molecular nature of the toxin and antitoxin components, TA systems are categorised into different types. Type III TA systems, the focus of this review, are composed of a toxic endoribonuclease neutralised by a non-coding RNA antitoxin in a pseudoknotted configuration. Bioinformatic analysis shows that the Type III systems can be classified into subtypes. These TA systems were originally discovered through a phage resistance phenotype arising due to a process akin to an altruistic suicide; the phenomenon of abortive infection. Some Type III TA systems are bifunctional and can stabilise plasmids during vegetative growth and sporulation. Features particular to Type III systems are explored here, emphasising some of the characteristics of the RNA antitoxin and how these may affect the co-evolutionary relationship between toxins and cognate antitoxins in their quaternary structures. Finally, an updated analysis of the distribution and diversity of these systems are presented and discussed. PMID:27690100

Analysis of the temporal effects on grating evolution in photopolymer

NASA Astrophysics Data System (ADS)

Kelly, John V.; Gleeson, Michael R.; Close, Ciara E.; O'Neill, Feidhlim T.; Sheridan, John T.; Gallego, Sergi; Neipp, Cristian

2006-04-01

The nonlocal polymerization driven diffusion model is used to describe holographic grating formation in acrylamidebased photopolymer. The free radical chain polymerization process results in polymer being generated nonlocal both in space and time to the point of chain initiation. A Gaussian spatial material response function and an exponential temporal material response function are used to account for these effects. In this paper we firstly examine the nature of the temporal evolution of grating formation for short recording periods. It is shown that in this case, temporal effects become most notable and the inclusion of the nonlocal temporal response function is shown to be necessary to accurately describe the process. In particular, brief post exposure selfamplification of the refractive index modulation is noted. This is attributed to continued chain growth for a brief period after exposure. Following this a slight decay in the grating amplitude also occurs. This we believe is due to the continued diffusion of monomer after exposure. Since the sinusoidal recording pattern generates a monomer concentration gradient during the recording process monomer diffusion occurs both during and after exposure. The evolution of the refractive index modulation is determined by the respective refractive index values of the recording material components. From independent measurements it is noted that the refractive index value of the monomer is slightly less than that of the background material. Therefore as monomer diffuses back into the dark regions, a reduction in overall refractive index modulation occurs. Volume changes occurring within the material also affect the nature of grating evolution. To model these effects we employ a free volume concept. Due to the fact that the covalent single carbon bond in the polymer is up to 50% shorter than the van der Waals bond in the liquid monomer state, free volume is created when monomer is converted to polymer. For each bond conversion we assume a hole is generated which then collapses at some characteristic rate constant. Incorporating each of these effects into our model, the model is then solved using a Finite-Difference Time- Domain method (FDTD). The Lorentz-Lorenz relation is used to determine the overall evolution refractive index modulation and the corresponding diffraction efficiency of the resulting grating is calculated using Rigorous Coupled Wave Analysis (RCWA). Fits are then carried out to experimental data for 1 second exposures. Good quality fits are achieved and material parameters extracted. Monomer diffusion rates are determined to be of the order of D ~ 10 -10 cm 2/s and the time constant of the nonlocal material temporal response function being of the order of τ n ~ 10 -2s. Material shrinkage occurring over these recording periods is also determined.

Spatially resolved quantitative mapping of thermomechanical properties and phase transition temperatures using scanning probe microscopy

DOEpatents

Jesse, Stephen; Kalinin, Sergei V; Nikiforov, Maxim P

2013-07-09

An approach for the thermomechanical characterization of phase transitions in polymeric materials (polyethyleneterephthalate) by band excitation acoustic force microscopy is developed. This methodology allows the independent measurement of resonance frequency, Q factor, and oscillation amplitude of a tip-surface contact area as a function of tip temperature, from which the thermal evolution of tip-surface spring constant and mechanical dissipation can be extracted. A heating protocol maintained a constant tip-surface contact area and constant contact force, thereby allowing for reproducible measurements and quantitative extraction of material properties including temperature dependence of indentation-based elastic and loss moduli.

Prebiotic chemistry and nucleic acid replication

NASA Technical Reports Server (NTRS)

Orgel, L. E.; Lohrmann, R.

1974-01-01

Recent work is reviewed on some reactions that could have occurred on the primitive earth and that could have played a part in the evolution of a self-replicating system. The transition from the primitive atmosphere to the simplest replicating molecules is considered in four stages: (1) the formation of a 'prebiotic soup' of organic precursors, including the purine and pyrimidine bases and the pentose sugars; (2) the condensation of these precursors and inorganic phosphate to form monomeric nucleotides and activated nucleotide derivatives; (3) the polymerization of nucleotide derivatives to oligonucleotides; and (4) the complementary replication of oligonucleotides in a template-directed process that depends on Watson-Crick base pairing.

PUFoam : A novel open-source CFD solver for the simulation of polyurethane foams

NASA Astrophysics Data System (ADS)

Karimi, M.; Droghetti, H.; Marchisio, D. L.

2017-08-01

In this work a transient three-dimensional mathematical model is formulated and validated for the simulation of polyurethane (PU) foams. The model is based on computational fluid dynamics (CFD) and is coupled with a population balance equation (PBE) to describe the evolution of the gas bubbles/cells within the PU foam. The front face of the expanding foam is monitored on the basis of the volume-of-fluid (VOF) method using a compressible solver available in OpenFOAM version 3.0.1. The solver is additionally supplemented to include the PBE, solved with the quadrature method of moments (QMOM), the polymerization kinetics, an adequate rheological model and a simple model for the foam thermal conductivity. The new solver is labelled as PUFoam and is, for the first time in this work, validated for 12 different mixing-cup experiments. Comparison of the time evolution of the predicted and experimentally measured density and temperature of the PU foam shows the potentials and limitations of the approach.

Kinetic control over pathway complexity in supramolecular polymerization through modulating the energy landscape by rational molecular design.

PubMed

Ogi, Soichiro; Fukui, Tomoya; Jue, Melinda L; Takeuchi, Masayuki; Sugiyasu, Kazunori

2014-12-22

Far-from-equilibrium thermodynamic systems that are established as a consequence of coupled equilibria are the origin of the complex behavior of biological systems. Therefore, research in supramolecular chemistry has recently been shifting emphasis from a thermodynamic standpoint to a kinetic one; however, control over the complex kinetic processes is still in its infancy. Herein, we report our attempt to control the time evolution of supramolecular assembly in a process in which the supramolecular assembly transforms from a J-aggregate to an H-aggregate over time. The transformation proceeds through a delicate interplay of these two aggregation pathways. We have succeeded in modulating the energy landscape of the respective aggregates by a rational molecular design. On the basis of this understanding of the energy landscape, programming of the time evolution was achieved through adjusting the balance between the coupled equilibria. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Chemical constraints on the contribution of population III stars to cosmic reionization

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

Kulkarni, Girish; Hennawi, Joseph F.; Rollinde, Emmanuel

2014-05-20

Recent studies have highlighted that galaxies at z = 6-8 fall short of producing enough ionizing photons to reionize the intergalactic medium, and suggest that Population III stars could resolve this tension, because their harder spectra can produce ∼10 × more ionizing photons than Population II. We use a semi-analytic model of galaxy formation, which tracks galactic chemical evolution, to gauge the impact of Population III stars on reionization. Population III supernovae produce distinct metal abundances, and we argue that the duration of the Population III era can be constrained by precise relative abundance measurements in high-z damped Lyα absorbersmore » (DLAs), which provide a chemical record of past star formation. We find that a single generation of Population III stars can self-enrich galaxies above the critical metallicity Z {sub crit} = 10{sup –4} Z {sub ☉} for the Population III-to-II transition, on a very short timescale t {sub self-enrich} ∼ 10{sup 6} yr, owing to the large metal yields and short lifetimes of Population III stars. This subsequently terminates the Population III era, so they contribute ≳ 50% of the ionizing photons only for z ≳ 30, and at z = 10 contribute <1%. The Population III contribution can be increased by delaying metal mixing into the interstellar medium. However, comparing the resulting metal abundance pattern to existing measurements in z ≲ 6 DLAs, we show that the observed [O/Si] ratios of absorbers rule out Population III stars being a major contributor to reionization. Future abundance measurements of z ∼ 7-8 QSOs and gamma-ray bursts should probe the era when the chemical vestiges of Population III star formation become detectable.« less

The Cosmic Century

NASA Astrophysics Data System (ADS)

Longair, Malcolm S.

2013-04-01

Part I. Stars and Stellar Evolution up to the Second World War: 1. The legacy of the nineteenth century; 2. The classification of stellar spectra; 3. Stellar structure and evolution; 4. The end points of stellar evolution; Part II. The Large-Scale Structure of the Universe, 1900-1939: 5. The Galaxy and the nature of spiral nebulae; 6. The origins of astrophysical cosmology; Part III. The Opening up of the Electromagnetic Spectrum: 7. The opening up of the electromagnetic spectrum and the new astronomies; Part IV. The Astrophysics of Stars and Galaxies since 1945: 8. Stars and stellar evolution; 9. The physics of the interstellar medium; 10. The physics of galaxies and clusters of galaxies; 11. High-energy astrophysics; Part V. Astrophysical Cosmology since 1945: 12. Astrophysical cosmology; 13. The determination of cosmological parameters; 14. The evolution of galaxies and active galaxies with cosmic epoch; 15. The origin of galaxies and the large-scale structure of the Universe; 16. The very early Universe; References; Name index; Object index; Subject index.

Synthetic Strategies in the Preparation of Polymer/Inorganic Hybrid Nanoparticles

PubMed Central

Hood, Matthew A.; Mari, Margherita; Muñoz-Espí, Rafael

2014-01-01

This article reviews the recent advances and challenges in the preparation of polymer/inorganic hybrid nanoparticles. We mainly focus on synthetic strategies, basing our classification on whether the inorganic and the polymer components have been formed in situ or ex situ, of the hybrid material. Accordingly, four types of strategies are identified and described, referring to recent examples: (i) ex situ formation of the components and subsequent attachment or integration, either by covalent or noncovalent bonding; (ii) in situ polymerization in the presence of ex situ formed inorganic nanoparticles; (iii) in situ precipitation of the inorganic components on or in polymer structures; and (iv) strategies in which both polymer and inorganic component are simultaneously formed in situ. PMID:28788665

Desmin filaments studied by quasi-elastic light scattering.

PubMed Central

Hohenadl, M; Storz, T; Kirpal, H; Kroy, K; Merkel, R

1999-01-01

We studied polymers of desmin, a muscle-specific type III intermediate filament protein, using quasi-elastic light scattering. Desmin was purified from chicken gizzard. Polymerization was induced either by 2 mM MgCl(2) or 150 mM NaCl. The polymer solutions were in the semidilute regime. We concluded that the persistence length of the filaments is between 0.1 and 1 microm. In all cases, we found a hydrodynamic diameter of desmin filaments of 16-18 nm. The filament dynamics exhibits a characteristic frequency in the sense that correlation functions measured on one sample but at different scattering vectors collapse onto a single master curve when time is normalized by the experimentally determined initial decay rate. PMID:10512839

Exploring gene-culture interactions: insights from handedness, sexual selection and niche-construction case studies.

PubMed

Laland, Kevin N

2008-11-12

Genes and culture represent two streams of inheritance that for millions of years have flowed down the generations and interacted. Genetic propensities, expressed throughout development, influence what cultural organisms learn. Culturally transmitted information, expressed in behaviour and artefacts, spreads through populations, modifying selection acting back on populations. Drawing on three case studies, I will illustrate how this gene-culture coevolution has played a critical role in human evolution. These studies explore (i) the evolution of handedness, (ii) sexual selection with a culturally transmitted mating preference, and (iii) cultural niche construction and human evolution. These analyses shed light on how genes and culture shape each other, and on the significance of feedback mechanisms between biological and cultural processes.

Phylogenetic and Evolutionary Patterns in Microbial Carotenoid Biosynthesis Are Revealed by Comparative Genomics

PubMed Central

Klassen, Jonathan L.

2010-01-01

Background Carotenoids are multifunctional, taxonomically widespread and biotechnologically important pigments. Their biosynthesis serves as a model system for understanding the evolution of secondary metabolism. Microbial carotenoid diversity and evolution has hitherto been analyzed primarily from structural and biosynthetic perspectives, with the few phylogenetic analyses of microbial carotenoid biosynthetic proteins using either used limited datasets or lacking methodological rigor. Given the recent accumulation of microbial genome sequences, a reappraisal of microbial carotenoid biosynthetic diversity and evolution from the perspective of comparative genomics is warranted to validate and complement models of microbial carotenoid diversity and evolution based upon structural and biosynthetic data. Methodology/Principal Findings Comparative genomics were used to identify and analyze in silico microbial carotenoid biosynthetic pathways. Four major phylogenetic lineages of carotenoid biosynthesis are suggested composed of: (i) Proteobacteria; (ii) Firmicutes; (iii) Chlorobi, Cyanobacteria and photosynthetic eukaryotes; and (iv) Archaea, Bacteroidetes and two separate sub-lineages of Actinobacteria. Using this phylogenetic framework, specific evolutionary mechanisms are proposed for carotenoid desaturase CrtI-family enzymes and carotenoid cyclases. Several phylogenetic lineage-specific evolutionary mechanisms are also suggested, including: (i) horizontal gene transfer; (ii) gene acquisition followed by differential gene loss; (iii) co-evolution with other biochemical structures such as proteorhodopsins; and (iv) positive selection. Conclusions/Significance Comparative genomics analyses of microbial carotenoid biosynthetic proteins indicate a much greater taxonomic diversity then that identified based on structural and biosynthetic data, and divides microbial carotenoid biosynthesis into several, well-supported phylogenetic lineages not evident previously. This phylogenetic framework is applicable to understanding the evolution of specific carotenoid biosynthetic proteins or the unique characteristics of carotenoid biosynthetic evolution in a specific phylogenetic lineage. Together, these analyses suggest a “bramble” model for microbial carotenoid biosynthesis whereby later biosynthetic steps exhibit greater evolutionary plasticity and reticulation compared to those closer to the biosynthetic “root”. Structural diversification may be constrained (“trimmed”) where selection is strong, but less so where selection is weaker. These analyses also highlight likely productive avenues for future research and bioprospecting by identifying both gaps in current knowledge and taxa which may particularly facilitate carotenoid diversification. PMID:20582313

Fragmentation during primordial star formation

NASA Astrophysics Data System (ADS)

Dutta, Jayanta

Understanding the physics of the very first stars in the universe, the so-called Population III (or Pop III) stars, is crucial in determining how the universe evolved into what we observe today. In the standard model of Pop III star formation, the baryonic matter, mainly atomic hydrogen, collapses gravitationally into small Dark Matter (DM) minihalos. However, so far there is little understanding on how the thermal, dynamical and chemical evolution of the primordial gas depend on the initial configuration of the minihalos (for example, rotation of the unstable clumps inside minihalos, turbulence, formation of molecular hydrogen and cosmic variance of the minihalos). We use the modified version of the Gadget-2 code, a three-dimensional smoothed particle hydrodynamics (SPH) simulations, to follow the evolution of the collapsing gas in both idealized as well as more realistic minihalos. Unlike some earlier cosmological calculations, the implementation of sink particles allows us to follow the evolution of the accretion disk that builds up in the centre of each minihalo and fragments. We find that the fragmentation behavior depends on the adopted choice of three-body H2 formation rate coefficient. The increasing cooling rate during rapid conversion of the atomic to molecular hydrogen is offset by the heating due to gas contraction. We propose that the H2 cooling, the heating due to H2 formation and compressional heating together set a density and temperature structure in the disk that favors fragmentation. We also find that the cloud's initial degree of rotation has a significant effect on the thermal and dynamical evolution of the collapsing gas. Clouds with higher rotation exhibit spiral-arm-like structures that become gravitationally unstable to fragmentation on several scales. These type of clouds tend to fragment more and have lower accretion rates compared to their slowly rotating counterparts. In addition, we find that the distribution of specific angular momentum (L) of the gas follows a power-law relation with the enclosed gas mass (M), L ∝ M1.125, which is controlled by the gravitational and pressure torque, and does not depend on the cloud's initial degree of rotation and turbulence.

Anisotropic Bianchi type-III model in Palatini f (R) gravity

NASA Astrophysics Data System (ADS)

Banik, Debika Kangsha; Banik, Sebika Kangsha; Bhuyan, Kalyan

2017-03-01

We derive exact solutions for anisotropic Bianchi type-III cosmological model in the Palatini formalism of f (R) gravity using Dynamical System Approach. For the f (R) of the form f(R) =R-β /Rn and f(R) =R+α Rm , we have found the fixed points describing the radiation-dominated, matter dominated and de Sitter evolution periods. Fixed points have also been found which have non-vanishing shear playing a very significant role in describing the anisotropy present in the early universe. In addition, we have also found that the spatial curvature affect isotropisation of this cosmological model.

Radical-Mediated Enzymatic Polymerizations

PubMed Central

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

2016-01-01

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

Experimental evolution in biofilm populations

PubMed Central

Steenackers, Hans P.; Parijs, Ilse; Foster, Kevin R.; Vanderleyden, Jozef

2016-01-01

Biofilms are a major form of microbial life in which cells form dense surface associated communities that can persist for many generations. The long-life of biofilm communities means that they can be strongly shaped by evolutionary processes. Here, we review the experimental study of evolution in biofilm communities. We first provide an overview of the different experimental models used to study biofilm evolution and their associated advantages and disadvantages. We then illustrate the vast amount of diversification observed during biofilm evolution, and we discuss (i) potential ecological and evolutionary processes behind the observed diversification, (ii) recent insights into the genetics of adaptive diversification, (iii) the striking degree of parallelism between evolution experiments and real-life biofilms and (iv) potential consequences of diversification. In the second part, we discuss the insights provided by evolution experiments in how biofilm growth and structure can promote cooperative phenotypes. Overall, our analysis points to an important role of biofilm diversification and cooperation in bacterial survival and productivity. Deeper understanding of both processes is of key importance to design improved antimicrobial strategies and diagnostic techniques. PMID:26895713

Experimental evolution in biofilm populations.

PubMed

Steenackers, Hans P; Parijs, Ilse; Dubey, Akanksha; Foster, Kevin R; Vanderleyden, Jozef

2016-05-01

Biofilms are a major form of microbial life in which cells form dense surface associated communities that can persist for many generations. The long-life of biofilm communities means that they can be strongly shaped by evolutionary processes. Here, we review the experimental study of evolution in biofilm communities. We first provide an overview of the different experimental models used to study biofilm evolution and their associated advantages and disadvantages. We then illustrate the vast amount of diversification observed during biofilm evolution, and we discuss (i) potential ecological and evolutionary processes behind the observed diversification, (ii) recent insights into the genetics of adaptive diversification, (iii) the striking degree of parallelism between evolution experiments and real-life biofilms and (iv) potential consequences of diversification. In the second part, we discuss the insights provided by evolution experiments in how biofilm growth and structure can promote cooperative phenotypes. Overall, our analysis points to an important role of biofilm diversification and cooperation in bacterial survival and productivity. Deeper understanding of both processes is of key importance to design improved antimicrobial strategies and diagnostic techniques. © FEMS 2016.

21 CFR 177.2250 - Filters, microporous polymeric.

Code of Federal Regulations, 2014 CFR

2014-04-01

... 21 Food and Drugs 3 2014-04-01 2014-04-01 false Filters, microporous polymeric. 177.2250 Section... Repeated Use § 177.2250 Filters, microporous polymeric. Microporous polymeric filters identified in... liquid food. (a) Microporous polymeric filters consist of a suitably permeable, continuous, polymeric...

Photo-responsive polymeric micelles.

PubMed

Huang, Yu; Dong, Ruijiao; Zhu, Xinyuan; Yan, Deyue

2014-09-07

Photo-responsive polymeric micelles have received increasing attention in both academic and industrial fields due to their efficient photo-sensitive nature and unique nanostructure. In view of the photo-reaction mechanism, photo-responsive polymeric micelles can be divided into five major types: (1) photoisomerization polymeric micelles, (2) photo-induced rearrangement polymeric micelles, (3) photocleavage polymeric micelles, (4) photo-induced crosslinkable polymeric micelles, and (5) photo-induced energy conversion polymeric micelles. This review highlights the recent advances of photo-responsive polymeric micelles, including the design, synthesis and applications in various biomedical fields. Especially, the influence of different photo-reaction mechanisms on the morphology, structure and properties of the polymeric micelles is emphasized. Finally, the possible future directions and perspectives in this emerging area are briefly discussed.

Body composition in Pan paniscus compared with Homo sapiens has implications for changes during human evolution.

PubMed

Zihlman, Adrienne L; Bolter, Debra R

2015-06-16

The human body has been shaped by natural selection during the past 4-5 million years. Fossils preserve bones and teeth but lack muscle, skin, fat, and organs. To understand the evolution of the human form, information about both soft and hard tissues of our ancestors is needed. Our closest living relatives of the genus Pan provide the best comparative model to those ancestors. Here, we present data on the body composition of 13 bonobos (Pan paniscus) measured during anatomical dissections and compare the data with Homo sapiens. These comparative data suggest that both females and males (i) increased body fat, (ii) decreased relative muscle mass, (iii) redistributed muscle mass to lower limbs, and (iv) decreased relative mass of skin during human evolution. Comparison of soft tissues between Pan and Homo provides new insights into the function and evolution of body composition.

Clonal evolution of chemotherapy-resistant urothelial carcinoma.

PubMed

Faltas, Bishoy M; Prandi, Davide; Tagawa, Scott T; Molina, Ana M; Nanus, David M; Sternberg, Cora; Rosenberg, Jonathan; Mosquera, Juan Miguel; Robinson, Brian; Elemento, Olivier; Sboner, Andrea; Beltran, Himisha; Demichelis, Francesca; Rubin, Mark A

2016-12-01

Chemotherapy-resistant urothelial carcinoma has no uniformly curative therapy. Understanding how selective pressure from chemotherapy directs the evolution of urothelial carcinoma and shapes its clonal architecture is a central biological question with clinical implications. To address this question, we performed whole-exome sequencing and clonality analysis of 72 urothelial carcinoma samples, including 16 matched sets of primary and advanced tumors prospectively collected before and after chemotherapy. Our analysis provided several insights: (i) chemotherapy-treated urothelial carcinoma is characterized by intra-patient mutational heterogeneity, and the majority of mutations are not shared; (ii) both branching evolution and metastatic spread are very early events in the natural history of urothelial carcinoma; (iii) chemotherapy-treated urothelial carcinoma is enriched with clonal mutations involving L1 cell adhesion molecule (L1CAM) and integrin signaling pathways; and (iv) APOBEC-induced mutagenesis is clonally enriched in chemotherapy-treated urothelial carcinoma and continues to shape the evolution of urothelial carcinoma throughout its lifetime.

Clonal Evolution of Chemotherapy-resistant Urothelial Carcinoma

PubMed Central

Faltas, Bishoy M.; Prandi, Davide; Tagawa, Scott T.; Molina, Ana M.; Nanus, David M.; Sternberg, Cora; Rosenberg, Jonathan; Mosquera, Juan Miguel; Robinson, Brian; Elemento, Olivier; Sboner, Andrea; Beltran, Himisha; Demichelis, Francesca; Rubin, Mark A.

2017-01-01

Chemotherapy-resistant urothelial carcinoma (UC) has no uniformly curative therapy. Understanding how selective pressure from chemotherapy directs UC’s evolution and shapes its clonal architecture is a central biological question with clinical implications. To address this question, we performed whole-exome sequencing and clonality analysis of 72 UCs including 16 matched sets of primary and advanced tumors prospectively collected before and after chemotherapy. Our analysis provided several insights: (i) chemotherapy-treated UC is characterized by intra-patient mutational heterogeneity and the majority of mutations are not shared, (ii) both branching evolution and metastatic spread are very early events in the natural history of UC; (iii) chemotherapy-treated UC is enriched with clonal mutations involving L1-cell adhesion molecule (L1CAM) and integrin signaling pathways; (iv) APOBEC induced-mutagenesis is clonally-enriched in chemotherapy-treated UC and continues to shape UC’s evolution throughout its lifetime. PMID:27749842

Body composition in Pan paniscus compared with Homo sapiens has implications for changes during human evolution

PubMed Central

Zihlman, Adrienne L.; Bolter, Debra R.

2015-01-01

The human body has been shaped by natural selection during the past 4–5 million years. Fossils preserve bones and teeth but lack muscle, skin, fat, and organs. To understand the evolution of the human form, information about both soft and hard tissues of our ancestors is needed. Our closest living relatives of the genus Pan provide the best comparative model to those ancestors. Here, we present data on the body composition of 13 bonobos (Pan paniscus) measured during anatomical dissections and compare the data with Homo sapiens. These comparative data suggest that both females and males (i) increased body fat, (ii) decreased relative muscle mass, (iii) redistributed muscle mass to lower limbs, and (iv) decreased relative mass of skin during human evolution. Comparison of soft tissues between Pan and Homo provides new insights into the function and evolution of body composition. PMID:26034269

Feature Profile Evolution of SiO2 Trenches In Fluorocarbon Plasmas

NASA Technical Reports Server (NTRS)

Hwang, Helen; Govindan, T. R.; Meyyappan, M.; Arunachalam, Valli; Rauf, Shahid; Coronell, Dan; Carroll, Carol W. (Technical Monitor)

1999-01-01

Etching of silicon microstructures for semiconductor manufacturing in chlorine plasmas has been well characterized. The etching proceeds in a two-part process, where the chlorine neutrals passivate the Si surface and then the ions etch away SiClx. However, etching in more complicated gas mixtures and materials, such as etching of SiO2 in Ar/C4F8, requires knowledge of the ion and neutral distribution functions as a function of angle and velocity, in addition to modeling the gas surface reactions. In order to address these needs, we have developed and integrated a suite of models to simulate the etching process from the plasma reactor level to the feature profile evolution level. This arrangement allows for a better understanding, control, and prediction of the influence of equipment level process parameters on feature profile evolution. We are currently using the HPEM (Hybrid Plasma Equipment Model) and PCMCM (Plasma Chemistry Monte Carlo Model) to generate plasma properties and ion and neutral distribution functions for argon/fluorocarbon discharges in a GEC Reference Cell. These quantities are then input to the feature scale model, Simulation of Profile Evolution by Level Sets (SPELS). A surface chemistry model is used to determine the interaction of the incoming species with the substrate material and simulate the evolution of the trench profile. The impact of change of gas pressure and inductive power on the relative flux of CFx and F to the wafer, the etch and polymerization rates, and feature profiles will be examined. Comparisons to experimental profiles will also be presented.

Chromium(iii) oxidation by biogenic manganese oxides with varying structural ripening.

PubMed

Tang, Yuanzhi; Webb, Samuel M; Estes, Emily R; Hansel, Colleen M

2014-09-20

Manganese (Mn) oxides, which are generally considered biogenic in origin within natural systems, are the only oxidants of Cr(iii) under typical environmental conditions. Yet the influence of Mn biooxide mineral structural evolution on Cr(iii) oxidation under varying geochemical conditions is unknown. In this study we examined the role of light, organic carbon, pH, and the structure of biogenic Mn oxides on Cr(iii) oxidation. Aging of Mn oxides produced by a marine bacterium within the widespread Roseobacter clade resulted in structural ripening from a colloidal hexagonal to a particulate triclinic birnessite phase. The structurally diverse Mn oxides were then reacted with aqueous Cr(iii) within artificial seawater in the presence or absence of carbon and light. Here we found that Cr(iii) oxidation capacity was highest at near neutral pH and in the combined presence of carbon and light. Mn oxide ripening from a hexagonal to a triclinic birnessite phase led to decreased Cr(iii) oxidation in the presence of carbon and light, whereas no change in reactivity was observed in the absence of carbon and/or in the dark. As only minimal Cr(iii) oxidation was observed in the absence of Mn oxides, these results strongly point to coupled Mn oxide- and photo-induced generation of organic and/or oxygen radicals involved in Cr(iii) oxidation. Based on Mn oxide concentration and structural trends, we postulate that Mn(ii) produced from the oxidation of Cr(iii) by the primary Mn oxide is recycled in the presence of organics and light conditions, (re)generating secondary hexagonal birnessite and thereby allowing for continuous oxidation of Cr(iii). In the absence of this Mn oxide regeneration, Cr(iii) induced structural ripening of the hexagonal birnessite precludes further Cr(iii) oxidation. These results highlight the complexity of reactions involved in Mn oxide mediated Cr(iii) oxidation and suggest that photochemical carbon reactions are requisite for sustained Cr(iii) oxidation and persistence of reactive Mn oxides.

A probabilistic damage model of stress-induced permeability anisotropy during cataclastic flow

NASA Astrophysics Data System (ADS)

Zhu, Wenlu; MontéSi, Laurent G. J.; Wong, Teng-Fong

2007-10-01

A fundamental understanding of the effect of stress on permeability evolution is important for many fault mechanics and reservoir engineering problems. Recent laboratory measurements demonstrate that in the cataclastic flow regime, the stress-induced anisotropic reduction of permeability in porous rocks can be separated into 3 different stages. In the elastic regime (stage I), permeability and porosity reduction are solely controlled by the effective mean stress, with negligible permeability anisotropy. Stage II starts at the onset of shear-enhanced compaction, when a critical yield stress is attained. In stage II, the deviatoric stress exerts primary control over permeability and porosity evolution. The increase in deviatoric stress results in drastic permeability and porosity reduction and considerable permeability anisotropy. The transition from stage II to stage III takes place progressively during the development of pervasive cataclastic flow. In stage III, permeability and porosity reduction becomes gradual again, and permeability anisotropy diminishes. Microstructural observations on deformed samples using laser confocal microscopy reveal that stress-induced microcracking and pore collapse are the primary forms of damage during cataclastic flow. A probabilistic damage model is formulated to characterize the effects of stress on permeability and its anisotropy. In our model, the effects of both effective mean stress and differential stress on permeability evolution are calculated. By introducing stress sensitivity coefficients, we propose a first-order description of the dependence of permeability evolution on different loading paths. Built upon the micromechanisms of deformation in porous rocks, this unified model provides new insight into the coupling of stress and permeability.

Models of fold-related hysteresis

NASA Astrophysics Data System (ADS)

Shtern, Vladimir

2018-05-01

Hysteresis is a strongly nonlinear physics phenomenon observed in many fluid mechanics flows. This paper composes evolution equations of the minimal nonlinearity and dimension which describe three hysteresis kinds related to a fold catastrophe formed by (i) two fold bifurcations, (ii) fold and transcritical bifurcations, and (iii) fold and subcritical bifurcations.

Interdisciplinary Studies Program. Teacher's Guide: Part III.

ERIC Educational Resources Information Center

Valencia Community Coll., Orlando, FL.

This teacher's guide was developed for the third of four courses in Valencia Community College's Interdisciplinary Studies program, a 2-year core general education curriculum which chronologically examines the major developments in the evolution of human knowledge. The guide provides an introductory overview of the course's topic (i.e., Western…

The eleventh and twelfth data releases of the Sload Digital Sky Survey: final data from SDSS-III

DOE PAGES

Alam, S.; Slosar, A.; Albareti, F. D.; ...

2015-07-01

The third generation of the Sloan Digital Sky Survey (SDSS-III) took data from 2008 to 2014 using the original SDSS wide-field imager, the original and an upgraded multi-object fiber-fed optical spectrograph, a new near-infrared high-resolution spectrograph, and a novel optical interferometer. All of the data from SDSS-III are now made public. In particular, this paper describes Data Release 11 (DR11) including all data acquired through 2013 July, and Data Release 12 (DR12) adding data acquired through 2014 July (including all data included in previous data releases), marking the end of SDSS-III observing. Relative to our previous public release (DR10), DR12more » adds one million new spectra of galaxies and quasars from the Baryon Oscillation Spectroscopic Survey (BOSS) over an additional 3000 deg 2 of sky, more than triples the number of H-band spectra of stars as part of the Apache Point Observatory (APO) Galactic Evolution Experiment (APOGEE), and includes repeated accurate radial velocity measurements of 5500 stars from the Multi-object APO Radial Velocity Exoplanet Large-area Survey (MARVELS). The APOGEE outputs now include the measured abundances of 15 different elements for each star. In total, SDSS-III added 5200 deg 2 of ugriz imaging; 155,520 spectra of 138,099 stars as part of the Sloan Exploration of Galactic Understanding and Evolution 2 (SEGUE-2) survey; 2,497,484 BOSS spectra of 1,372,737 galaxies, 294,512 quasars, and 247,216 stars over 9376 deg 2; 618,080 APOGEE spectra of 156,593 stars; and 197,040 MARVELS spectra of 5513 stars. Since its first light in 1998, SDSS has imaged over 1/3 of the Celestial sphere in five bands and obtained over five million astronomical spectra.« less

The eleventh and twelfth data release of the Sloan Digital Sky Survey: Final data from SDSS-III

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

Alam, Shadab; Albareti, Franco D.; Prieto, Carlos Allende

2015-07-20

The third generation of the Sloan Digital Sky Survey (SDSS-III) took data from 2008 to 2014 using the original SDSS wide-field imager, the original and an upgraded multi-object fiber-fed optical spectrograph, a new near-infrared high-resolution spectrograph, and a novel optical interferometer. All of the data from SDSS-III are now made public. In particular, this paper describes Data Release 11 (DR11) including all data acquired through 2013 July, and Data Release 12 (DR12) adding data acquired through 2014 July (including all data included in previous data releases), marking the end of SDSS-III observing. Relative to our previous public release (DR10), DR12more » adds one million new spectra of galaxies and quasars from the Baryon Oscillation Spectroscopic Survey (BOSS) over an additional 3000 deg 2 of sky, more than triples the number of H-band spectra of stars as part of the Apache Point Observatory (APO) Galactic Evolution Experiment (APOGEE), and includes repeated accurate radial velocity measurements of 5500 stars from the Multi-object APO Radial Velocity Exoplanet Large-area Survey (MARVELS). The APOGEE outputs now include the measured abundances of 15 different elements for each star. In total, SDSS-III added 5200 deg 2 of ugriz imaging; 155,520 spectra of 138,099 stars as part of the Sloan Exploration of Galactic Understanding and Evolution 2 (SEGUE-2) survey; 2,497,484 BOSS spectra of 1,372,737 galaxies, 294,512 quasars, and 247,216 stars over 9376 deg 2; 618,080 APOGEE spectra of 156,593 stars; and 197,040 MARVELS spectra of 5513 stars. Since its first light in 1998, SDSS has imaged over 1/3 of the Celestial sphere in five bands and obtained over five million astronomical spectra.« less

THE ELEVENTH AND TWELFTH DATA RELEASES OF THE SLOAN DIGITAL SKY SURVEY: FINAL DATA FROM SDSS-III

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

Alam, Shadab; Albareti, Franco D.; Prieto, Carlos Allende

2015-07-15

The third generation of the Sloan Digital Sky Survey (SDSS-III) took data from 2008 to 2014 using the original SDSS wide-field imager, the original and an upgraded multi-object fiber-fed optical spectrograph, a new near-infrared high-resolution spectrograph, and a novel optical interferometer. All of the data from SDSS-III are now made public. In particular, this paper describes Data Release 11 (DR11) including all data acquired through 2013 July, and Data Release 12 (DR12) adding data acquired through 2014 July (including all data included in previous data releases), marking the end of SDSS-III observing. Relative to our previous public release (DR10), DR12more » adds one million new spectra of galaxies and quasars from the Baryon Oscillation Spectroscopic Survey (BOSS) over an additional 3000 deg{sup 2} of sky, more than triples the number of H-band spectra of stars as part of the Apache Point Observatory (APO) Galactic Evolution Experiment (APOGEE), and includes repeated accurate radial velocity measurements of 5500 stars from the Multi-object APO Radial Velocity Exoplanet Large-area Survey (MARVELS). The APOGEE outputs now include the measured abundances of 15 different elements for each star. In total, SDSS-III added 5200 deg{sup 2} of ugriz imaging; 155,520 spectra of 138,099 stars as part of the Sloan Exploration of Galactic Understanding and Evolution 2 (SEGUE-2) survey; 2,497,484 BOSS spectra of 1,372,737 galaxies, 294,512 quasars, and 247,216 stars over 9376 deg{sup 2}; 618,080 APOGEE spectra of 156,593 stars; and 197,040 MARVELS spectra of 5513 stars. Since its first light in 1998, SDSS has imaged over 1/3 of the Celestial sphere in five bands and obtained over five million astronomical spectra.« less

Evolution of Class III treatment in orthodontics.

PubMed

Ngan, Peter; Moon, Won

2015-07-01

Angle, Tweed, and Moyers classified Class III malocclusions into 3 types: pseudo, dentoalveolar, and skeletal. Clinicians have been trying to identify the best timing to intercept a Class III malocclusion that develops as early as the deciduous dentition. With microimplants as skeletal anchorage, orthopedic growth modification became more effective, and it also increased the scope of camouflage orthodontic treatment for patients who were not eligible for orthognathic surgery. However, orthodontic treatment combined with orthognathic surgery remains the only option for patients with a severe skeletal Class III malocclusion or a craniofacial anomaly. Distraction osteogenesis can now be performed intraorally at an earlier age. The surgery-first approach can minimize the length of time that the malocclusion needs to worsen before orthognathic surgery. Finally, the use of computed tomography scans for 3-dimensional diagnosis and treatment planning together with advances in imaging technology can improve the accuracy of surgical movements and the esthetic outcomes for these patients. Copyright © 2015 American Association of Orthodontists. Published by Elsevier Inc. All rights reserved.

Comparison of toxicity rankings of six aircraft cabin polymers by lethality and by incapacitation in rats.

PubMed

Sanders, D C; Endecott, B R; Chaturvedi, A K

1992-10-01

Polymeric aircraft cabin materials have the potential to produce toxic gases in fires. Lethality (LC50) in animal models is a standard index to rank polymers on the basis of their combustion toxicity. However, the use of times-to-incapacitation (ti) may be more realistic for predicting relative escape times from a fire. Therefore, LC50 and ti for polymers, polyamide (I), polystyrene (II), Nylon 6/6 (III), polysulfone (IV), polyethylene (V) and chlorinated polyethylene (VI), of different chemical classes were determined and compared. Male rats, 12/fuel loading, were exposed to the pyrolysis products from selected weights of each polymer for 30 min in a 265-L combustion/exposure system, and LC50 values were determined following a 14-d observation period. For each polymer, ti was measured at 16 g and at its respective LC50 using the inability of rats (n greater than or equal to 12) to walk in rotating cages as a criterion for incapacitation. LC50 (45.7-87.5 mg/L) of the polymers had the order of I less than II approximately III less than IV less than V less than VI, while their ti (6.6-21.1 min) at 16 g (60 mg/L) had the order of III approximately I less than V approximately II less than VI less than IV. Based on ti at LC50, polymers were grouped into III & V; I, II & VI; and IV. LC50 and ti did not exhibit the same relative toxic hazard rankings for these polymers; ti were also not equal at the LC50 concentrations. These findings demonstrate the possible involvement of different mechanisms of action for the combustion products of these polymers at the selected end points.

Fluoride-selective optical sensor based on aluminum(III)-octaethylporphyrin in thin polymeric film: further characterization and practical application.

PubMed

Badr, Ibrahim H A; Meyerhoff, Mark E

2005-10-15

More detailed analytical studies of a new fluoride-selective optical sensor based on the use of aluminum(III)-octaethylporphyrin and a lipophilic pH indicator (4',5'-dibromofluorescein octadecyl ester; ETH-7075) within a thin plasticized poly(vinyl chloride) film are reported. The sensor exhibits extraordinary optical selectivity for fluoride over a wide range of other anions, including anions with far more positive free energies of hydration (e.g., perchlorate, thiocyanate, nitrate, etc.). UV-visible spectrophotometric studies of the sensing films indicate that fluoride interacts with the Al(III) center of the porphyrin structure, yielding both a change in the Soret band lambda(max) of the porphyrin and a change in the protonation state of the pH indicator within the film. The same change in spectral properties of the metalloporphyrin occurs in the absence of added pH indicator or with added tetraphenylborate derivative anionic sites, but optical responses to fluoride in these cases are shown to be irreversible. The presence of the pH indicator and the simultaneous fluoride/proton coextraction equilibrium chemistry is shown to greatly enhance the reversibility of fluoride binding to the Al(III) porphyrin. Optical response toward fluoride can be observed in the range of 0.1 microM-1.6 mM. Optical selectivity coefficients of <10(-6) for common anions (e.g., sulfate, chloride, nitrate, etc.) and <10(-4) for perchlorate and thiocyanate are obtained. Measurements of fluoride in drinking water via the new optical sensor are shown to correlate well with values obtained for the same samples using a classical LaF3-based fluoride ion-selective electrode method.

Fluoride Selective Optical Sensor Based on Aluminum(III)-Octaethylporphyrin in Thin Polymeric Film: Further Characterization and Practical Application

PubMed Central

Badr, Ibrahim H. A.; Meyerhoff, Mark E.

2008-01-01

More detailed analytical studies of a new fluoride selective optical sensor based on the use of aluminum(III)-octaethylporphyrin and a lipophilic pH indicator (4′,5′-dibromofluorescein octadecyl ester; ETH-7075) within a thin plasticized poly(vinyl chloride) film are reported. The sensor exhibits extraordinary optical selectivity for fluoride over a wide range of other anions, including anions with far more positive free energies of hydration (e.g., perchlorate, thiocyanate, nitrate, etc.). UV-VIS spectrophotometric studies of the sensing films indicate that fluoride interacts with the Al(III) center of the porphyrin structure, yielding both a change in the Soret band λmax of the porphyrin as well as a change in the protonation state of the pH indicator within the film. The same change in spectral properties of the metalloporphyrin occurs in the absence of added pH indicator or with added tetraphenylborate derivative anionic sites, but optical responses to fluoride in these cases are shown to be irreversible. The presence of the pH indicator and the simultaneous fluoride/proton coextraction equilibrium chemistry is shown to greatly enhance the reversibility of fluoride binding to the Al(III) porphyrin. Optical response toward fluoride can be observed in the range of 0.1 μM to 1.6 mM. Optical selectivity coefficients of < 10−6 for common anions (e.g., sulfate, chloride, nitrate etc.) and < 10−4 for perchlorate and thiocyanate are obtained. Measurements of fluoride in drinking water via the new optical sensor are shown to correlate well with values obtained for the same samples using a classical LaF3 based fluoride ion-selective electrode method. PMID:16223262

Chromium speciation in oxide-type compounds: application to minerals, gems, aqueous solutions and silicate glasses

NASA Astrophysics Data System (ADS)

Farges, François

2009-09-01

Cr K-edge XANES spectra were obtained for a variety of Cr-bearing model compounds containing Cr(II), Cr(III), Cr(IV), Cr(V) and Cr(VI), in which the Cr-site symmetry is D4h, Oh and Td. The centroid position of the pre-edge feature is a better indicator of the Cr valence than the edge position. In Cr-rich oxides, higher-energy transitions must be excluded in order to refine a robust valence for Cr. The pre-edge for chromates is not unique and varies as a function of the CrO4 2- moiety distortion, which is often related to Cr-polymerization (monochromate vs. dichromate). Both the analogy with the Mn K-pre-edge information and ab initio FEFF calculations of the pre-edge feature for Cr(III) and Cr(VI) confirm the experimental trends. This methodology is applied to the Cr K-edge pre-edge feature collected in gems (emerald, spinel and ruby), the layered minerals fuchsite and kämmererite, two Cr-bearing aqueous solutions and a set of sodo-calcic silicate glasses used for bottling sparkling white wine. In emerald and fuchsite, the Cr-site is differently distorted than its ruby or spinel counterpart. In a Cr(III)-bearing aqueous solution and sodo-calcic glass, no evidence for Cr(III) with Td and C3v symmetry is detected. However, minor amounts of chromate moieties (most likely monomeric) are detected in a glass synthesized in air. Preliminary spectra for the wine bottle glass suggest that only trace amounts of chromates might possibly be present in these glasses.

An immuno-wall microdevice exhibits rapid and sensitive detection of IDH1-R132H mutation specific to grade II and III gliomas

PubMed Central

Yamamichi, Akane; Kasama, Toshihiro; Ohka, Fumiharu; Suzuki, Hiromichi; Kato, Akira; Motomura, Kazuya; Hirano, Masaki; Ranjit, Melissa; Chalise, Lushun; Kurimoto, Michihiro; Kondo, Goro; Aoki, Kosuke; Kaji, Noritada; Tokeshi, Manabu; Matsubara, Toshio; Senga, Takeshi; Kaneko, Mika K.; Suzuki, Hidenori; Hara, Masahito; Wakabayashi, Toshihiko; Baba, Yoshinobu; Kato, Yukinari; Natsume, Atsushi

2016-01-01

Abstract World Health Organization grade II and III gliomas most frequently occur in the central nervous system (CNS) in adults. Gliomas are not circumscribed; tumor edges are irregular and consist of tumor cells, normal brain tissue, and hyperplastic reactive glial cells. Therefore, the tumors are not fully resectable, resulting in recurrence, malignant progression, and eventual death. Approximately 69–80% of grade II and III gliomas harbor mutations in the isocitrate dehydrogenase 1 gene (IDH1), of which 83–90% are found to be the IDH1-R132H mutation. Detection of the IDH1-R132H mutation should help in the differential diagnosis of grade II and III gliomas from other types of CNS tumors and help determine the boundary between the tumor and normal brain tissue. In this study, we established a highly sensitive antibody-based device, referred to as the immuno-wall, to detect the IDH1-R132H mutation in gliomas. The immuno-wall causes an immunoreaction in microchannels fabricated using a photo-polymerizing polymer. This microdevice enables the analysis of the IDH1 status with a small sample within 15 min with substantially high sensitivity. Our results suggested that 10% content of the IDH1-R132H mutation in a sample of 0.33 μl volume, with 500 ng protein, or from 500 cells is theoretically sufficient for the analysis. The immuno-wall device will enable the rapid and highly sensitive detection of the IDH1-R132H mutation in routine clinical practice. PMID:27877908

Emerging principles of regulatory evolution.

PubMed

Prud'homme, Benjamin; Gompel, Nicolas; Carroll, Sean B

2007-05-15

Understanding the genetic and molecular mechanisms governing the evolution of morphology is a major challenge in biology. Because most animals share a conserved repertoire of body-building and -patterning genes, morphological diversity appears to evolve primarily through changes in the deployment of these genes during development. The complex expression patterns of developmentally regulated genes are typically controlled by numerous independent cis-regulatory elements (CREs). It has been proposed that morphological evolution relies predominantly on changes in the architecture of gene regulatory networks and in particular on functional changes within CREs. Here, we discuss recent experimental studies that support this hypothesis and reveal some unanticipated features of how regulatory evolution occurs. From this growing body of evidence, we identify three key operating principles underlying regulatory evolution, that is, how regulatory evolution: (i) uses available genetic components in the form of preexisting and active transcription factors and CREs to generate novelty; (ii) minimizes the penalty to overall fitness by introducing discrete changes in gene expression; and (iii) allows interactions to arise among any transcription factor and downstream CRE. These principles endow regulatory evolution with a vast creative potential that accounts for both relatively modest morphological differences among closely related species and more profound anatomical divergences among groups at higher taxonomical levels.

Replaying the tape of life in the twenty-first century.

PubMed

Orgogozo, Virginie

2015-12-06

Should the tape of life be replayed, would it produce similar living beings? A classical answer has long been 'no', but accumulating data are now challenging this view. Repeatability in experimental evolution, in phenotypic evolution of diverse species and in the genes underlying phenotypic evolution indicates that despite unpredictability at the level of basic evolutionary processes (such as apparition of mutations), a certain kind of predictability can emerge at higher levels over long time periods. For instance, a survey of the alleles described in the literature that cause non-deleterious phenotypic differences among animals, plants and yeasts indicates that similar phenotypes have often evolved in distinct taxa through independent mutations in the same genes. Does this mean that the range of possibilities for evolution is limited? Does this mean that we can predict the outcomes of a replayed tape of life? Imagining other possible paths for evolution runs into four important issues: (i) resolving the influence of contingency, (ii) imagining living organisms that are different from the ones we know, (iii) finding the relevant concepts for predicting evolution, and (iv) estimating the probability of occurrence for complex evolutionary events that occurred only once during the evolution of life on earth.

Impact of bariatric surgery on apolipoprotein C-III levels and lipoprotein distribution in obese human subjects.

PubMed

Maraninchi, Marie; Padilla, Nadège; Béliard, Sophie; Berthet, Bruno; Nogueira, Juan-Patricio; Dupont-Roussel, Jeanine; Mancini, Julien; Bégu-Le Corroller, Audrey; Dubois, Noémie; Grangeot, Rachel; Mattei, Catherine; Monclar, Marion; Calabrese, Anastasia; Guérin, Carole; Desmarchelier, Charles; Nicolay, Alain; Xiao, Changting; Borel, Patrick; Lewis, Gary F; Valéro, René

Elevated apolipoprotein C-III (apoC-III) has been postulated to contribute to the atherogenic dyslipidemia seen in obesity and insulin-resistant states, mainly by impairing plasma triglyceride-rich lipoprotein (TRL) metabolism. Bariatric surgery is associated with improvements of several obesity-associated metabolic abnormalities, including a reduction in plasma triglycerides (TGs) and an increase in plasma high-density lipoprotein cholesterol (HDL-C). We investigated the specific effect of bariatric surgery on apoC-III concentrations in plasma, non-HDL, and HDL fractions in relation to lipid profile parameters evolution. A total of 132 obese subjects undergoing bariatric surgery, gastric bypass (n = 61) or sleeve gastrectomy (n = 71), were studied 1 month before surgery and 6 and 12 months after surgery. Plasma apoC-III, non-HDL-apoC-III, and HDL-apoC-III concentrations were markedly reduced after surgery and strongly associated with reduction in plasma TG. This decrease was accompanied by a redistribution of apoC-III from TRL to HDL fractions. In multivariate analysis, plasma apoC-III was the strongest predictor of TG reduction after surgery, and the increase of HDL-C was positively associated with plasma adiponectin and negatively with body mass index. Marked reduction of apoC-III and changes in its distribution between TRL and HDL consistent with a better lipid profile are achieved in obese patients after bariatric surgery. These apoC-III beneficial modifications may have implications in dyslipidemia improvement and contribute to cardiovascular risk reduction after surgery. Copyright © 2017 National Lipid Association. Published by Elsevier Inc. All rights reserved.

Radiation-induced polymerization of glass-forming systems. IV. Effect of the homogeneity of polymerization phase and polymer concentration on temperature dependence of initial polymerization rate

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

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

1973-06-01

The effect of homogeneity of polymerization phase and monomer concentration on the temperature dependence of initial polymerization rate was studied in the radiation-induced radical polymerization of binary systems consisting of glass-forming monomer and solvent. In the polymerization of a completely homogeneous system such as HEMA-propylene glycol, a maximum and a minimum in polymerization rates as a function of temperature, characteristic of the polymerization in glass-forming systems, were observed for all monomer concentrations. However, in the heterogeneous polymerization systems such as HEMA-triacetin and HEMAisoamyl acetate, maximum and minimum rates were observed in monomer-rich compositions but not at low monomer concentrations. Furthermore,more » in the HEMA-dioctyl phthalate polymerization system, which is extremely heterogeneous, no maximum and minimum rates were observed at any monomer concentration. The effect of conversion on the temperature dependence of polymerization rate in homogeneous bulk polymerization of HEMA and GMA was investigated. Maximum and minimum rates were observed clearly in conversions less than 10% in the case of HEMA and less than 50% in the case of GMA, but the maximum and minimum changed to a mere inflection in the curve at higher conversions. A similar effect of polymer concentration on the temperature dependence of polymerization rate in the GMA-poly(methyl methacrylate) system was also observed. It is deduced that the change in temperature dependence of polymerization rate is attributed to the decrease in contribution of mutual termination reaction of growing chain radicals to the polymerization rate. (auth)« less

Isomer separation and effect of the degree of polymerization on the gas-phase structure of chondroitin sulfate oligosaccharides analyzed by ion mobility and tandem mass spectrometry.

PubMed

Poyer, Salomé; Lopin-Bon, Chrystel; Jacquinet, Jean-Claude; Salpin, Jean-Yves; Daniel, Régis

2017-12-15

Chondroitin sulfate (CS) glycosaminoglycans are bioactive sulfated polysaccharides comprising repeating units of uronic acid and N-acetyl galactose sulfated at various positions. The optimal length and sulfation pattern of the CS bioactive sequences remain elusive so that structure-activity relationships cannot be easily established. Development of efficient analytical methods allowing the differentiation of the various sulfation patterns of CS sequences is therefore of particular importance to correlate their biological functions to the sulfation pattern. Discrimination of different oligomers (dp2 to dp6) of synthetic chondroitin sulfate isomers was evaluated by electrospray ionization tandem mass spectrometry (ESI-MS/MS) in the negative-ion mode from deprotonated and alkali adduct species. In addition, ion mobility mass spectrometry (IMS-MS) was used to study the influence of both the degree of polymerization and sulfate group location on the gas-phase conformation of CS oligomers. ESI-MS/MS spectra of chondroitin sulfate isomers show characteristic product ions exclusively from alkali adduct species (Li, Na, K and Cs). Whatever the alkali adducts studied, MS/MS of chondroitin oligosaccharides sulfated at position 6 yields a specific product ion at m/z 139 while CS oligosaccharides sulfated at position 4 show a specific product ion at m/z 154. Being observed for the different CS oligomers di-, tetra- and hexasaccharides, these fragment ions are considered as diagnostic ions for chondroitin 6-O-sulfate and chondroitin 4-O-sulfate, respectively. IMS-MS experiments reveal that collision cross-sections (CCS) of CS oligomers with low charge states evolved linearly with degrees of polymerization indicating a similar gas-phase conformation. This study allows the fast and unambiguous differentiation of CS isomers sulfated at position 6 or 4 for both saturated and unsaturated analogues from MS/MS experiments. In addition, the CCS linear evolution of CS oligomers in function of the degree of polymerization indicates that no folding occurs even for hexasaccharides. Copyright © 2017 John Wiley & Sons, Ltd.

Advanced analysis of polymer emulsions: Particle size and particle size distribution by field-flow fractionation and dynamic light scattering.

PubMed

Makan, Ashwell C; Spallek, Markus J; du Toit, Madeleine; Klein, Thorsten; Pasch, Harald

2016-04-15

Field flow fractionation (FFF) is an advanced fractionation technique for the analyses of very sensitive particles. In this study, different FFF techniques were used for the fractionation and analysis of polymer emulsions/latexes. As model systems, a pure acrylic emulsion and emulsions containing titanium dioxide were prepared and analyzed. An acrylic emulsion polymerization was conducted, continuously sampled from the reactor and subsequently analyzed to determine the particle size, radius of gyration in specific, of the latex particles throughout the polymerization reaction. Asymmetrical flow field-flow fractionation (AF4) and sedimentation field-flow fractionation (SdFFF), coupled to a multidetector system, multi-angle laser light scattering (MALLS), ultraviolet (UV) and refractive index (RI), respectively, were used to investigate the evolution of particle sizes and particle size distributions (PSDs) as the polymerization progressed. The obtained particle sizes were compared against batch-mode dynamic light scattering (DLS). Results indicated differences between AF4 and DLS results due to DLS taking hydration layers into account, whereas both AF4 and SdFFF were coupled to MALLS detection, hence not taking the hydration layer into account for size determination. SdFFF has additional separation capabilities with a much higher resolution compared to AF4. The calculated radii values were 5 nm larger for SdFFF measurements for each analyzed sample against the corresponding AF4 values. Additionally a low particle size shoulder was observed for SdFFF indicating bimodality in the reactor very early during the polymerization reaction. Furthermore, different emulsions were mixed with inorganic species used as additives in cosmetics and coatings such as TiO2. These complex mixtures of species were analyzed to investigate the retention and particle interaction behavior under different AF4 experimental conditions, such as the mobile phase. The AF4 system was coupled online to inductively coupled plasma mass spectrometry (ICP-MS) for elemental speciation and identification of the inorganic additive. SdFFF had a larger separation power to distinguish different particle size populations whereas AF4 had the capability of separating the organic particles and inorganic TiO2 particles, with high resolution. Copyright © 2016 Elsevier B.V. All rights reserved.

Polymeric heart valves for surgical implantation, catheter-based technologies and heart assist devices.

PubMed

Bezuidenhout, Deon; Williams, David F; Zilla, Peter

2015-01-01

Efficient function and long-term durability without the need for anticoagulation, coupled with the ability to be accommodated in many different types of patient, are the principal requirements of replacement heart valves. Although the clinical use of valves appeared to have remained steady for several decades, the evolving demands for the elderly and frail patients typically encountered in the developed world, and the needs of much younger and poorer rheumatic heart disease patients in the developing world have now necessitated new paradigms for heart valve technologies and associated materials. This includes further consideration of durable elastomeric materials. The use of polymers to produce flexible leaflet valves that have the benefits of current commercial bioprosthetic and mechanical valves without any of their deficiencies has been held desirable since the mid 1950s. Much attention has been focused on thermoplastic polyurethanes in view of their generally good physico-chemical properties and versatility in processing, coupled with the improving biocompatibility and stability of recent formulations. Accelerated in vitro durability of between 600 and 1000 million cycles has been achieved using polycarbonate urethanes, and good resistance to degradation, calcification and thrombosis in vivo has been shown with some polysiloxane-based polyurethanes. Nevertheless, polymeric valves have remained relegated to use in temporary ventricular assist devices for bridging heart failure patients to transplantation. Some recent studies suggest that there is a greater degree of instability in thermoplastic materials than hitherto believed so that significant challenges remain in the search for the combination of durability and biocompatibility that would allow polymeric valves to become a clinical reality for surgical implantation. Perhaps more importantly, they could become candidates for use in situations where minimally invasive transcatheter procedures are used to replace diseased valves. Being amenable to relatively inexpensive mass production techniques, the attainment of this goal could benefit very large numbers of patients in developing and emerging countries who currently have no access to treatment for rheumatic heart disease that is so prevalent in these areas. This review discusses the evolution and current status of polymeric valves in wide-ranging circumstances.

Neurosis, psychodynamics, and DSM-III. A history of the controversy.

PubMed

Bayer, R; Spitzer, R L

1985-02-01

The adoption of DSM-III by the American Psychiatric Association has been viewed as representing a major advance for psychiatry and as an indication of the emergence of a broad professional consensus on diagnostic issues. The process of drafting the new manual was not, however, free of conflict. This article presents a narrative account of the controversies over the role of psychodynamic formulations in DSM-III and the more focused, though sharply contested, symbolic dispute over the inclusion of neurosis in the nomenclature. It traces the evolution of these disputes and focuses on the interplay of scientific and political considerations as psychiatrists committed to differing professional and therapeutic paradigms confronted each other for more than two years as the profession sought to develop a new manual that would improve the level of reliability of psychiatric diagnosis.

Deciphering the biodiversity of Listeria monocytogenes lineage III strains by polyphasic approaches.

PubMed

Zhao, Hanxin; Chen, Jianshun; Fang, Chun; Xia, Ye; Cheng, Changyong; Jiang, Lingli; Fang, Weihuan

2011-10-01

Listeria monocytogenes is a foodborne pathogen of humans and animals. The majority of human listeriosis cases are caused by strains of lineages I and II, while lineage III strains are rare and seldom implicated in human listeriosis. We revealed by 16S rRNA sequencing the special evolutionary status of L. monocytogenes lineage III, which falls between lineages I and II strains of L. monocytogenes and the non-pathogenic species L. innocua and L. marthii in the dendrogram. Thirteen lineage III strains were then characterized by polyphasic approaches. Biochemical reactions demonstrated 8 biotypes, internalin profiling identified 10 internal-in types clustered in 4 groups, and multilocus sequence typing differentiated 12 sequence types. These typing schemes show that lineage III strains represent the most diverse population of L. monocytogenes, and comprise at least four subpopulations IIIA-1, IIIA-2, HIB, and IIIC. The in vitro and in vivo virulence assessments showed that two lineage IIIA-2 strains had reduced pathogenicity, while the other lineage III strains had comparable virulence to lineages I and II. The HIB strains are phylogenetically distinct from other sub-populations, providing additional evidence that this sublineage represents a novel lineage. The two biochemical reactions L-rhamnose and L-lactate alkalinization, and 10 internalins were identified as potential markers for lineage III subpopulations. This study provides new insights into the biodiversity and population structure of lineage III strains, which are important for understanding the evolution of the L. mono-cytogenes-L. innocua clade.

[Evaluation of pressure ulcers area using the softwares Motic and AutoCAD®].

PubMed

Reis, Camila Letícia Dias dos; Cavalcante, Janaína Mortosa; Rocha Júnior, Edvar Ferreira da; Neves, Rinaldo Souza; Santana, Levy Aniceto; Guadagnin, Renato da Veiga; Brasil, Lourdes Mattos

2012-01-01

Pressure ulcer is a lesion that affects skin layers in some regions of the body and its healing can be followed up using image processing. The analysis of pressure ulcer area is relevant to evaluate its evolution and response to therapeutic procedures. Such areas can be evaluated through contour marking with the softwares Motic and AutoCAD®. In this study 35 volunteers computed areas from two grade III pressure ulcers using these instruments. It was possible to conclude that results are clinically equivalent and so can be considered to follow up healing evolution from pressure ulcers.

Altruism: Its characteristics and evolution

PubMed Central

Darlington, P. J.

1978-01-01

Altruism is a group phenomenon in which some genes or individuals, which must be presumed to be selfish, benefit others at cost to themselves. The presumption of selfishness and the fact of altruism are reconciled by kin-group selection and by reciprocal altruism. Kin-group selection is clearly visible only in special cases; its role even among social insects may be overestimated; it is probably usually inhibited by competition. However, reciprocal altruism is ubiquitous. All altruism is: (i) potentially reciprocal; (ii) potentially profitable to altruists as well as to recipients; (iii) environmentally determined, usually by position of individuals in group or environmental situations; and (iv) a net-gain lottery. These generalizations are illustrated by four idealized cases; the difficulty of applying them to real cases is illustrated by alarm-calling in groups of birds. Although altruism is a group phenomenon, it evolves by individual selection, by processes equivalent to co-evolutions. Its evolution is: (i) opposed by competition; (ii) costly, complex, and slow, and tending to produce an imprecise flexible altruism rather than a precisely detailed one; and (iii) supplemented by group selection (differential extinction of groups). That altruism in human beings conforms to these generalizations is a good working hypothesis. However, analysis does not “take the altruism out of (human) altruism.” Humans do not calculate it, but behave altruistically because they have human altruistic emotions. PMID:272654

Post-discharge evolution of reactive species in the water activated by a surface air plasma: a modeling study

NASA Astrophysics Data System (ADS)

Liu, Z. C.; Liu, D. X.; Chen, C.; Liu, Z. J.; Yang, A. J.; Rong, M. Z.; Chen, H. L.; Kong, M. G.

2018-05-01

Plasma-activated water (PAW) has been reported to sustain a bactericidal ability for months. However, many reactive species regarded as the main antibacterial agents in PAW have short lifetimes of less than one second. In order to explain the prolonged antibacterial ability of PAW and predict how to extend its effective time, we studied the post-discharge evolution of reactive species in PAW based on a system-level model reported previously. Three common storage conditions for PAW were considered within the post-discharge time of 14 d: (I) leaving the residual gas and PAW in the sealed reactor; (II) leaving PAW in the open air; (III) sealing the container of PAW. In comparison, storage condition III was the best condition to preserve the long-lived species including H2O2 and HNO2/, whereas storage condition I was the best method to preserve the short-lived species including OH, HO2 and ONOOH/ONOO‑. It suggests that the gas–liquid mass transfer plays an important role in the evolution of reactive species. We also found that O2NOOH/O2NOO‑ had an almost one order of magnitude higher concentration and a longer residue time than those of ONOOH/ONOO‑. This distinction suggests that the biological effect of O2NOOH/O2NOO‑ may be important.

The Apache Point Observatory Galactic Evolution Experiment (APOGEE) and its successor, APOGEE-2

NASA Astrophysics Data System (ADS)

Majewski, S. R.; APOGEE Team; APOGEE-2 Team

2016-09-01

The Apache Point Observatory Galactic Evolution Experiment (APOGEE) of Sloan Digital Sky Survey III (SDSS-III) has produced a large catalog of high resolution ({R = 22 500}), high quality (S/N > 100), infrared (H-band) spectra for stars throughout all stellar populations of the Milky Way, including in regions veiled by significant dust opacity. APOGEE's half million spectra collected on > 163 000 unique stars, with time series information via repeat visits to each star, are being applied to numerous problems in stellar populations, Galactic astronomy, and stellar astrophysics. From among the early results of the APOGEE project - which span from measurements of Galactic dynamics, to multi-element chemical maps of the disk and bulge, new views of the interstellar medium, explorations of stellar companions, the chemistry of star clusters, and the discovery of rare stellar species - I highlight a few results that demonstrate APOGEE's unique ability to sample and characterize the Galactic disk and bulge. Plans are now under way for an even more ambitious successor to APOGEE: the six-year, dual-hemisphere APOGEE-2 project. Both phases of APOGEE feature a strong focus on targets having asteroseismological measurements from either Kepler or {CoRoT}, from which it is possible to derive relatively precise stellar ages. The combined APOGEE and APOGEE-2 databases of stellar chemistry, dynamics and ages constitute an unusually comprehensive, systematic and homogeneous resource for constraining models of Galactic evolution.

Influence of different components in a TPV PP/EPDM based with low hardness

NASA Astrophysics Data System (ADS)

Gheller, J.; Jacobi, M. M.

2014-05-01

Thermoplastic vulcanizates (TPVs) are a class of polymeric material obtained by dynamic vulcanization of an elastomer in a melted thermoplastic matrix. This work intend to evaluate different variables in the production of low hardness TPVs made of polypropylene (PP) and ethylene propylene rubber (EPDM), as well the optimization of the variables looking for TPVs with improved performance. In the Study I the influence of PP crystallinity were evaluated, in the Study II the effects of different amounts of dicumyl peroxide (DCP) were evaluated and in the Study III the amount of the phenolic resin were evaluated. This extended abstract presents, in a more detailed way, the results considering the curative phenolic resin content (Study III). The others results and discussions are briefly described in the results and discussions section. The compounds were obtained in a closed mixing chamber and their processability properties, swelling, hardness and tensile strength were evaluated. With the results obtained were possible to evaluate the influence of different ingredients in the TPVs properties. The results were discussed and presented looking for a better understanding of the influence of this variable in the final product, as well the correlation between then.

Anodic electrodeposition of NiTSPP from aqueous basic media.

PubMed

Pérez-Morales, Marta; Muñoz, Eulogia; Martín-Romero, María T; Camacho, Luis

2005-06-07

The oxidative electrodeposition of NiTSPP (tetrakis(4-sulfonatophenyl) Ni porphyrin) on ITO electrode from 0.1 M NaOH aqueous solution has been studied, and UV-visible and reflection FTIR spectroscopies have been used to analyze the composition of such film. By use of UV-vis spectroscopy, small absorbance of the film and an almost nulling effect on the Soret band of the porphyrin along the Ni(III)/Ni(II) redox process were observed. The reflection FTIR spectroscopy detected the presence of Ni-OH groups in the reduced film and as well the state of the porphyrin molecules as radical cation. Moreover, the porphyrin has been quantified by means of the area of the vibration bands assigned to the sulfonate groups by using as reference a Langmuir-Blodgett film containing a known surface concentration of NiTSPP. These results lead us propose the formation of a conductor salt by electrocrystallization, with stoichiometries TSPP/Ni(II)(OH)2 and TSPP/Ni(III)OOH, for its reduced and oxidized forms, respectively. In these two forms, the porphyrin rings will be present as radical cation, which may be stabilized through its dimerization or polymerization.

Elastomeric enriched biodegradable polyurethane sponges for critical bone defects: a successful case study reducing donor site morbidity.

PubMed

Lavrador, Catarina; Mascarenhas, Ramiro; Coelho, Paulo; Brites, Cláudia; Pereira, Alfredo; Gogolewski, Sylwester

2016-03-01

Bone substitutes have been a critical issue as the natural source can seldom provide enough bone to support full healing. No bone substitute complies with all necessary functions and characteristics that an autograft does. Polyurethane sponges have been used as a surgical alternative to cancellous bone grafts for critical bone defect donor sites. Critical bone defects were created on the tibial tuberosity and iliac crest using an ovine model. In group I (control-untreated), no bone regeneration was observed in any animal. In group II (defects left empty but covered with a microporous polymeric membrane), the new bone bridged the top ends in all animals. In groups III and IV, bone defects were implanted with polyurethane scaffolds modified with biologically active compounds, and bone regeneration was more efficient than in group II. In groups III and IV there were higher values of bone regeneration specific parameters used for evaluation (P < 0.05) although the comparison between these groups was not possible. The results obtained in this study suggest that biodegradable polyurethane substitutes modified with biologically active substances may offer an alternative to bone graft, reducing donor site morbidity associated with autogenous cancellous bone harvesting.

Fractographic study of epoxy fractured under mode I loading and mixed mode I/III loading

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

Ren, Fei; Wang, Jy-An John; Bertelsen, Williams D.

2011-01-01

Fiber reinforced polymeric composite materials are widely used in structural components such as wind turbine blades, which are typically subject to complicated loading conditions. Thus, material response under mixed mode loading is of great significance to the reliability of these structures. Epoxy is a thermosetting polymer that is currently used in manufacturing wind turbine blades. The fracture behavior of epoxy is relevant to the mechanical integrity of the wind turbine composite materials. In this study, a novel fracture testing methodology, the spiral notch torsion test (SNTT), was applied to study the fracture behavior of an epoxy material. SNTT samples weremore » tested using either monotonic loading or cyclic loading, while both mode I and mixed mode I/III loading conditions were used. Fractographic examination indicated the epoxy samples included in this study were prone to mode I failure even when the samples were subject to mixed mode loading. Different fatigue precracks were observed on mode I and mixed mode samples, i.e. precracks appeared as a uniform band under mode I loading, and a semi-ellipse under mixed mode loading. Fracture toughness was also estimated using quantitative fractography.« less

Tris(2-(1H-pyrazol-1-yl)pyridine)cobalt(III) as p-type dopant for organic semiconductors and its application in highly efficient solid-state dye-sensitized solar cells.

PubMed

Burschka, Julian; Dualeh, Amalie; Kessler, Florian; Baranoff, Etienne; Cevey-Ha, Ngoc-Lê; Yi, Chenyi; Nazeeruddin, Mohammad K; Grätzel, Michael

2011-11-16

Chemical doping is an important strategy to alter the charge-transport properties of both molecular and polymeric organic semiconductors that find widespread application in organic electronic devices. We report on the use of a new class of Co(III) complexes as p-type dopants for triarylamine-based hole conductors such as spiro-MeOTAD and their application in solid-state dye-sensitized solar cells (ssDSCs). We show that the proposed compounds fulfill the requirements for this application and that the discussed strategy is promising for tuning the conductivity of spiro-MeOTAD in ssDSCs, without having to rely on the commonly employed photo-doping. By using a recently developed high molar extinction coefficient organic D-π-A sensitizer and p-doped spiro-MeOTAD as hole conductor, we achieved a record power conversion efficiency of 7.2%, measured under standard solar conditions (AM1.5G, 100 mW cm(-2)). We expect these promising new dopants to find widespread applications in organic electronics in general and photovoltaics in particular.

Structure of the heterotrimeric complex that regulates type III secretion needle formation

PubMed Central

Quinaud, Manuelle; Plé, Sophie; Job, Viviana; Contreras-Martel, Carlos; Simorre, Jean-Pierre; Attree, Ina; Dessen, Andréa

2007-01-01

Type III secretion systems (T3SS), found in several Gram-negative pathogens, are nanomachines involved in the transport of virulence effectors directly into the cytoplasm of target cells. T3SS are essentially composed of basal membrane-embedded ring-like structures and a hollow needle formed by a single polymerized protein. Within the bacterial cytoplasm, the T3SS needle protein requires two distinct chaperones for stabilization before its secretion, without which the entire T3SS is nonfunctional. The 2.0-Å x-ray crystal structure of the PscE-PscF55–85-PscG heterotrimeric complex from Pseudomonas aeruginosa reveals that the C terminus of the needle protein PscF is engulfed within the hydrophobic groove of the tetratricopeptide-like molecule PscG, indicating that the macromolecular scaffold necessary to stabilize the T3SS needle is totally distinct from chaperoned complexes between pilus- or flagellum-forming molecules. Disruption of specific PscG–PscF interactions leads to impairment of bacterial cytotoxicity toward macrophages, indicating that this essential heterotrimer, which possesses homologs in a wide variety of pathogens, is a unique attractive target for the development of novel antibacterials. PMID:17470796

An insight into polymerization-induced self-assembly by dissipative particle dynamics simulation.

PubMed

Huang, Feng; Lv, Yisheng; Wang, Liquan; Xu, Pengxiang; Lin, Jiaping; Lin, Shaoliang

2016-08-14

Polymerization-induced self-assembly is a one-pot route to produce concentrated dispersions of block copolymer nano-objects. Herein, dissipative particle dynamics simulations with a reaction model were employed to investigate the behaviors of polymerization-induced self-assembly. The polymerization kinetics in the polymerization-induced self-assembly were analyzed by comparing with solution polymerization. It was found that the polymerization rate enhances in the initial stage and decreases in the later stage. In addition, the effects of polymerization rate, length of macromolecular initiators, and concentration on the aggregate morphologies and formation pathway were studied. The polymerization rate and the length of the macromolecular initiators are found to have a marked influence on the pathway of the aggregate formations and the final structures. Morphology diagrams were mapped correspondingly. A comparison between simulation results and experimental findings is also made and an agreement is shown. This work can enrich our knowledge about polymerization-induced self-assembly.

Chain Breakage in the Supercooled Liquid - Liquid Transition and Re-entry of the λ-transition in Sulfur.

PubMed

Zhang, Linji; Ren, Yang; Liu, Xiuru; Han, Fei; Evans-Lutterodt, Kenneth; Wang, Hongyan; He, Yali; Wang, Junlong; Zhao, Yong; Yang, Wenge

2018-03-14

Amorphous sulfur was prepared by rapid compression of liquid sulfur at temperatures above the λ-transition for to preserve the high-temperature liquid structure. We conducted synchrotron high-energy X-ray diffraction and Raman spectroscopy to diagnose the structural evolution of amorphous sulfur from room temperature to post-λ-transition temperature. Discontinuous changes of the first and second peaks in atomic pair-distribution-function, g(r), were observed during the transition from amorphous to liquid sulfur. The average first-neighbor coordination numbers showed an abrupt drop from 1.92 to 1.81. The evolution of the chain length clearly shows that the transition was accompanied by polymeric chains breaking. Furthermore, a re-entry of the λ-transition structure was involved in the heating process. The amorphous sulfur, which inherits the post-λ-transition structure from its parent melts, transformed to the pre-λ-transition liquid structure at around 391 K. Upon further heating, the pre-λ-transition liquid transformed to a post-λ-transition structure through the well-known λ-transition process. This discovery offers a new perspective on amorphous sulfur's structural inheritance from its parent liquid and has implications for understanding the structure, evolution and properties of amorphous sulfur and its liquids.

Towards high water permeability in triazine-framework-based microporous membranes for dehydration of ethanol.

PubMed

Tang, Yu Pan; Wang, Huan; Chung, Tai Shung

2015-01-01

The microstructural evolution of a series of triazine framework-based microporous (TFM) membranes under different conditions has been explored in this work. The pristine TFM membrane is in situ fabricated in the course of polymer synthesis via a facile Brønsted-acid-catalyzed cyclotrimerizaiton reaction. The as-synthesized polymer exhibits a microporous network with high thermal stability. The free volume size of the TFM membranes gradually evolved from a unimodal distribution to a bimodal distribution under annealing, as analyzed by positron annihilation lifetime spectroscopy (PALS). The emergence of the bimodal distribution is probably ascribed to the synergetic effect of quenching and thermal cyclization reaction. In addition, the fractional free volume (FFV) of the membranes presents a concave trend with increasing annealing temperature. Vapor sorption tests reveal that the mass transport properties are closely associated with the free volume evolution, which provides an optimal condition for dehydration of biofuels. A promising separation performance with extremely high water permeability has been attained for dehydration of an 85 wt % ethanol aqueous solution at 45 °C. The study on the free volume evolution of the TFM membranes may provide useful insights about the microstructure and mass transport behavior of the microporous polymeric materials. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

CHANGES IN THE LEGAL AND PSYCHIATRIC CONCEPTS OF OBJECTIVE CAUSE.

PubMed

Mester, Roberto; Margolin, Jacob

2014-12-01

As it can be observed in court rulings and psychiatric diagnostic criteria, the characteristics of the medico-legal concept of objective cause are undergoing evolutions in the psychiatric as well as in the legal areas. In this paper, we will analyze and discuss those evolutions, using two types of materials: (a) A recent Israeli Supreme Court ruling related to an appeal of an army officer who claimed to have developed a psychiatric disorder due to his military service. (B) The changes in the diagnostic criteria of Post-Traumatic Stress Disorder (PTSD) from the DSM-III through the DSM-IV till the recently published DSM-V. Awareness and understanding of those evolutions are helpful for psychiatrists in the process of preparing professional reports and/or acting as expert witnesses in Courts.

Kin-selected cooperation without lifetime monogamy: human insights and animal implications.

PubMed

Kramer, Karen L; Russell, Andrew F

2014-11-01

Recent phylogenetic analyses suggest that monogamy precedes the evolution of cooperative breeding involving non-breeding helpers. The rationale: only through monogamy can helper-recipient relatedness coefficients match those of parent-offspring. Given that humans are cooperative breeders, these studies imply a monogamy bottleneck during hominin evolution. However, evidence from multiple sources is not compelling. In reconciliation, we propose that selection against cooperative breeding under alternative mating patterns will be mitigated by: (i) kin discrimination, (ii) reduced birth-intervals, and (iii) constraints on independent breeding, particularly for premature and post-fertile individuals. We suggest that such alternatives require consideration to derive a complete picture of the selection pressures acting on the evolution of cooperative breeding in humans and other animals. Copyright © 2014 Elsevier Ltd. All rights reserved.

Extreme [O III] Emitters at z ∼ 0.5

NASA Astrophysics Data System (ADS)

Li, Zhihui; Malkan, Matthew A.

2018-06-01

We have found a sample of extreme emission-line galaxies (EELGs) with strong [O III]λ5007 emission at z ∼ 0.5. Using broadband photometric selection and requiring small uncertainties in photometry, we searched the 14th Data Release of the Sloan Digital Sky Survey (SDSS) and found 2658 candidates with strong i-band excess (i – z ≤ r – i – 0.7). We further obtained 649 SDSS spectra of these objects, and visually identified 22 [O III] emitters lying at 0.40 < z < 0.63. Having constructed their ultraviolet–infrared spectral energy distributions, we found that they have fairly blue r – W2 and red W1 – W4 colors, indicative of strong, warm dust emission. Their rest-frame [O III]λ5007 equivalent widths are mostly 200–600 Å, and their high [O III]λ5007/Hβ ratios put them at the boundary of star-forming galaxies and active galactic nuclei on line ratio classification diagrams. The typical E(B–V) and electron temperature of [O III] emitters are ∼0.1–0.3 mag and ∼104 K, respectively. The lowest metallicity of our [O III] emitters with S/N[O III]λ4363 > 3 is 12 + log(O/H) = {7.98}-0.02+0.12, with a median value of {8.24}-0.04+0.05. Our [O III] emitters exhibit remarkably high line luminosity—18/22 have L [O III]λ5007 > 5 × 1042 erg s‑1 and 5/22 have L [O III]λ5007 > 1043 erg s‑1. Their estimated volume number density at z ∼ 0.5 is ∼2 × 10‑8 Mpc‑3, with L [O III]λ5007 down to ∼3 × 1042 erg s‑1. The cumulative number distribution of EELGs across different redshifts is indicative of a strong redshift evolution at the bright end of the [O III] luminosity function.

Phases of Feminist Re-Vision in the Psychology of Personality.

ERIC Educational Resources Information Center

Torrey, Jane W.

1987-01-01

Reviews McIntosh's 1983 theory on the five-phase evolution of scholarship required by increasing feminism. Documents the sequence of the five phases using references to scholarly literature on the psychology of personality. Elaborates on Phase III in which investigators study women as inherently different from men and urges further study and…

Density and magnetic fluctuations in type III-ELM pedestal evolution in JET: experimental and numerical characterization

NASA Astrophysics Data System (ADS)

De Masi, G.; Predebon, I.; Spagnolo, S.; Meneses, L.; Delabie, E.; Lupelli, I.; Hillesheim, J. C.; Maggi, C.; Contributors, JET

2018-04-01

Density and magnetic fluctuation measurements in low-β type-III ELM discharges are obtained in the Joint European Torus (JET). They are observed during the inter-ELM pedestal evolution, after the LH transition phase, at about 60-70 kHz. Density fluctuations are measured with a correlation reflectometer system installed on the low-field side and they are localized at the pedestal top. Magnetic fluctuations with a spatial scale k_yρ_i˜ 0.1 are measured through a high resolution coil array. The main features and the relations with local plasma parameters are presented. The nature of these fluctuations is discussed along with linear gyrokinetic simulations. Ion temperature gradient (ITG) modes are the dominant instabilities in the frequency range of interest. In terms of radial localization, typical oscillation frequency and qualitative relation with the possible linear drive, ITG modes are consistent with the experimental density fluctuations measurements. Micro-tearing modes (MTMs), found unstable with a lower growth rate, appear a possible explanation for magnetic fluctuations in terms of typical wavenumbers and direction of propagation.

Ion beam nanopatterning of III-V semiconductors: Consistency of experimental and simulation trends within a chemistry-driven theory

DOE PAGES

El-Atwani, O.; Norris, S. A.; Ludwig, K.; ...

2015-12-16

In this study, several proposed mechanisms and theoretical models exist concerning nanostructure evolution on III-V semiconductors (particularly GaSb) via ion beam irradiation. However, making quantitative contact between experiment on the one hand and model-parameter dependent predictions from different theories on the other is usually difficult. In this study, we take a different approach and provide an experimental investigation with a range of targets (GaSb, GaAs, GaP) and ion species (Ne, Ar, Kr, Xe) to determine new parametric trends regarding nanostructure evolution. Concurrently, atomistic simulations using binary collision approximation over the same ion/target combinations were performed to determine parametric trends onmore » several quantities related to existing model. A comparison of experimental and numerical trends reveals that the two are broadly consistent under the assumption that instabilities are driven by chemical instability based on phase separation. Furthermore, the atomistic simulations and a survey of material thermodynamic properties suggest that a plausible microscopic mechanism for this process is an ion-enhanced mobility associated with energy deposition by collision cascades.« less

THE TIME EVOLUTION OF HH 1 FROM FOUR EPOCHS OF HST IMAGES

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

Raga, A. C.; Esquivel, A.; Reipurth, B.

We present an analysis of four epochs of Hα and [S ii] λλ 6716/6731 Hubble Space Telescope (HST) images of HH 1. For determining proper motions, we explore a new method based on the analysis of spatially degraded images obtained convolving the images with wavelet functions of chosen widths. With this procedure, we are able to generate maps of proper motion velocities along and across the outflow axis, as well as (angularly integrated) proper motion velocity distributions. From the four available epochs, we find the time evolution of the velocities, intensities, and spatial distribution of the line emission. We find that overmore » the last two decades HH 1 shows a clear acceleration. Also, the Hα and [S ii] intensities first dropped and then recovered in the more recent (2014) images. Finally, we show a comparison between the two available HST epochs of [O iii] λ 5007 (1994 and 2014), in which we see a clear drop in the value of the [O iii]/Hα ratio.« less

Length distributions of Au-catalyzed III-V nanowires in different regimes of the diffusion-induced growth

NASA Astrophysics Data System (ADS)

Berdnikov, Y.; Zhiglinsky, A. A.; Rylkova, M. V.; Dubrovskii, V. G.

2017-11-01

We present a model for kinetic broadening effects on the length distributions of Au-catalyzed III-V nanowires obtained in the growth regime with adatom diffusion from the substrate and the nanowire sidewalls to the top. We observe three different regimes for the length distribution evolution with time. For short growth times, the length distribution is sub-Poissonian, converting to broader than Poissonian with increasing the mean length above a certain threshold value. After the diffusion flux from the nanowire sidewalls has stabilized, the length distribution variance increases linearly with the mean length, as in the Poissonian process.

Reliability Improvement in III-V Concentrator Solar Cells by Means of Perimeter Protection

NASA Astrophysics Data System (ADS)

González, José R.; Vázquez, Manuel; Núñez, Neftalí; Algora, Carlos; Espinet, Pilar

2010-10-01

This paper presents the evolution in the strategy to assess the reliability of III-V solar cells and a new thermal ageing test carried out over GaAs single junction solar cells at three different temperatures (130, 150 and 170° C). The perimeter of the solar cells has been protected with silicone, which seems to be an effective way of enhancing the reliability of the solar cells. A preliminary analysis of the results indicates a mean time to failure (MTTF) one order of magnitude larger than the one obtained in a previous thermal test with the perimeter uncoated.

Liquid crystalline tactoids: ordered structure, defective coalescence and evolution in confined geometries

NASA Astrophysics Data System (ADS)

Wang, Pei-Xi; MacLachlan, Mark J.

2017-12-01

Tactoids are liquid crystalline microdroplets that spontaneously nucleate from isotropic dispersions, and transform into macroscopic anisotropic phases. These intermediate structures have been found in a range of molecular, polymeric and colloidal liquid crystals. Typically only studied by polarized optical microscopy, these ordered but easily deformable microdroplets are now emerging as interesting components for structural investigations and developing new materials. In this review, we highlight the structure, property and transformation of tactoids in different compositions, but especially cellulose nanocrystals. We have selected references that illustrate the diversity and most exciting developments in tactoid research, while capturing the historical development of this field. This article is part of a discussion meeting issue `New horizons for cellulose nanotechnology'.

FAST TRACK COMMUNICATION: Poly(methyl methacrylate)-palladium clusters nanocomposite formation by supersonic cluster beam deposition: a method for microstructured metallization of polymer surfaces

NASA Astrophysics Data System (ADS)

Ravagnan, Luca; Divitini, Giorgio; Rebasti, Sara; Marelli, Mattia; Piseri, Paolo; Milani, Paolo

2009-04-01

Nanocomposite films were fabricated by supersonic cluster beam deposition (SCBD) of palladium clusters on poly(methyl methacrylate) (PMMA) surfaces. The evolution of the electrical conductance with cluster coverage and microscopy analysis show that Pd clusters are implanted in the polymer and form a continuous layer extending for several tens of nanometres beneath the polymer surface. This allows the deposition, using stencil masks, of cluster-assembled Pd microstructures on PMMA showing a remarkably high adhesion compared with metallic films obtained by thermal evaporation. These results suggest that SCBD is a promising tool for the fabrication of metallic microstructures on flexible polymeric substrates.

Ribosomes: Ribozymes that Survived Evolution Pressures but Is Paralyzed by Tiny Antibiotics

NASA Astrophysics Data System (ADS)

Yonath, Ada

An impressive number of crystal structures of ribosomes, the universal cellular machines that translate the genetic code into proteins, emerged during the last decade. The determination of ribosome high resolution structure, which was widely considered formidable, led to novel insights into the ribosomal function, namely, fidelity, catalytic mechanism, and polymerize activities. They also led to suggestions concerning its origin and shed light on the action, selectivity and synergism of ribosomal antibiotics; illuminated mechanisms acquiring bacterial resistance and provided structural information for drug improvement and design. These studies required the pioneering and implementation of advanced technologies, which directly influenced the remarkable increase of the number of structures deposited in the Protein Data Bank.

Different routes to the glass transition: A comparison between chemical and physical vitrification

NASA Astrophysics Data System (ADS)

Caponi, Silvia; Corezzi, Silvia

2012-07-01

Despite the differences in the molecular processes involved in chemical and physical vitrification, surprising similarities are observed in the dynamics and in the thermodynamical properties of the resulting glasses. We report on a systematic study of reactive glass-formers undergoing a process of progressive polymerization of the constituent molecules via the formation of irreversible chemical bonds. The formation of most of the materials used in engineering plastics and the hardening of natural and synthetic resins, including epoxy resins, are based on chemical vitrification. The clear analogies characterizing the dynamic evolution of physical and chemical glass-formers, on the time scale of the structural and the low-frequency vibrational dynamics, are briefly reviewed.

An experimental study of the PTC properties of polymers with carbon black fillers

NASA Astrophysics Data System (ADS)

Lin, Jianlian

The Positive Temperature Coefficient (PTC) phenomenon, first discovered by Harman in 1957, is defined as the sharp increase of the electrical resistivity of the material with temperature, especially at the Curie transition temperature. Polymeric PTC materials have been widely used since 1975 as self-regulating components, over current or over heat protectors, sensors, etc. In this project a detailed study of polymeric PTC materials has been carried out. Polymeric PTC materials consist of a non-conducting polymeric phase in which conductive particles, such as CB's, are added. Previously most of the studies of the polymer matrices of PTC materials were limited to single component semi-crystalline polymers, such as HDPE, LDPE, EVA etc. In this work, the PTC effects of carbon black filled binary polymer blends, such as LDPE/EPDM, HDPD/EPDM, HDPE/EVA, etc. are mainly studied. For the LDPE/EPDM/CB system, it is found that the PTC intensity of the blends after gamma-ray irradiation increases by almost 5 orders of magnitude compared with that of irradiated LDPE/CB compound. This increase in PTC intensity is due to the greater thermal expansion coefficient of the rubber (EPDM) phase. In addition, a comparison of E-beam and gamma-ray irradiation is made and the resulting effect on the PTC properties of LDPE/EPDM/CB blends is studied in detail. It is found that with higher dose of gamma-ray, the material undergoes significant radiation damage, while irradiation with E-beam prevents radiation damage due to shorter exposure time. The influence of using treated carbon blacks on the PTC/NTC effects of the composites is also studied. The polymer blends filled with oxidized carbon black display higher PTC intensity followed by a weaker NTC effect, which is due to stronger interactions between oxidized CB's & polymer. It is concluded that strong interactions between polymers and fillers suppress the NTC effect. Finally ESR analysis is used to study the interactions between the polymer blends and fillers. It is found that relatively high structure CB's (CSF-III) have a strong interaction with the polymer blend. Based on all the work done, it is concluded that a blend of high polymer with a crystalline rubber filled with relatively high structure carbon blacks that is irradiated by E-beam will be a good polymer PTC material.

Heparin molecularly imprinted polymer thin flm on gold electrode by plasma-induced graft polymerization for label-free biosensor.

PubMed

Orihara, Kouhei; Hikichi, Atsushi; Arita, Tomohiko; Muguruma, Hitoshi; Yoshimi, Yasuo

2018-03-20

Heparin, a highly sulfated glycosaminoglycan, is an important biomaterial having biological and therapeutic functionalities such as anticoagulation, regeneration, and protein stabilization. This study addresses a label-free quartz crystal microbalance (QCM) biosensor for heparin detection based on a macromolecularly imprinted polymer (MIP) as an artificial recognition element. We demonstrate the novel strategy for MIP in the form of thin film on a gold (Au) electrode with the plasma-induced graft polymerization (PIP) technique. The procedure of PIP is as follows: (i) Hexamethyldisiloxane plasma-polymerized thin film (PPF) as a pre-coating scaffold of active species for PIP (post-polymerization) is deposited on an Au electrode. (ii) The PPF/Au electrode is soaked in an water solution containing heparin (template), (2-(methacryloxy)-ethyl)trimethylammonium chloride acrylamide (functional monomer), acrylamide, and N,N-methylenebisacrylamide (crosslinker). Double bonds of monomer and crosslinker attacked by residually active species in pre-coating PPF cause radical chain reaction. Consequently, a growing polymer network of 20 nm thickness of PIP-MIP thin film is formed and grafted on the PPF/Au surface. (iii) The PIP-MIP/PPF/Au is washed by sodium chloride solution so as to remove the template. Non-imprinted polymer (NIP) is carried out like the same procedure without a template. The AFM, XPS, and QCM measurements show that the PIP process facilitates macromolecularly surface imprinting of template heparin where the template is easily removed and is rapidly rebound to PIP-MIP without a diffusional barrier. The heparin-PIP-MIP specifically binds to heparin compared with heparin analog chondroitin sulfate C (selective factor: 4.0) and a detectable range of heparin in the presence of CS (0.1 wt%) was 0.001-0.1 wt%. The PIP-NIP does not show selectivity between them. The evaluated binding kinetics are association (k a  = 350 ± 100 M -1  s -1 ), dissociation (k d  = (5.0 ± 2.0) × 10 -4  s -1 ), and binding (K D  = 1.3 ± 0.6 μM) constants, demonstrating that the PIP-MIP as a synthetic antibody can be applied to analytical chemistry. Copyright © 2018 Elsevier B.V. All rights reserved.

PECVD de composes de silicium sur polymeres: Etude de la premiere phase du depot

NASA Astrophysics Data System (ADS)

Dennler, Gilles

Since their first introduction in the early 90's, transparent barriers against oxygen and/or water vapor permeation through polymers, such as SiO 2, are the object of increasing interest in the food and pharmaceutical packaging industries, and more recently for the encapsulation of organic-based displays. It is now well known that these thin layers possess barrier properties only if they are thicker than a certain critical thickness, dc. For example, dc is around 12 nm in the case of SiO2 on KaptonRTM PI; below this value, the measured "Oxygen Transmission Rate" (OTR, in standard cm3/m2/day/bar) is roughly the same as that of the uncoated polymer. Until now, no detailed research has been carried out to explain this observation, but a hypothesis was proposed in the literature, based on island-like growth structure of the coating for d ≤ dc. According to this hypothesis, the surface energy of the polymeric substrates is so low that the Volmer-Weber (island-coalescence) growth mode occurs. We have aimed to verify this explanation, that is, to study the initial phase of silicon-compound (SiO2 and SiN) growth on four different polymeric substrates, namely polyimide (KaptonRTM PI), polycarbonate (LexanRTM PC), polypropylene (PP), and polyethyleneterephthalate (MylarRTM PET). Three different deposition methods were used, namely reactive evaporation of SiO, radio-frequency (RF) Plasma Enhanced Chemical Vapor Deposition (RF PECVD), and Distributed Electron Cyclotron Resonance (DECR) PECVD. In this latter case, the substrates were placed in three different positions: (i) in the active glow zone, (ii) downstream, and (iii) downstream, but shielded from photon emission (e.g. VUV) from the plasma. Angle-Resolved X-Ray Photoelectron Spectroscopy (ARXPS), Rutherford Backscattering Spectroscopy (RBS), and Scanning Electron Microscopy (SEM), the latter performed after Reactive Ion Etching (RIE) by oxygen plasma, revealed that growth indeed occurs in a Volmer-Weber mode in the case of evaporated films. The island coalescence was observed to occur at d = 1.2 nm, at which point the sticking coefficient of precursor species changes drastically. Finally, we have investigated the presence of an "interphase" between deposited coatings and the polymeric substrate. (Abstract shortened by UMI.)

Partially degradable fibers and microvascular materials formed from the fibers

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

Dong, Hefei; Pety, Stephen J.; Sottos, Nancy R.

A partially degradable polymeric fiber includes a thermally degradable polymeric core and a coating surrounding at least a portion of the core. The thermally degradable polymeric core includes a polymeric matrix including a poly(hydroxyalkanoate), and a metal selected from the group consisting of an alkali earth metal and a transition metal, in the core polymeric matrix. The concentration of the metal in the polymeric matrix is at least 0.1 wt %. The partially degradable polymeric fiber may be used to form a microvascular system containing one or more microfluidic channels.

Microbial mobilization of plutonium and other actinides from contaminated soil

DOE PAGES

Francis, A. J.; Dodge, C. J.

2015-12-01

Here we examined the dissolution of Pu, U, and Am in contaminated soil from the Nevada Test Site (NTS) due to indigenous microbial activity. Scanning transmission x-ray microscopy (STXM) analysis of the soil showed that Pu was present in its polymeric form and associated with Fe- and Mn- oxides and aluminosilicates. Uranium analysis by x-ray diffraction (μ-XRD) revealed discrete U-containing mineral phases, viz., schoepite, sharpite, and liebigite; synchrotron x-ray fluorescence (μ-XRF) mapping showed its association with Fe- and Ca-phases; and μ-x-ray absorption near edge structure (μ-XANES) confirmed U(IV) and U(VI) oxidation states. Addition of citric acid or glucose to themore » soil and incubated under aerobic or anaerobic conditions enhanced indigenous microbial activity and the dissolution of Pu. Detectable amount of Am and no U was observed in solution. In the citric acid-amended sample, Pu concentration increased with time and decreased to below detection levels when the citric acid was completely consumed. In contrast, with glucose amendment, Pu remained in solution. Pu speciation studies suggest that it exists in mixed oxidation states (III/IV) in a polymeric form as colloids. Although Pu(IV) is the most prevalent and generally considered to be more stable chemical form in the environment, our findings suggest that under the appropriate conditions, microbial activity could affect its solubility and long-term stability in contaminated environments.« less

Microbial mobilization of plutonium and other actinides from contaminated soil

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

Francis, A. J.; Dodge, C. J.

Here we examined the dissolution of Pu, U, and Am in contaminated soil from the Nevada Test Site (NTS) due to indigenous microbial activity. Scanning transmission x-ray microscopy (STXM) analysis of the soil showed that Pu was present in its polymeric form and associated with Fe- and Mn- oxides and aluminosilicates. Uranium analysis by x-ray diffraction (μ-XRD) revealed discrete U-containing mineral phases, viz., schoepite, sharpite, and liebigite; synchrotron x-ray fluorescence (μ-XRF) mapping showed its association with Fe- and Ca-phases; and μ-x-ray absorption near edge structure (μ-XANES) confirmed U(IV) and U(VI) oxidation states. Addition of citric acid or glucose to themore » soil and incubated under aerobic or anaerobic conditions enhanced indigenous microbial activity and the dissolution of Pu. Detectable amount of Am and no U was observed in solution. In the citric acid-amended sample, Pu concentration increased with time and decreased to below detection levels when the citric acid was completely consumed. In contrast, with glucose amendment, Pu remained in solution. Pu speciation studies suggest that it exists in mixed oxidation states (III/IV) in a polymeric form as colloids. Although Pu(IV) is the most prevalent and generally considered to be more stable chemical form in the environment, our findings suggest that under the appropriate conditions, microbial activity could affect its solubility and long-term stability in contaminated environments.« less

Thiolated chitosans.

PubMed

Bernkop-Schnürch, Andreas; Hornof, Margit; Guggi, Davide

2004-01-01

The derivatization of the primary amino groups of chitosan with coupling reagents bearing thiol functions leads to the formation of thiolated chitosans. So far, three types of thiolated chitosans have been generated: chitosan-cysteine conjugates, chitosan-thioglycolic acid conjugates and chitosan-4-thio-butyl-amidine conjugates. Various properties of chitosan are improved by this immobilization of thiol groups. Due to the formation of disulfide bonds with mucus glycoproteins, the mucoadhesiveness is 6--100-fold augmented (I). The permeation of paracellular markers through intestinal mucosa can be enhanced 1.6--3-fold utilizing thiolated instead of unmodified chitosan (II). Moreover, thiolated chitosans display in situ-gelling features, due to the pH-dependent formation of inter- as well as intra-molecular disulfide bonds (III). This latter process provides a strong cohesion and stability of carrier matrices being based on thiolated chitosans (IV). Consequently, thiolated chitosans can guarantee a prolonged controlled release of embedded therapeutic ingredients (V). The potential of thiolated chitosans has meanwhile also been demonstrated in vivo. A significant pharmacological efficacy of 1.3% of orally given salmon calcitonin, for instance, could be achieved utilizing thiolated chitosan as polymeric drug carrier matrix, while no effect was reached using unmodified chitosan. According to these results thiolated chitosans represent a promising new category of polymeric excipients in particular for the non-invasive administration of hydrophilic macromolecules. Further applications such as their use as scaffold materials in tissue engineering or as coating material for stents seem feasible.

Contribution of extracellular polymeric substances from Shewanella sp. HRCR-1 biofilms to U(VI) immobilization.

PubMed

Cao, Bin; Ahmed, Bulbul; Kennedy, David W; Wang, Zheming; Shi, Liang; Marshall, Matthew J; Fredrickson, Jim K; Isern, Nancy G; Majors, Paul D; Beyenal, Haluk

2011-07-01

The goal of this study was to quantify the contribution of extracellular polymeric substances (EPS) to U(VI) immobilization by Shewanella sp. HRCR-1. Through comparison of U(VI) immobilization using cells with bound EPS (bEPS) and cells with minimal EPS, we show that (i) bEPS from Shewanella sp. HRCR-1 biofilms contribute significantly to U(VI) immobilization, especially at low initial U(VI) concentrations, through both sorption and reduction; (ii) bEPS can be considered a functional extension of the cells for U(VI) immobilization and they likely play more important roles at lower initial U(VI) concentrations; and (iii) the U(VI) reduction efficiency is dependent upon the initial U(VI) concentration and decreases at lower concentrations. To quantify the relative contributions of sorption and reduction to U(VI) immobilization by EPS fractions, we isolated loosely associated EPS (laEPS) and bEPS from Shewanella sp. HRCR-1 biofilms grown in a hollow fiber membrane biofilm reactor and tested their reactivity with U(VI). We found that, when reduced, the isolated cell-free EPS fractions could reduce U(VI). Polysaccharides in the EPS likely contributed to U(VI) sorption and dominated the reactivity of laEPS, while redox active components (e.g., outer membrane c-type cytochromes), especially in bEPS, possibly facilitated U(VI) reduction.

The conductivity measurements applied for the evaluation of controlled release of chlorhexidine from thermosensitive N-isopropylacrylamide derivative microgels.

PubMed

Musiał, Witold; Kokol, Vanja; Voncina, Bojana

2009-01-01

The aim of the work was the evaluation of the conductivity changes in aqueous environment, consisting of chlorhexidine, and N-isopropylacrylamide derivative microgel, during increasing the temperature between 25 degrees C and 42 degrees C, as a prerequisite to develop the this microgel for controlled release of chlorhexidine, when alterations in temperature are involved. Conductivity of studied systems underwent specific alterations, when temperature increased. For the system with polymer PNM I the values of conductivity were in the range 104,47 microS/cm - 134,70 microS/ cm, for temperature range 25 degrees C and 42 degrees C. In the case of PNM II - CX system, respective values reached 91,75 microS/cm - 135,95 microS/cm. The lowest conductivity values were observed when PNM III - CX mixture was studied: 96,90 microS/cm and 117,37 microS/cm. When a complex of derivatives of N-isopropylacrylamide with chlorhexidine undergoes thermal alteration, there is a potential to obtain controlled release of chlorhexidine from the polymeric bead in the range between 25 degrees C and 42 degrees C. The affinity of chlorhexidine to the polymer may be assessed in this systems applying the conductivity measurements. The solubility of chlorhexidine in the polymeric systems should be in future evaluated, to determine role of this factor in the conductivity alterations.

Chiral recognition of proteins having L-histidine residues on the surface with lanthanide ion complex incorporated-molecularly imprinted fluorescent nanoparticles.

PubMed

Uzun, Lokman; Uzek, Recep; Senel, Serap; Say, Ridvan; Denizli, Adil

2013-08-01

In this study, lanthanide ion complex incorporated molecularly imprinted fluorescent nanoparticles were synthesized. A combination of three novel approaches was applied for the purpose. First, lanthanide ions [Terbium(III)] were complexed with N-methacryloyl-L-histidine (MAH), polymerizable derivative of L-histidine amino acid, in order to incorporate the complex directly into the polymeric backbone. At the second stage, L-histidine molecules imprinted nanoparticles were utilized instead of whole protein imprinting in order to avoid whole drawbacks such as fragility, complexity, denaturation tendency, and conformation dependency. At the third stage following the first two steps mentioned above, imprinted L-histidine was coordinated with cupric ions [Cu(II)] to conduct the study under mild conditions. Then, molecularly imprinted fluorescent nanoparticles synthesized were used for L-histidine adsorption from aqueous solution to optimize conditions for adsorption and fluorimetric detection. Finally, usability of nanoparticles was investigated for chiral biorecognition using stereoisomer, D-histidine, racemic mixture, D,L-histidine, proteins with surface L-histidine residue, lysozyme, cytochrome C, or without ribonuclease A. The results revealed that the proposed polymerization strategy could make significant contribution to the solution of chronic problems of fluorescent component introduction into polymers. Additionally, the fluorescent nanoparticles reported here could be used for selective separation and fluorescent monitoring purposes. Copyright © 2013 Elsevier B.V. All rights reserved.

Contribution of Extracellular Polymeric Substances from Shewanella sp. HRCR-1 Biofilms to U(VI) Immobilization

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

Cao, Bin; Ahmed, B.; Kennedy, David W.

2011-06-05

The goal of this study was to quantify the contribution of extracellular polymeric substances (EPS) in U(VI) immobilization by Shewanella sp. HRCR-1. Through comparison of U(VI) immobilization using cells with bound EPS (bEPS) and cells without EPS, we showed that i) bEPS from Shewanella sp. HRCR-1 biofilms contributed significantly to U(VI) immobilization, especially at low initial U(VI) concentrations, through both sorption and reduction; ii) bEPS could be considered as a functional extension of the cells for U(VI) immobilization and they likely play more important roles at initial U(VI) concentrations; and iii) U(VI) reduction efficiency was found to be dependent uponmore » initial U(VI) concentration and the efficiency decreased at lower concentrations. To quantify relative contribution of sorption and reduction in U(VI) immobilization by EPS fractions, we isolated loosely associated EPS (laEPS) and bEPS from Shewanella sp. HRCR-1 biofilms grown in a hollow fiber membrane biofilm reactor and tested their reactivity with U(V). We found that, when in reduced form, the isolated cell-free EPS fractions could reduce U(VI). Polysaccharides in the EPS likely contributed to U(VI) sorption and dominated reactivity of laEPS while redox active components (e.g., outer membrane c-type cytochromes), especially in bEPS, might facilitate U(VI) reduction.« less

Redshift evolution of the dynamical properties of massive galaxies from SDSS-III/BOSS

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

Beifiori, Alessandra; Saglia, Roberto P.; Bender, Ralf

2014-07-10

We study the redshift evolution of the dynamical properties of ∼180, 000 massive galaxies from SDSS-III/BOSS combined with a local early-type galaxy sample from SDSS-II in the redshift range 0.1 ≤ z ≤ 0.6. The typical stellar mass of this sample is M{sub *} ∼2 × 10{sup 11} M{sub ☉}. We analyze the evolution of the galaxy parameters effective radius, stellar velocity dispersion, and the dynamical to stellar mass ratio with redshift. As the effective radii of BOSS galaxies at these redshifts are not well resolved in the Sloan Digital Sky Survey (SDSS) imaging we calibrate the SDSS size measurementsmore » with Hubble Space Telescope/COSMOS photometry for a sub-sample of galaxies. We further apply a correction for progenitor bias to build a sample which consists of a coeval, passively evolving population. Systematic errors due to size correction and the calculation of dynamical mass are assessed through Monte Carlo simulations. At fixed stellar or dynamical mass, we find moderate evolution in galaxy size and stellar velocity dispersion, in agreement with previous studies. We show that this results in a decrease of the dynamical to stellar mass ratio with redshift at >2σ significance. By combining our sample with high-redshift literature data, we find that this evolution of the dynamical to stellar mass ratio continues beyond z ∼ 0.7 up to z > 2 as M{sub dyn}/M{sub *} ∼(1 + z){sup –0.30±0.12}, further strengthening the evidence for an increase of M{sub dyn}/M{sub *} with cosmic time. This result is in line with recent predictions from galaxy formation simulations based on minor merger driven mass growth, in which the dark matter fraction within the half-light radius increases with cosmic time.« less

The geomorphology and evolution of aeolian landforms within a river valley in a semi-humid environment: A case study from Mainling Valley, Qinghai-Tibet Plateau

NASA Astrophysics Data System (ADS)

Zhou, Na; Zhang, Chun-Lai; Wu, Xiao-Xu; Wang, Xun-ming; Kang, Li-qiang

2014-11-01

This paper systematically analyzes a valley's aeolian landforms in a semi-humid region and presents a model of its contemporary evolution. Mainling Valley of the Yarlung Zangbo River on the Qinghai-Tibet Plateau was chosen as the case study for the analysis of morphometric characteristics and the evolution sequence of aeolian landforms via field data and remote sensing images. The aeolian landforms were primarily composed of aeolian sand belts on river terraces and dunes (sheets) on hillside slopes. Three types of aeolian sand belts were identified based on their dune types. In type I belts, an erosive air stream combined with relatively high vegetation cover (10%) produced sparsely distributed parabolic dunes with a high variability of dune heights; in type II belts, the continual reworking by the erosive air stream in combination with low vegetation cover (3%) formed more densely distributed barchans and transitional dunes with a moderate variability of dune heights; and in type III belts, the gradual evolution from an erosive sand-laden air stream to a saturated sand-laden air stream in combination with low vegetation cover (2%) produced the densest crescentic dunefields but with the least variability in dune heights. Dune sizes increase, dune shapes become uniform, and dune distribution becomes close from type I to III belts. Lateral linking and merging of the dunes were also observed within the belts. Together this evidence indicates that an evolution sequence may exist. Aeolian dunefields in the belt appear to evolve from embryonic parabolic dunefields to adolescent barchan dunefields and, subsequently, to mature compound crescentic dunefields. As the aeolian sand belt evolves into the mature stage, sand accumulations at the foot of the mountain valley can be steps for sand accumulation on valley-side slopes.

Carboxyl-functionalized magnetic microparticle carrier for isolation and identification of DNA in dairy products

NASA Astrophysics Data System (ADS)

Horák, Daniel; Rittich, Bohuslav; Španová, Alena

2007-04-01

Magnetite nanoparticles about 14 nm in diameter were obtained by chemical coprecipitation of Fe(II) and Fe(III) salts with aqueous ammonia in the presence of poly(ethylene glycol) (PEG). Magnetic poly(glycidyl methacrylate) (PGMA) microspheres about 1 μm in diameter were prepared by dispersion polymerization of GMA in aqueous ethanol in the presence of PEG-coated magnetite nanoparticles. The microspheres were hydrolyzed and carboxyl groups introduced by oxidation with KMnO4. The particles reversibly bound bacterial DNA of Bifidobacterium and Lactobacillus genera in the presence of high concentrations of PEG 6000 and sodium chloride from crude cell lysates of various dairy products (butter milk, cheese, yoghurt, probiotic tablets) or from cell lyophilisates. The presence of Bifidobacterium and Lactobacillus DNA in samples was confirmed by PCR amplification.

Self-Assembly of Optical Molecules with Supramolecular Concepts

PubMed Central

Okamoto, Ken; Chithra, Parayalil; Richards, Gary J.; Hill, Jonathan P.; Ariga, Katsuhiko

2009-01-01

Fabrication of nano-sized objects is one of the most important issues in nanoscience and nanotechnology. Soft nanomaterials with flexible properties have been given much attention and can be obtained through bottom-up processing from functional molecules, where self-assembly based on supramolecular chemistry and designed assembly have become crucial processes and techniques. Among the various functional molecules, dyes have become important materials in certain areas of nanotechnology and their self-assembling behaviors have been actively researched. In this short review, we briefly introduce recent progress in self-assembly of optical molecules and dyes, based mainly on supramolecular concepts. The introduced examples are classified into four categories: self-assembly of (i) low-molecular-weight dyes and (ii) polymeric dyes and dye self-assembly (iii) in nanoscale architectures and (iv) at surfaces. PMID:19564931

Porous polymer networks and ion-exchange media and metal-polymer composites made therefrom

DOEpatents

Kanatzidis, Mercouri G; Katsoulidis, Alexandros

2015-03-10

Porous polymeric networks and composite materials comprising metal nanoparticles distributed in the polymeric networks are provided. Also provided are methods for using the polymeric networks and the composite materials in liquid- and vapor-phase waste remediation applications. The porous polymeric networks, are highly porous, three-dimensional structures characterized by high surface areas. The polymeric networks comprise polymers polymerized from aldehydes and phenolic molecules.

Porous polymer networks and ion-exchange media and metal-polymer composites made therefrom

DOEpatents

Kanatzidis, Mercouri G.; Katsoulidis, Alexandros

2016-10-18

Porous polymeric networks and composite materials comprising metal nanoparticles distributed in the polymeric networks are provided. Also provided are methods for using the polymeric networks and the composite materials in liquid- and vapor-phase waste remediation applications. The porous polymeric networks, are highly porous, three-dimensional structures characterized by high surface areas. The polymeric networks comprise polymers polymerized from aldehydes and phenolic molecules.

Expanding the eco-evolutionary context of herbicide resistance research.

PubMed

Neve, Paul; Busi, Roberto; Renton, Michael; Vila-Aiub, Martin M

2014-09-01

The potential for human-driven evolution in economically and environmentally important organisms in medicine, agriculture and conservation management is now widely recognised. The evolution of herbicide resistance in weeds is a classic example of rapid adaptation in the face of human-mediated selection. Management strategies that aim to slow or prevent the evolution of herbicide resistance must be informed by an understanding of the ecological and evolutionary factors that drive selection in weed populations. Here, we argue for a greater focus on the ultimate causes of selection for resistance in herbicide resistance studies. The emerging fields of eco-evolutionary dynamics and applied evolutionary biology offer a means to achieve this goal and to consider herbicide resistance in a broader and sometimes novel context. Four relevant research questions are presented, which examine (i) the impact of herbicide dose on selection for resistance, (ii) plant fitness in herbicide resistance studies, (iii) the efficacy of herbicide rotations and mixtures and (iv) the impacts of gene flow on resistance evolution and spread. In all cases, fundamental ecology and evolution have the potential to offer new insights into herbicide resistance evolution and management. © 2014 Society of Chemical Industry.

Risk, mobility or population size? Drivers of technological richness among contact-period western North American hunter-gatherers.

PubMed

Collard, Mark; Buchanan, Briggs; O'Brien, Michael J; Scholnick, Jonathan

2013-11-19

Identifying factors that influence technological evolution in small-scale societies is important for understanding human evolution. There have been a number of attempts to identify factors that influence the evolution of food-getting technology, but little work has examined the factors that affect the evolution of other technologies. Here, we focus on variation in technological richness (total number of material items and techniques) among recent hunter-gatherers from western North America and test three hypotheses: (i) technological richness is affected by environmental risk, (ii) population size is the primary determinant of technological richness, and (iii) technological richness is constrained by residential mobility. We found technological richness to be correlated with a proxy for environmental risk-mean rainfall for the driest month-in the manner predicted by the risk hypothesis. Support for the hypothesis persisted when we controlled for shared history and intergroup contact. We found no evidence that technological richness is affected by population size or residential mobility. These results have important implications for unravelling the complexities of technological evolution.

Risk, mobility or population size? Drivers of technological richness among contact-period western North American hunter–gatherers

PubMed Central

Collard, Mark; Buchanan, Briggs; O'Brien, Michael J.; Scholnick, Jonathan

2013-01-01

Identifying factors that influence technological evolution in small-scale societies is important for understanding human evolution. There have been a number of attempts to identify factors that influence the evolution of food-getting technology, but little work has examined the factors that affect the evolution of other technologies. Here, we focus on variation in technological richness (total number of material items and techniques) among recent hunter–gatherers from western North America and test three hypotheses: (i) technological richness is affected by environmental risk, (ii) population size is the primary determinant of technological richness, and (iii) technological richness is constrained by residential mobility. We found technological richness to be correlated with a proxy for environmental risk—mean rainfall for the driest month—in the manner predicted by the risk hypothesis. Support for the hypothesis persisted when we controlled for shared history and intergroup contact. We found no evidence that technological richness is affected by population size or residential mobility. These results have important implications for unravelling the complexities of technological evolution. PMID:24101622

Nano-network with dual temperature and pH responsiveness based on copolymers of 2-hydroxyethyl methacrylate with 3,9-divinyl-2,4,8,10-tetraoxaspiro[5.5]-undecane

NASA Astrophysics Data System (ADS)

Chiriac, Aurica P.; Nita, Loredana E.; Nistor, Manuela T.

2011-12-01

This study refers to the synthesis of a nano-network with dual temperature and pH responsiveness based on the 2-hydroxyethyl methacrylate (HEMA) copolymers with a comonomer with spiroacetal moiety and crosslinking capacity, namely 3,9-divinyl-2,4,8,10-tetraoxaspiro[5.5]-undecane (U). The copolymers were synthesized by radical emulsion polymerization, using 4,4'-azobis(cyanopentanoic acid) as initiator, in the presence of sodium lauryl sulfate as tensioactive agent and poly(vinyl alcohol) as protective colloid. Three copolymer variants were taken into study resulted from the different ratio between the comonomers (HEMA/U), which was about 98/2, 95/5, and 90/10, respectively. The copolymers were characterized by FTIR and thermal analysis. The copolymers sensitivity was evidenced by studying the evolution of the hydrodynamic radius and zeta potential of the polymeric particles as a function of pH. Thus, the particles size increases with the comonomer amount, from 193 nm in case of the homopolymer up to 253 nm for the copolymer with maximum content of the comonomer (10%). The increase of the particle hydrodynamic radius with the growth of temperature was also put into evidence.

Coupled Phases and Combinatorial Selection in Fluctuating Hydrothermal Pools: A Scenario to Guide Experimental Approaches to the Origin of Cellular Life

PubMed Central

Damer, Bruce; Deamer, David

2015-01-01

Hydrothermal fields on the prebiotic Earth are candidate environments for biogenesis. We propose a model in which molecular systems driven by cycles of hydration and dehydration in such sites undergo chemical evolution in dehydrated films on mineral surfaces followed by encapsulation and combinatorial selection in a hydrated bulk phase. The dehydrated phase can consist of concentrated eutectic mixtures or multilamellar liquid crystalline matrices. Both conditions organize and concentrate potential monomers and thereby promote polymerization reactions that are driven by reduced water activity in the dehydrated phase. In the case of multilamellar lipid matrices, polymers that have been synthesized are captured in lipid vesicles upon rehydration to produce a variety of molecular systems. Each vesicle represents a protocell, an “experiment” in a natural version of combinatorial chemistry. Two kinds of selective processes can then occur. The first is a physical process in which relatively stable molecular systems will be preferentially selected. The second is a chemical process in which rare combinations of encapsulated polymers form systems capable of capturing energy and nutrients to undergo growth by catalyzed polymerization. Given continued cycling over extended time spans, such combinatorial processes will give rise to molecular systems having the fundamental properties of life. PMID:25780958

Polymer therapeutics: Top 10 selling pharmaceuticals - what next?

PubMed

Duncan, Ruth

2014-09-28

At the time of the first issue of the Journal of Controlled Release (JCR), polymeric drugs, polymer-drug and protein conjugates and block copolymer micelles carrying bound drugs, i.e. polymer therapeutics, were still regarded as scientific curiosities with little or no prospect of generating practical to use medicines. How this perception has changed. Many major Pharma now have R&D programmes in this area and in 2013 two polymer therapeutics, Copaxone and Neulasta, are featured in the Top 10 US pharmaceutical sales list. Although there are a growing number of marketed products (e.g. PEGylated proteins, a PEG-aptamer and oral polymeric sequestrants), and the first follow-on (generic products) are emerging, the first polymer-drug conjugates and block copolymer micelle products (as covalent conjugates) have yet to enter routine clinical use. Industrial familiarity and recent advances in the underpinning scientific disciplines will no doubt accelerate the transfer of polymer therapeutics into clinically useful medicines and imaging agents. This short personal perspective reflects on the current status of polymer therapeutics and the future opportunities to improve their successful translation. It adds to recent and historical reviews that comprehensively document the evolution of the field since JCR was born. Copyright © 2014 Elsevier B.V. All rights reserved.

Investigation of Solution Polymerizations in Microgravity and 1 G

NASA Technical Reports Server (NTRS)

Kennedy, Alvin P.

1998-01-01

The in-situ dielectric spectra for the solution polymerization of polydiacetylene has been successfully measured. The results show a distinct difference between the response for the bulk solution and surface polymerization. It also shows a low frequency peak in the dissipation factor which is present in both the bulk and surface polymerizations. These features may prove to be significant indicators for important polymerization processes. Future studies will investigate the mechanisms responsible for these dielectric responses. This technique will eventually be used to monitor microgravity polymerizations and provide in-situ data on how microgravity affects solution polymerization.

Thermally Stable, Piezoelectric and Pyroelectric Polymeric Substrates and Method Relating Thereto

NASA Technical Reports Server (NTRS)

Simpson, Joycelyn O. (Inventor); St.Claire, Terry L. (Inventor)

2002-01-01

A thermally stable, piezoelectric and pyroelectric polymeric substrate was prepared, This thermally stable, piezoelectric and pyroelectric polymeric substrate may be used to prepare electromechanical transducers, thermomechanical transducers, accelerometers, acoustic sensors, infrared sensors, pressure sensors, vibration sensors, impact sensors. in-situ temperature sensors, in-situ stress/strain sensors, micro actuators, switches. adjustable fresnel lenses, speakers, tactile sensors, weather sensors, micro positioners, ultrasonic devices, power generators, tunable reflectors, microphones, and hydrophones. The process for preparing these polymeric substrates includes: providing a polymeric substrate having a softening temperature greater than 100 C; depositing a metal electrode material onto the polymer film; attaching a plurality of electrical leads to the metal electrode coated polymeric substrates; heating the metal electrode coated polymeric substrate in a low dielectric medium; applying a voltage to the heated metal electrode coated polymeric substrate to induce polarization; and cooling the polarized metal electrode coated polymeric electrode while maintaining a constant voltage.

Thermally Stable, Piezoelectric and Pyroelectric Polymeric Substrates

NASA Technical Reports Server (NTRS)

Simpson, Joycely O. (Inventor); St.Clair, Terry L. (Inventor)

1999-01-01

A thermally stable, piezoelectric and pyroelectric polymeric substrate was prepared. This thermally stable, piezoelectric and pyroelectric polymeric substrate may be used to prepare electromechanical transducers, thermomechanical transducers, accelerometers. acoustic sensors, infrared sensors, pressure sensors, vibration sensors, impact sensors, in-situ temperature sensors, in-situ stress/strain sensors, micro actuators, switches, adjustable fresnel lenses, speakers, tactile sensors. weather sensors, micro positioners, ultrasonic devices, power generators, tunable reflectors, microphones, and hydrophones. The process for preparing these polymeric substrates includes: providing a polymeric substrate having a softening temperature greater than 1000 C; depositing a metal electrode material onto the polymer film; attaching a plurality of electrical leads to the metal electrode coated polymeric substrate; heating the metal electrode coated polymeric substrate in a low dielectric medium; applying a voltage to the heated metal electrode coated polymeric substrate to induce polarization; and cooling the polarized metal electrode coated polymeric electrode while maintaining a constant voltage.

Method of Making Thermally Stable, Piezoelectric and Proelectric Polymeric Substrates

NASA Technical Reports Server (NTRS)

Simpson, Joycelyn O. (Inventor); St.Clair, Terry L. (Inventor)

1999-01-01

A thermally stable, piezoelectric and pyroelectric polymeric substrate was prepared. This thermally stable, piezoelectric and pyroelectric polymeric substrate may be used to prepare electromechanical transducers, thermomechanical transducers, accelerometers, acoustic sensors, infrared sensors, pressure sensors, vibration sensors, impact sensors. in-situ temperature sensors, in-situ stress/strain sensors, micro actuators, switches, adjustable fresnel lenses, speakers, tactile sensors, weather sensors, micro positioners, ultrasonic devices, power generators, tunable reflectors, microphones, and hydrophones. The process for preparing these polymeric substrates includes: providing a polymeric substrate having a softening temperature greater than 100 C; depositing a metal electrode material onto the polymer film; attaching a plurality of electrical leads to the metal electrode coated polymeric substrate; heating the metal electrode coated polymeric substrate in a low dielectric medium: applying a voltage to the heated metal electrode coated polymeric substrate to induce polarization; and cooling the polarized metal electrode coated polymeric electrode while maintaining a constant voltage.