Science.gov

Sample records for arg-specific bifunctional crosslinkers

  1. Bifunctional crosslinking ligands for transthyretin

    PubMed Central

    Mangione, P. Patrizia; Deroo, Stéphanie; Ellmerich, Stephan; Bellotti, Vittorio; Kolstoe, Simon; Wood, Stephen P.; Robinson, Carol V.; Smith, Martin D.; Tennent, Glenys A.; Broadbridge, Robert J.; Council, Claire E.; Thurston, Joanne R.; Steadman, Victoria A.; Vong, Antonio K.; Swain, Christopher J.; Pepys, Mark B.; Taylor, Graham W.

    2015-01-01

    Wild-type and variant forms of transthyretin (TTR), a normal plasma protein, are amyloidogenic and can be deposited in the tissues as amyloid fibrils causing acquired and hereditary systemic TTR amyloidosis, a debilitating and usually fatal disease. Reduction in the abundance of amyloid fibril precursor proteins arrests amyloid deposition and halts disease progression in all forms of amyloidosis including TTR type. Our previous demonstration that circulating serum amyloid P component (SAP) is efficiently depleted by administration of a specific small molecule ligand compound, that non-covalently crosslinks pairs of SAP molecules, suggested that TTR may be also amenable to this approach. We first confirmed that chemically crosslinked human TTR is rapidly cleared from the circulation in mice. In order to crosslink pairs of TTR molecules, promote their accelerated clearance and thus therapeutically deplete plasma TTR, we prepared a range of bivalent specific ligands for the thyroxine binding sites of TTR. Non-covalently bound human TTR–ligand complexes were formed that were stable in vitro and in vivo, but they were not cleared from the plasma of mice in vivo more rapidly than native uncomplexed TTR. Therapeutic depletion of circulating TTR will require additional mechanisms. PMID:26400472

  2. Acid–base bifunctional shell cross-linked micelle nanoreactor for one-pot tandem reaction

    SciTech Connect

    Lee, Li -Chen; Lu, Jie; Weck, Marcus; Jones, Christopher W.

    2015-12-29

    Shell cross-linked micelles (SCMs) containing acid sites in the shell and base sites in the core are prepared from amphiphilic poly(2-oxazoline) triblock copolymers. The materials are utilized as two-chamber nanoreactors for a prototypical acid-base bifunctional tandem deacetalization-nitroaldol reaction. Furthermore, the acid and base sites are localized in different regions of the micelle, allowing the two steps in the reaction sequence to largely proceed in separate compartments, akin to the compartmentalization that occurs in biological systems.

  3. A bifunctional monocyclic beta-lactam cross-links across the active site of beta-lactamase.

    PubMed

    Ahluwalia, R; Day, R A; Nauss, J

    1995-01-17

    A 4-alkoxy-2-azetidinone behaves as a bifunctional active site-directed inhibitor of the class A beta-lactamase from Bacillus cereus 569/H. It cross-links SER 70 and LYS 234 as it binds in a approximately 1:1 ratio. The cross-linked enzyme is irreversibly inhibited while the secondary structure is partially stabilized under conditions when the native enzyme is otherwise converted to a form with no detectable secondary structure by circular dichroism. PMID:7826374

  4. Bifunctional Crosslinking Agents Enhance Anion Exchange Membrane Efficacy for Vanadium Redox Flow Batteries.

    PubMed

    Wang, Wenpin; Xu, Min; Wang, Shubo; Xie, Xiaofeng; Lv, Yafei; Ramani, Vijay K

    2014-06-01

    A series of cross-linked fluorinated poly (aryl ether oxadiazole) membranes (FPAEOM) derivatized with imidazolium groups were prepared. Poly (N-vinylimidazole) (PVI) was used as the bifunctional cross-linking agent to: a) lower vanadium permeability, b) enhance dimensional stability, and c) concomitantly provide added ion exchange capacity in the resultant anion exchange membranes. At a molar ratio of PVI to FPAEOM of 1.5, the resultant membrane (FPAEOM-1.5 PVI) had an ion exchange capacity of 2.2 meq g-1, a vanadium permeability of 6.8×10-7 cm2 min-1, a water uptake of 68 wt.%, and an ionic conductivity of 22.0 mS cm-1, all at 25°C. Single cells prepared with the FPAEOM-1.5 PVI membrane exhibited a higher coulombic efficiency (> 92%) and energy efficiency (> 86%) after 40 test cycles in vanadium redox flow battery. The imidazolium cation showed high chemical stability in highly acidic and oxidizing vanadium solution as opposed to poor stability in alkaline solutions. Based on our DFT studies, this was attributed to the lower HOMO energy (-7.265 eV) of the HSO4- ion (compared to the OH- ion; -5.496 eV) and the larger HOMO-LUMO energy gap (6.394 eV) of dimethylimidazolium bisulfate ([DMIM] [HSO4]) as compared to [DMIM] [OH] (5.387 eV). PMID:24884171

  5. Azidopropylvinylsulfonamide as a New Bifunctional Click Reagent for Bioorthogonal Conjugations: Application for DNA-Protein Cross-Linking.

    PubMed

    Dadová, Jitka; Vrábel, Milan; Adámik, Matej; Brázdová, Marie; Pohl, Radek; Fojta, Miroslav; Hocek, Michal

    2015-11-01

    N-(3-Azidopropyl)vinylsulfonamide was developed as a new bifunctional bioconjugation reagent suitable for the cross-linking of biomolecules through copper(I)-catalyzed azide-alkyne cycloaddition and thiol Michael addition reactions under biorthogonal conditions. The reagent is easily clicked to an acetylene-containing DNA or protein and then reacts with cysteine-containing peptides or proteins to form covalent cross-links. Several examples of bioconjugations of ethynyl- or octadiynyl-modified DNA with peptides, p53 protein, or alkyne-modified human carbonic anhydrase with peptides are given. PMID:26377361

  6. Composite Films of Poly(vinyl alcohol) and Bifunctional Cross-linking Cellulose Nanocrystals.

    PubMed

    Sirviö, Juho Antti; Honkaniemi, Samuli; Visanko, Miikka; Liimatainen, Henrikki

    2015-09-01

    Long and flexible cellulose nanofibrils or stiff and short cellulose nanocrystals (CNCs) are both promising lightweight materials with high strength and the potential to serve as reinforcing agents in many polymeric materials. In this study, bifunctional reactive cellulose nanocrystals (RCNCs) with carboxyl and aldehyde functionalities were used as reinforcements to prepare acetal-bonding cross-linked poly(vinyl alcohol) (PVA) films. Two RCNCs were obtained through the mechanical homogenization of partially carboxylated dialdehyde cellulose (DAC) with a residual aldehyde content of 0.55 and 1.93 mmol/g and a carboxyl content of 1.65 and 1.93 mmol/g, respectively. The mechanical, thermal, and barrier properties of PVA-RCNC films with a variable mass ratio of RCNCs (0.5-10%) were determined. Reference CNCs without reactive aldehydes were obtained through the reduction of aldehyde functionalities to primary hydroxide groups, and their reinforcing effect was compared to RCNCs. With the addition of 10% acetal-bonding RCNCs with respect to PVA weight, the tensile strength and Young's modulus were up to 2-fold greater than those of pure PVA film. An addition of only 0.5% RCNCs improved the tensile strength of the PVA film by 66% and the modulus by 61%. In comparison, a significantly lower reinforcing effect (19% with CNC loading of 0.5%) was found using reference CNCs. PVA's effective oxygen barrier and thermal properties were preserved when RCNCs were introduced into the films. PMID:26280660

  7. The use of bifunctional polyethyleneglycol derivatives for coupling of proteins to and cross-linking of collagen matrices.

    PubMed

    Chen, J-S; Noah, E M; Pallua, N; Steffens, G C M

    2002-11-01

    The realization of three-dimensional (3D) degradable matrices which slowly release bio-active components represents a major challenge in the field of tissue engineering. In this paper we report on the usage of commercially available bifunctional agents for both the covalent coupling of proteins to and the cross-linking of collagen matrices. Proteins - horse radish peroxidase (HRP) was used as a model protein - were cross-linked with either a homobifunctional (disuccinimidyldisuccinatepolyethylene-glycol) or a heterobifunctional (N-hydroxysuccinimidylvinylsulfonepolyethyleneglycol) agent. In the case of the heterobifunctional cross-linking agent the collagen matrices were previously modified with succinimidylacetylthioacetate in order to introduce sulfhydryl groups. As compared with control experiments a 10-fold and 50-fold increase of immobilized proteins were achieved with the homobifunctional and heterobifunctional cross-linker resp. The HRP-PEG conjugates demonstrated a better long-term stability as compared to the non-treated HRP. The effects of the cross-linking agents and the thiolation reagent succinimidylacetylthio acetate on the in vitro degradation of the collagen matrices by collagenase were also investigated. In particular the reaction with succinimidylacetylthio acetate appears to offer interesting opportunities both for coupling active proteins and modulating the degradation times of collagen matrices. PMID:15348172

  8. Bifunctional alkylating agent-mediated MGMT-DNA cross-linking and its proteolytic cleavage in 16HBE cells.

    PubMed

    Cheng, Jin; Ye, Feng; Dan, Guorong; Zhao, Yuanpeng; Wang, Bin; Zhao, Jiqing; Sai, Yan; Zou, Zhongmin

    2016-08-15

    Nitrogen mustard (NM), a bifunctional alkylating agent (BAA), contains two alkyl arms and can act as a cross-linking bridge between DNA and protein to form a DNA-protein cross-link (DPC). O(6)-methylguanine-DNA methyltransferase (MGMT), a DNA repair enzyme for alkyl adducts removal, is found to enhance cell sensitivity to BAAs and to promote damage, possibly due to its stable covalent cross-linking with DNA mediated by BAAs. To investigate MGMT-DNA cross-link (mDPC) formation and its possible dual roles in NM exposure, human bronchial epithelial cell line 16HBE was subjected to different concentrations of HN2, a kind of NM, and we found mDPC was induced by HN2 in a concentration-dependent manner, but the mRNA and total protein of MGMT were suppressed. As early as 1h after HN2 treatment, high mDPC was achieved and the level maintained for up to 24h. Quick total DPC (tDPC) and γ-H2AX accumulation were observed. To evaluate the effect of newly predicted protease DVC1 on DPC cleavage, we applied siRNA of MGMT and DVC1, MG132 (proteasome inhibitor), and NMS-873 (p97 inhibitor) and found that proteolysis plays a role. DVC1 was proven to be more important in the cleavage of mDPC than tDPC in a p97-dependent manner. HN2 exposure induced DVC1 upregulation, which was at least partially contributed to MGMT cleavage by proteolysis because HN2-induced mDPC level and DNA damage was closely related with DVC1 expression. Homologous recombination (HR) was also activated. Our findings demonstrated that MGMT might turn into a DNA damage promoter by forming DPC when exposed to HN2. Proteolysis, especially DVC1, plays a crucial role in mDPC repair. PMID:27342729

  9. Creation of catalytically active particles from enzymes crosslinked with a natural bifunctional agent--homocysteine thiolactone.

    PubMed

    Stroylova, Yulia Y; Semenyuk, Pavel I; Asriyantz, Regina A; Gaillard, Cedric; Haertlé, Thomas; Muronetz, Vladimir I

    2014-09-01

    The current study describes an approach to creation of catalytically active particles with increased stability from enzymes by N-homocysteinylation, a naturally presented protein modification. Enzymatic activities and properties of two globular tetrameric enzymes glyceraldehyde-3-phosphate dehydrogenase (GAPDH) and lactate dehydrogenase (LDH) were studied before and after N-homocysteinylation. Modification of these proteins concerns the accessible lysine residues and introduces an average of 2-2,5 homocysteine residues per protein monomer. Formation of a range of aggregates was observed for both enzymes, which assemble via formation of intermolecular noncovalent bonds and by disulfide bonds. It was demonstrated that both studied enzymes retain their catalytic activities on modification and the subsequent formation of oligomeric forms. At low concentrations of homocysteine thiolactone, modification of GAPDH leads not only to prevention of spontaneous inactivation but also increases thermal stability of this enzyme on heating to 80°C. A moderate reduction of the activity of GAPDH observed in case of its crosslinking with 50-fold excess of homocysteine thiolactone per lysine is probably caused by hindered substrate diffusion. Spherical particles of 100 nm and larger diameters were observed by transmission electron microscopy and atomic force microscope techniques after modification of GAPDH with different homocysteine thiolactone concentrations. In case of LDH, branched fibril-like aggregates were observed under the same conditions. Interestingly, crosslinked samples of both proteins were found to have reversible thermal denaturation profiles, indicating that modification with homocysteine thiolactone stabilizes the spatial structure of these enzymes. PMID:24912753

  10. Cross-linking with bifunctional reagents and its application to the study of the molecular symmetry and the arrangement of subunits in hexameric protein oligomers.

    PubMed

    Azem, Abdussalam; Tsfadia, Yossi; Hajouj, Omar; Shaked, Isabella; Daniel, Ezra

    2010-04-01

    Cross-linking with a bifunctional reagent and subsequent SDS gel electrophoresis is a simple but effective method to study the symmetry and arrangement of subunits in oligomeric proteins. In this study, theoretical expressions for the description of cross-linking patterns were derived for protein homohexamers through extension of the method used for tetramers by Hajdu et al. (1976). The derived equations were used for the analysis of cross-linking by glutardialdehyde of four protein hexamers: beef liver glutamate dehydrogenase (GDH), jack bean urease, hemocyanin from the spiny lobster Panulirus pencillatus (PpHc), Escherichia coli glutamate decarboxylase (GDC) and for analysis of published data on the cross-linking of hexameric E. coli rho by dimethyl suberimidate. Best fit models showed that the subunits in the first four proteins are arranged according to D(3) symmetry in two layers, each subunit able to cross-link to three neighboring subunits for GDH and urease, or to four for PpHc and GDC. The findings indicate a dimer-of-trimers eclipsed arrangement of subunits for GDH and urease and a trimer-of-dimers staggered one for PpHc and GDC. In rho, the subunits are arranged according to D(3) symmetry in a trimer-of-dimers ring. The conclusions from cross-linking of GDH and GDC, PpHc and rho are consistent with results from X-ray crystal structure, those for urease with findings from electron microscopy. PMID:20005307

  11. Lactogen receptors in rat Leydig cells: analysis of their structure with bifunctional cross-linking reagents

    SciTech Connect

    Bonifacino, J.S.; Dufau, M.L.

    1985-04-01

    (/sup 125/I)Iodohuman GH was found to bind to receptors with specificity for lactogenic hormones in a Triton X-100 extract from Leydig cell membranes displaying an affinity constant of 3.8 X 10(/sup 9/) M-1 and a binding capacity of 167 fmol/mg protein. Cross-linking of solubilized (/sup 125/I)iodohuman GH-receptor complexes with disuccinimidyl suberate followed by analysis by sodium dodecyl sulfate-gel electrophoresis in the presence of beta-mercaptoethanol and autoradiography resulted in the appearance of bands with apparent mol wt of 113,000, 103,000, 59,000, and 53,000. The appearance of these bands was prevented by incubation in the presence of lactogenic hormones. By using a two-dimensional electrophoresis technique (first dimension under nonreducing conditions; second dimension under reducing conditions), it was demonstrated that a fraction of the mol wt 59,000 species can be released from the mol wt 103,000 species upon cleavage of disulfide bonds. These results suggest the existence of lactogen receptor species with approximate mol wt of 91,000, 81,000, 37,000, and 31,000 in Triton X-100 extracts from Leydig cell membranes if the contribution of the free hormone (mol wt, 22,000) is subtracted. A fraction of the mol wt 37,000 subunits appears to be contained within the 81,000 species linked through disulfide bonds.

  12. Cross-linked informofers.

    PubMed Central

    Prosvirnin, V V; Ruzidic, S; Samarina, O P

    1979-01-01

    The proteins of 30S RNP particles containing pre-mRNA (hnRNA) were cross-linked with bifunctional reagents (dimethyl-suberimidate and dimethyl-3,3'-dithiobispropionimidate). Further treatment with 1 or 2 M NaCl dissociates all RNA from protein. However, a significant part of protein particles--informofers being cross-linked survived high salt treatment. Their sedimentation coefficients were close to those of original particles. No RNA could be detected in the informofers even after labeling the cells with a precursor for a long period of time. Sodium dodecylsulfate or urea dissociated cross-linked informofers into oligomeric polypeptides. They could be dissociated by beta-mercaptoethanol treatment if a reversible cross-linked reagent had been used. The resulting polypeptides were represented by informatin. RNP particles (30S RNP or poly-particles) were reconstituted upon mixing of cross-linked informofers with pre-mRNA and removal of 2 M NaCl. PMID:503864

  13. MTBE OXIDATION BY BIFUNCTIONAL ALUMINUN

    EPA Science Inventory

    Bifunctional aluminum, prepared by sulfating zero-valent aluminum with sulfuric acid, is an innovative extension of zero-valent metal (ZVM) technology for ground water remediation. Bifunctional aluminum has a dual functionality of simultaneously decomposing both reductively- an...

  14. MTBE OXIDATION BY BIFUNCTIONAL ALUMINUM

    EPA Science Inventory

    Bifunctional aluminum, prepared by sulfating zero-valent aluminum with sulfuric acid, has a dual functionality of simultaneously decomposing both reductively- and oxidatively-degradable contaminants. In this work, the use of bifunctional aluminum for the degradation of methyl te...

  15. Bifunctional alkaline oxygen electrodes

    NASA Technical Reports Server (NTRS)

    Swette, L.; Kackley, N.; Mccatty, S. A.

    1991-01-01

    The authors describe the identification and testing of electrocatalysts and supports for the positive electrode of moderate-temperature, single-unit, rechargeable alkaline fuel cells. Recent work on Na(x)Pt3O4, a potential bifunctional catalyst, is described, as well as the application of novel approaches to the development of more efficient bifunctional electrode structures. The three dual-character electrodes considered here showed similar superior performance; the Pt/RhO2 and Rh/RhO2 electrodes showed slightly better performance than the Pt/IrO2 electrode. It is concluded that Na(x)Pt3O4 continues to be a promising bifunctional oxygen electrode catalyst but requires further investigation and development.

  16. Structural changes in photosystem II after treatment with the zero-length bifunctional cross-linker 1-ethyl-3-(3-dimethylaminopropyl)carbodi-imide: an electron microscopic study.

    PubMed Central

    Collins, R F; Flint, T D; Holzenburg, A; Ford, R C

    1996-01-01

    Two-dimensional (2D) crystals of photosystem II (PS II) treated with various concentrations of the zero-length crosslinker 1-ethyl-3-(3-dimethylaminopropyl))carbodi-imide (EDC) were analysed by electron microscopy in conjunction with crystallographic image processing. The preparations were characterized by SDS/PAGE and oxygen-evolution measurements, and the effectiveness of cross-linking was monitored by measuring the level of protection afforded against high concentrations of NaCl and CaCl2, which normally remove extrinsic proteins from PS II. We found that low concentrations of EDC (0.25%) increase the order of 2D crystals of PS II. Treatments with EDC concentrations higher than 0.5% did not improve the order of 2D crystals but induced gross structural changes, which were correlated with a decrease in oxygen evolution activity. Structural changes due to cross-linking did not affect packing or symmetry of the 2D crystals, further supporting the conclusion that PS II has a monomeric nature in vivo. PMID:8912698

  17. Tight bifunctional hierarchical catalyst.

    PubMed

    Højholt, Karen T; Vennestrøm, Peter N R; Tiruvalam, Ramchandra; Beato, Pablo

    2011-12-28

    A new concept to prepare tight bifunctional catalysts has been developed, by anchoring CoMo(6) clusters on hierarchical ZSM-5 zeolites for simultaneous use in HDS and hydrocracking catalysis. The prepared material displays a significant improved activity in HDS catalysis compared to the impregnated counterpart. PMID:22048337

  18. Crosslinked Polyamide

    DOEpatents

    Huang, Zhi H.; McDonald, William F.; Wright, Stacy C.; Taylor, Andrew C.

    2002-06-04

    A crosslinked polyamide material and a process for preparing the crosslinked polyamide material are disclosed. The crosslinked polyamide material comprises a crosslinked chemical combination of (1) a polyamide of the formula: ##STR1## wherein n is between about 50 and 10,000, wherein each R is between 1 and 50 carbon atoms alone and is optionally substituted with heteroatoms, oxygen, nitrogen, sulfur, or phosphorus and combinations thereof, wherein multiple of the R are in vertically aligned spaced relationship along a backbone forming the polyamide, and wherein two or more of the R contain an amino group; and (2) a crosslinking agent containing at least two functional groups capable of reacting with the amino groups of the polyamide. In one embodiment of the invention, the crosslinking agent is an aliphatic or aromatic isocyanate compound having 2 or more --N.dbd.C.dbd.O groups. In another embodiment of the invention, the crosslinking agent is an aliphatic aldehyde or aromatic aldehyde compound having 2 or more --CHO groups. In still another embodiment of the invention, the crosslinking agent is selected from a phosphine having the general formula (A).sub.2 P(B) and mixtures thereof, wherein A is hydroxyalkyl, and B is hydroxyalkyl, alkyl, or aryl. In yet another embodiment of the invention, the crosslinking agent is selected from the group consisting of epoxy resins having more than one epoxide group per molecule.

  19. In vivo kinetics of micronuclei induction by bifunctional alkylating antineoplastics.

    PubMed

    Morales-Ramírez, Pedro; Vallarino-Kelly, Teresita; Cruz-Vallejo, Virginia L; López-Iturbe, Rosario; Alvaro-Delgadillo, Horacio

    2004-05-01

    The aim of the present study was to determine in vivo the kinetics of micronucleated polychromatic erythrocyte (MN-PCE) induction in mice, as an approach for studying the mechanism of micronuclei induction by mitomycin C, cis-diamine dichloroplatinum, busulfan and bis-chloroethylnitrosourea, bifuctional alkylating antineoplastic agents having different patterns of crosslink induction. The kinetics of MN-PCE induction was established by scoring the frequency of MN-PCE in 2000 PCE in peripheral blood, for periods of 8 or 10 h after acute treatment and up to 80 h, with different doses of the agent. The kinetics of MN-PCE induction and particularly the times of maximal induction by different bifunctional alkylating agents were compared with the kinetics previously obtained for ethylnitrosourea, methylnitrosourea and 6-mercaptopurine, agents that cause MN-PCE mainly in the first, second and third divisions after exposure, respectively. The results obtained in the present study allow us to conclude that: (i) bifunctional alkylating agents have very different efficiencies of genotoxic and cytotoxic action; (ii) all assayed bifunctional alkylating agents induced micronuclei during the first cell division, owing to the mistaken repair of primary lesions, e.g. excision; (iii) busulfan and bis-chloroethylnitrosourea showed an additional late mechanism of micronuclei induction, which is expressed at the third division and seems to be related to the mismatch repair process. PMID:15123786

  20. Polymer-Supported Reagents: The Role of Bifunctionality in the Design of Ion-Selective Complexants

    SciTech Connect

    Alexandratos, S. D.

    2001-06-01

    The importance of multi-functionality in the preparation of ion-selective polymers is evident from the structure of enzymes where specific metal ions are bound through cooperative interactions among different amino acids. In synthetic polymers, ionic selectivity is enhanced when a chemical reaction is superimposed on an ion-exchange process. The concept of reactive ion exchange has been extended through the synthesis of crosslinked polymers whose metal ion selectivity is a function of reduction, coordination or precipitation reactions as determined by various covalently bound ligands. Development of three classes of dual mechanism bifunctional polymers, a new series of bifunctional diphosphonate polymers, and novel bifunctional ion-selective polymers with enhanced ionic accessibility has been accomplished.

  1. Bifunctional DTPA-type ligand

    SciTech Connect

    Gansow, O.A.; Brechbiel, M.W.

    1990-03-26

    The subject matter of the invention relates to bifunctional cyclohexyl DTPA ligands and methods of using these compounds. Specifically, such ligands are useful for radiolabeling proteins with radioactive metals, and can consequently be utilized with respect to radioimmunoimaging and/or radioimmunotherapy.

  2. Genetics Home Reference: D-bifunctional protein deficiency

    MedlinePlus

    ... Genetics Home Health Conditions D-bifunctional protein deficiency D-bifunctional protein deficiency Enable Javascript to view the ... boxes. Download PDF Open All Close All Description D-bifunctional protein deficiency is a disorder that causes ...

  3. Analyzing the Case for Bifunctional Catalysis.

    PubMed

    Andersen, Mie; Medford, Andrew J; Nørskov, Jens K; Reuter, Karsten

    2016-04-18

    Bifunctional coupling of two different catalytic site types has often been invoked to explain experimentally observed enhanced catalytic activities. We scrutinize such claims with generic scaling-relation-based microkinetic models that allow exploration of the theoretical limits for such a bifunctional gain for several model reactions. For sites at transition-metal surfaces, the universality of the scaling relations between adsorption energies largely prevents any improvements through bifunctionality. Only the consideration of systems that involve the combination of different materials, such as metal particles on oxide supports, offers hope for significant bifunctional gains. PMID:27005967

  4. Reversible PH Lability of Cross-Linked Vault Nanocapsules

    SciTech Connect

    Yu, M.; Ng, B.C.; Rome, L.H.; Tolbert, S.H.; Monbouquette, H.G.

    2009-05-28

    Vaults are ubiquitous, self-assembled protein nanocapsules with dimension in the sub-100 nm range that are conserved across diverse phyla from worms to humans. Their normal presence in humans at a copy number of over 10 000/cell makes them attractive as potential drug delivery vehicles. Toward this goal, bifunctional amine-reactive reagents are shown to be useful for the reversible cross-linking of recombinant vaults such that they may be closed and opened in a controllable manner.

  5. A dimethacrylate cross-linker cleavable under thermolysis or alkaline hydrolysis conditions: synthesis, polymerization, and degradation.

    PubMed

    Elladiou, Marios; Patrickios, Costas S

    2016-02-11

    We develop a new platform based on 2,6-pyridinediethanol diesters for introducing polymer degradability under thermolysis or alkaline hydrolysis conditions, with the latter being rare in polymers. Such labile diesters can be cross-linkers, bifunctional initiators and inimers. We demonstrate the power of this platform through the synthesis of the 2,6-pyridinediethanol dimethacrylate cross-linker, its controlled (co)polymerization, and the thermal and hydrolytic cleavage of its (co)polymers. PMID:26803938

  6. Tailored bifunctional polymer for plutonium monitoring.

    PubMed

    Paul, Sumana; Pandey, Ashok K; Kumar, Pranaw; Kaity, Santu; Aggarwal, Suresh K

    2014-07-01

    Monitoring of actinides with sophisticated conventional methods is affected by matrix interferences, spectral interferences, isobaric interferences, polyatomic interferences, and abundance sensitivity problems. To circumvent these limitations, a self-supported disk and membrane-supported bifunctional polymer were tailored in the present work for acidity-dependent selectivity toward Pu(IV). The bifunctional polymer was found to be better than the polymer containing either a phosphate group or a sulfonic acid group in terms of (i) higher Pu(IV) sorption efficiency at 3-4 mol L(-1) HNO3, (ii) selective preconcentration of Pu(IV) in the presence of a trivalent actinide such as Am(III), and (iii) preferential sorption of Pu(IV) in the presence of a large excess of U(VI). The bifunctional polymer was formed as a self-supported matrix by bulk polymerization and also as a 1-2 μm thin layer anchored on a microporous poly(ether sulfone) by surface grafting. The proportions of sulfonic acid and phosphate groups in both the self-supported disk and membrane-supported bifunctional polymer were found to be the same as expected from the mole proportions of monomers in polymerizing solutions used for syntheses. α radiography by a solid-state nuclear track detector indicated fairly homogeneous anchoring of the bifunctional polymer on the surface of the membrane. Pu(IV) preconcentrated on a single bifunctional bead was used for determination of the Pu isotopic composition by thermal ionization mass spectrometry. The membrane-supported bifunctional polymer was used for preconcentration and subsequent quantification of Pu(IV) by α spectrometry using the absolute efficiency at a fixed counting geometry. The analytical performance of the membrane-supported-bifunctional-polymer-based α spectrometry method was found to be highly reproducible for assay of Pu(IV) in a variety of complex samples. PMID:24901969

  7. Controlled degradation of hydrogels using multi-functional cross-linking molecules.

    PubMed

    Lee, Kuen Yong; Bouhadir, Kamal H; Mooney, David J

    2004-06-01

    Hydrogels, chemically cross-linked or physically entangled, have found a number of applications as novel delivery vehicles of drugs and cells. However, the narrow ranges of degradation rates and mechanical strength currently available from many hydrogels limits their applications. We have hypothesized that utilization of multi-functional cross-linking molecules to form hydrogels could provide a wider range and tighter control over the degradation rates and mechanical stiffness of gels than bi-functional cross-linking molecules. To address the possibility, we isolated alpha-L-guluronate residues of sodium alginate, and oxidized them to prepare poly(aldehyde guluronate) (PAG). Hydrogels were formed with either poly(acrylamide-co-hydrazide) (PAH) as a multi-functional cross-linking molecule or adipic acid dihydrazide (AAD) as a bi-functional cross-linking molecule. The initial properties and degradation behavior of both PAG gel types were monitored. PAG/PAH hydrogels showed higher mechanical stiffness before degradation and degraded more slowly than PAG/AAD gels, at the same concentration of cross-linking functional groups. The enhanced mechanical stiffness and prolonged degradation behavior could be attributed to the multiple attachment points of PAH in the gel at the same concentration of functional groups. This approach to regulating gel properties with multifunctional cross-linking molecules could be broadly used in hydrogels. PMID:14751730

  8. Photoinduced DNA Interstrand Cross-Link Formation by Naphthalene Boronates via a Carbocation.

    PubMed

    Wang, Yibin; Lin, Zechao; Fan, Heli; Peng, Xiaohua

    2016-07-18

    Most photoinduced DNA cross-link formation by a bifunctional aryl derivative is through a bisquinone methide. DNA cross-linking via a bisarylcarbocation remains a less explored area. We designed and synthesized a series of naphthalene boronates that produce DNA interstrand cross-links via a carbocation upon UV irradiation. A free radical was generated from the naphthalene boronates with 350 nm irradiation and further converted to a carbocation by electron transfer. The activation mechanism was determined using the orthogonal traps, 2,2,6,6-tetramethylpiperidin-1-oxyl (TEMPO) and methoxyamine that react with either the free radical or the carbocation but not both. This represents a novel example of photoinduced DNA cross-link formation via carbocations generated from a bisaryl derivative. This work provides information useful for the design of novel photoactivated DNA cross-linking agents. PMID:27189512

  9. Mechanical Characterization of a Bi-functional Tetronic Hydrogel Adhesive for Soft Tissues

    PubMed Central

    Sanders, Lindsey; Stone, Roland; Webb, C. Kenneth; Mefford, O. Thompson; Nagatomi, Jiro

    2014-01-01

    Although a number of tissue adhesives and sealants for surgical use are currently available, attaining a useful balance in high strength, high compliance, and low swelling has proven difficult. Recent studies have demonstrated that a 4-arm poly(propylene oxide)-poly(ethylene oxide) (PPO-PEO) block copolymer, Tetronic, can be chemically modified to form a hydrogel tissue adhesive21–23. Building on the success of these studies, the present study explored bi-functionalization of Tetronic with acrylates for chemical crosslinking of the hydrogel and N-hydroxysuccinimide (NHS) for reaction with tissue amines. The adhesive bond strengths of various uni- and bi-functional Tetronic blends (T1107 ACR: T1107 ACR/NHS) determined by lap shear testing ranged between 8 and 74 kPa, with the 75:25 (T1107 ACR: T1107 ACR/NHS) blend displaying the highest value. These results indicated that addition of NHS led to improvement of tissue bond strength over acrylation alone Furthermore, ex vivo pressure tests using the rat bladder demonstrated that the bi-functional Tetronic adhesive exhibited high compliance and maintained pressures under hundreds of filling and emptying cycles. Together, the results of the present study provided evidence that the bi-functional Tetronic adhesive with a proper blend ratio may be used to achieve an accurate balance in bulk and tissue bond strengths, as well as the compliance and durability for soft tissue such as the bladder. PMID:25111445

  10. Chemical Cross-linking of Neighboring Thylakoid Membrane Polypeptides 12

    PubMed Central

    Novak-Hofer, Ilse; Siegenthaler, Paul-Andre

    1978-01-01

    Cross-linking between protein components of whole spinach (Spinacia oleracea var. Nobel) thylakoids and of photosystem I- and II-enriched thylakoid fractions has been produced by reaction with the bifunctional imidoester dimethyl-3,3′-dithiobispropionimidate dihydrochloride as well as by the oxidation of intrinsic sulfydryl groups with an orthophenanthrolinecupric ion complex. The mixture of membrane proteins and their cross-linked products has been analyzed by two-dimensional sodium dodecyl sulfate electrophoresis, with a reductive cleavage step of the cross-linkages before the second dimension. Cross-linked aggregates up to a molecular weight of about 130 kilodaltons (kD) were analyzed, and it was inferred that the polypeptides appearing together in the same aggregates were neighbors within the membrane. In thylakoids as well as in isolated photosystem fractions, oligomers were formed by cross-linking polypeptides of the 60 to 90 kD range, among them the polypeptides of the chlorophyll-protein complex I. Polypeptides of 46, 19, and 12 kD were cross-linked to these complexes. Polypeptides of 25 and 22 kD, which are related to the chlorophyll-protein complex II, were cross-linked in thylakoids as well as in photosystem II fractions, suggesting that in the membrane these molecules are close together. In photosystem II fractions an oligomer having a molecular weight of about 60 kD was formed by cross-linking several polypeptides of different molecular weights: 40, 25, and 22 kD. Our cross-linking experiments show that protein interactions in the thylakoid membrane occurred mainly among the polypeptides of the two chlorophyll-protein complexes, thus suggesting an oligomeric nature of these apoproteins. ImagesFig. 1Fig. 2Fig. 3 PMID:16660519

  11. Synchrotron Small-Angle X-ray Scattering Study of Cross-Linked Polymeric Micelles.

    PubMed

    Kim, Hyun-Chul; Jin, Kyeong Sik; Lee, Se Guen; Kim, Eunjoo; Lee, Sung Jun; Jeong, Sang Won; Lee, Seung Woo; Kim, Kwang-Woo

    2016-06-01

    Polymeric micelles of methoxypoly(ethylene glycol)-b-poly(lactide) containing lysine units (mPEG-PLA-Lys4) were cross-linked by reacting of lysine moieties with a bifunctional bis(N-hydroxy-succinimide ester). The micelles were characterized in aqueous solution using dynamic light scattering, transmission electron microscopy, and synchrotron small-angle X-ray scattering. The mPEG-PLA-Lys4 was synthesized through the ring-opening polymerization of N6-carbobenzyloxy-L-lysine N-carboxyanhydride with amine-terminated mPEG-PLA and subsequent deprotection. The polymeric micelles showed enhanced micelle stability after cross-linking, which was confirmed by adding sodium dodecyl sulfate as a destabilizing agent. The average diameters measured via dynamic light scattering were 19.1 nm and 29.2 nm for non-cross-linked polymeric micelles (NCPMs) and cross-linked polymeric micelles (CPMs), respectively. The transmission electron microscopy images showed that the size of the polymeric micelles increased slightly due to cross-linking, which was in good agreement with the DLS measurements. The overall structures and internal structural changes of NCPMs and CPMs in aqueous solution were studied in detail using synchrotron X-ray scattering method. According to the structural parameters of X-ray scattering analysis, CPMs with a more densely packed core structure were formed by reacting bifunctional cross-linking agents with lysine amino groups located in the innermost core of the polymeric micelles. PMID:27427731

  12. The sunburn cell in hairless mouse epidermis: quantitative studies with UV-A radiation and mono- and bifunctional psoralens

    SciTech Connect

    Young, A.R.; Magnus, I.A.

    1982-10-01

    The production of the sunburn cell by UV-A radiation and topical psoralens in hairless mouse epidermis has been studied. It has been shown that the appearance of this cell is dependent on the dose of both UV-A radiation and of the psoralen. The time-course with 8-methoxypsoralen has peak sunburn cell numbers at 28 hr postirradiation. A comparison of 2 bifunctional (8-methoxypsoralen and 5-methoxypsoralen) and 2 monofunctional (angelicin and 3-carbethoxypsoralen) psoralens showed the former are more potent. This suggests that DNA crosslink lesions may play a rle in sunburn cell production.

  13. Bifunctional hydrogen bonds in monohydrated cycloether complexes.

    PubMed

    Vallejos, Margarita M; Angelina, Emilio L; Peruchena, Nélida M

    2010-03-01

    In this work, the cooperative effects implicated in bifunctional hydrogen bonds (H-bonds) were studied (in monohydrated six-membered cycloether) within the framework of the atoms in molecules (AIM) theory and of the natural bond orbitals (NBO) analysis. The study was carried out in complexes formed by six-membered cycloether compounds (tetrahydropyrane, 1,4-dioxane, and 1,3-dioxane) and a water molecule. These compounds were used as model systems instead of more complicated molecules of biological importance. All the results were obtained at the second-order Møller-Plesset (MP2) level theory using a 6-311++G(d,p) basis set. Attention was focused on the indicators of the cooperative effects that arise when a water molecule interacts simultaneously with a polar and a nonpolar portion of a six-membered cycloether (via bifunctional hydrogen bonds) and compared with conventional H-bonds where the water molecule only interacts with the polar portion of the cycloether. Different indicators of H-bonds strength, such as structural and spectroscopic data, electron charge density, population analysis, hyperconjugation energy and charge transference, consistently showed significant cooperative effects in bifunctional H-bonds. From the AIM, as well as from the NBO analysis, the obtained results allowed us to state that in the monohydrated six-membered cycloether, where the water molecule plays a dual role, as proton acceptor and proton donor, a mutual reinforcement of the two interactions occurs. Because of this feature, the complexes engaged by bifunctional hydrogen bonds are more stabilized than the complexes linked by conventional hydrogen bonds. PMID:20136161

  14. Matching Cross-linked Peptide Spectra: Only as Good as the Worse Identification*

    PubMed Central

    Trnka, Michael J.; Baker, Peter R.; Robinson, Philip J. J.; Burlingame, A. L.; Chalkley, Robert J.

    2014-01-01

    Chemical cross-linking mass spectrometry identifies interacting surfaces within a protein assembly through labeling with bifunctional reagents and identifying the covalently modified peptides. These yield distance constraints that provide a powerful means to model the three-dimensional structure of the assembly. Bioinformatic analysis of cross-linked data resulting from large protein assemblies is challenging because each cross-linked product contains two covalently linked peptides, each of which must be correctly identified from a complex matrix of potential confounders. Protein Prospector addresses these issues through a complementary mass modification strategy in which each peptide is searched and identified separately. We demonstrate this strategy with an analysis of RNA polymerase II. False discovery rates (FDRs) are assessed via comparison of cross-linking data to crystal structure, as well as by using a decoy database strategy. Parameters that are most useful for positive identification of cross-linked spectra are explored. We find that fragmentation spectra generally contain more product ions from one of the two peptides constituting the cross-link. Hence, metrics reflecting the quality of the spectral match to the less confident peptide provide the most discriminatory power between correct and incorrect matches. A support vector machine model was built to further improve classification of cross-linked peptide hits. Furthermore, the frequency with which peptides cross-linked via common acylating reagents fragment to produce diagnostic, cross-linker-specific ions is assessed. The threshold for successful identification of the cross-linked peptide product depends upon the complexity of the sample under investigation. Protein Prospector, by focusing the reliability assessment on the least confident peptide, is better able to control the FDR for results as larger complexes and databases are analyzed. In addition, when FDR thresholds are calculated separately

  15. Corneal cross-linking.

    PubMed

    Randleman, J Bradley; Khandelwal, Sumitra S; Hafezi, Farhad

    2015-01-01

    Since its inception in the late 1990s, corneal cross-linking has grown from an interesting concept to a primary treatment for corneal ectatic disease worldwide. Using a combination of ultraviolet-A light and a chromophore (vitamin B2, riboflavin), the cornea can be stiffened, usually with a single application, and progressive thinning diseases such as keratoconus arrested. Despite being in clinical use for many years, some of the underlying processes, such as the role of oxygen and the optimal treatment times, are still being worked out. More than a treatment technique, corneal cross-links represent a physiological principle of connective tissue, which may explain the enormous versatility of the method. We highlight the history of corneal cross-linking, the scientific underpinnings of current techniques, evolving clinical treatment parameters, and the use of cross-linking in combination with refractive surgery and for the treatment of infectious keratitis. PMID:25980780

  16. [Crosslinking in Keratoconus].

    PubMed

    Lang, S J; Reinhard, T

    2016-06-01

    Keratoconus leads to progressive thinning and protrusion of the cornea. Young patients exhibit the highest risk for progression. Corneal crosslinking was introduced in 1998 and is intended to prevent progression of keratoconus. Only a few prospective controlled trials have been published. Six randomised controlled trials have been published. All these trials confirmed the efficacy of crosslinking through keratometric data. In two trials, progression was reported in some patients of the treatment group. This indicates that not all patients benefit from corneal crosslinking. The risks of the procedure include corneal scarring, haze, endothelial cell damage and infections of the cornea. In order to avoid these risks, patients without progression should not be treated with crosslinking. PMID:27315291

  17. Mechanical characterization of a bifunctional Tetronic hydrogel adhesive for soft tissues.

    PubMed

    Sanders, Lindsey; Stone, Roland; Webb, Kenneth; Mefford, Thompson; Nagatomi, Jiro

    2015-03-01

    Although a number of tissue adhesives and sealants for surgical use are currently available, attaining a useful balance in high strength, high compliance, and low swelling has proven difficult. Recent studies have demonstrated that a four-arm poly(propylene oxide)-poly(ethylene oxide) block copolymer, Tetronic, can be chemically modified to form a hydrogel tissue adhesive (Cho et al., Acta Biomater 2012;8:2223-2232; Barrett et al., Adv Health Mater 2012;1-11; Balakrishnan, Evaluating mechanical performance of hydrogel-based adhesives for soft tissue applications. Clemson University, All Theses, Paper 1574: Tiger Prints; 2013). Building on the success of these studies, this study explored bifunctionalization of Tetronic with acrylates for chemical crosslinking of the hydrogel and N-hydroxysuccinimide (NHS) for reaction with tissue amines. The adhesive bond strengths of various uni and bifunctional Tetronic blends (T1107 ACR: T1107 ACR/NHS) determined by lap shear testing ranged between 8 and 74 kPa, with the 75:25 (T1107 ACR: T1107 ACR/NHS) blend displaying the highest value. These results indicated that addition of NHS led to improvement of tissue bond strength over acrylation alone. Furthermore, ex vivo pressure tests using the rat bladder demonstrated that the bifunctional Tetronic adhesive exhibited high compliance and maintained pressures under hundreds of filling and emptying cycles. Together, the results of this study provided evidence that the bifunctional Tetronic adhesive with a proper blend ratio may be used to achieve an accurate balance in bulk and tissue bond strengths, as well as the compliance and durability for soft tissue such as the bladder. PMID:25111445

  18. An enzymatic approach to bifunctional chelating agents.

    PubMed

    Minazzi, Paolo; Lattuada, Luciano; Menegotto, Ivan G; Giovenzana, Giovanni B

    2014-09-21

    Bifunctional chelating agents (BFCAs) combine the complexing properties of a multidentate ligand with the presence of a free reactive functional group, mainly devoted to conjugation purposes. Indeed, products obtained by conjugation of a BFCA to a biomolecule and coordination of a suitable metal ion are widely applied in medicine nowadays as diagnostic and therapeutic agents. BFCAs are generally prepared through multi-step syntheses and with extensive application of protection-deprotection strategies, due to the large number of functional groups involved. Hydrolytic enzymes, with their unique chemoselectivity, provided the best results in the preparation of three different BFCAs based on very useful and well known ligand platforms. PMID:25060174

  19. Crosslinked, porous, polyacrylate beads

    NASA Technical Reports Server (NTRS)

    Rembaum, Alan (Inventor); Yen, Shiao-Ping Siao (Inventor); Dreyer, William J. (Inventor)

    1976-01-01

    Uniformly-shaped, porous, round beads are prepared by the co-polymerization of an acrylic monomer and a cross-linking agent in the presence of 0.05 to 5% by weight of an aqueous soluble polymer such as polyethylene oxide. Cross-linking proceeds at high temperature above about 50.degree.C or at a lower temperature with irradiation. Beads of even shape and even size distribution of less than 2 micron diameter are formed. The beads will find use as adsorbents in chromatography and as markers for studies of cell surface receptors.

  20. Crosslinked, porous, polyacrylate beads

    NASA Technical Reports Server (NTRS)

    Rembaum, Alan (Inventor); Yen, Shiao-Ping S. (Inventor); Dreyer, William J. (Inventor)

    1977-01-01

    Uniformly-shaped, porous, round beads are prepared by the co-polymerization of an acrylic monomer and a cross-linking agent in the presence of 0.05 to 5% by weight of an aqueous soluble polymer such as polyethylene oxide. Cross-linking proceeds at high temperature above about 50.degree. C or at a lower temperature with irradiation. Beads of even shape and even size distribution of less than 2 micron diameter are formed. The beads will find use as adsorbents in chromatography and as markers for studies of cell surface receptors.

  1. Synthesis of a duplex oligonucleotide containing a nitrogen mustard interstrand DNA-DNA cross-link.

    PubMed

    Ojwang, J O; Grueneberg, D A; Loechler, E L

    1989-12-01

    Many cancer chemotherapeutic agents react with DNA and give adducts that block DNA replication, which is thought to result in cytotoxicity, especially in rapidly proliferating cells such as cancer cells. One class of these agents is bifunctionally reactive (e.g., the nitrogen mustards) and forms DNA-DNA cross-links. It is unknown whether inter- or intrastrand cross-links are more effective at blocking DNA replication. To evaluate this, a DNA shuttle vector is being constructed with an interstrand cross-link at a unique site. In the first step of this project, a duplex oligonucleotide containing an interstrand cross-link is isolated by denaturing polyacrylamide gel electrophoresis from the reaction of nitrogen mustard with two partially complementary oligodeoxynucleotides. The purified oligonucleotide product is characterized and shown to be cross-linked in a 5'-GAC-3' 3'-CTG-5' sequence by a nitrogen mustard moiety that is bound at the N(7)-position of the guanines in the opposing strands; the glycosylic bonds of these guanine adducts are stabilized in their corresponding imidazole ring-opened form. Nitrogen mustard is shown to react with a variety of oligonucleotides and, based upon these results, its preferred targets for interstrand cross-linking are 5'-GXC-3' sequences, where X can be any of the four deoxyribonucleotide bases. PMID:2819709

  2. Microbes encapsulated within crosslinkable polymers

    SciTech Connect

    Chidambaram, Devicharan; Liu, Ying; Rafailovich, Miriam H

    2013-02-05

    The invention relates to porous films comprising crosslinked electrospun hydrogel fibers. Viable microbes are encapsulated within the crosslinked electrospun hydrogel fibers. The crosslinked electrospun hydrogel fibers are water insoluble and permeable. The invention also relates to methods of making and using such porous films.

  3. Bifunctional Gallium-68 Chelators: Past, Present, and Future.

    PubMed

    Spang, Philipp; Herrmann, Christian; Roesch, Frank

    2016-09-01

    This article reviews the development of bifunctional chelates for synthesising (68)Ga radiopharmaceuticals. It structures the chelates into groups of macrocycles, nonmacrocycles, and chimeric derivatives. The most relevant bifunctional chelates are discussed in chelate structure, parameters of (68)Ga-labeling, and stability of the (68)Ga-chelate complexes. Furthermore those derivatives are included, where (67)Ga was applied instead of (68)Ga. A particular feature discussed is the ability of certain bifunctional chelate structures to function in kit-type preparation of the (68)Ga radiopharmaceuticals. Currently, nonmacrocyclic and chimeric derivates attract particular attention such as THP-derivates and DATA-derivates. PMID:27553464

  4. Preparation of ordered and crosslinked films from liquid crystalline vinyl ether monomers

    SciTech Connect

    Andersson, H.; Sahlen, F.; Gedde, U.W.; Hult, A.

    1993-12-31

    Highly ordered densely crosslinked liquid crystalline poly(vinyl ether) films have been prepared by in-situ photopolymerization of oriented bifunctional mesogenic vinyl ether monomers. Orientation was achieved either by a simple surface treatment, using an unidirectionally rubbed polyimide film or by a magnetic field. Polymerization from various monomer phases resulted in LC polymer network films with different molecular organizations. The films were analyzed with small-angle X-ray scattering, polarized light microscopy and infrared-dichroism measurements. It was shown that films with nematic, smectic A and smectic B structures were obtained, the latter having a very high degree of orientation.

  5. Nanoparticle Superlattices as Efficient Bifunctional Electrocatalysts for Water Splitting.

    PubMed

    Li, Jun; Wang, Yongcheng; Zhou, Tong; Zhang, Hui; Sun, Xuhui; Tang, Jing; Zhang, Lijuan; Al-Enizi, Abdullah M; Yang, Zhongqin; Zheng, Gengfeng

    2015-11-18

    The solar-driven water splitting process is highly attractive for alternative energy utilization, while developing efficient, earth-abundant, bifunctional catalysts for both oxygen evolution reaction and hydrogen evolution reaction has remained as a major challenge. Herein, we develop an ordered CoMnO@CN superlattice structure as an efficient bifunctional water-splitting electrocatalyst, in which uniform Co-Mn oxide (CoMnO) nanoparticles are coated with a thin, continuous nitrogen-doped carbon (CN) framework. The CoMnO nanoparticles enable optimized OER activity with effective electronic structure configuration, and the CN framework serves as an excellent HER catalyst. Importantly, the ordered superlattice structure is beneficial for enhanced reactive sites, efficient charge transfer, and structural stability. This bifunctional superlattice catalyst manifests optimized current densities and electrochemical stability in overall water splitting, outperforming most of the previously reported single- or bifunctional electrocatalysts. Combining with a silicon photovoltaic cell, this CoMnO@CN superlattice bifunctional catalyst enables unassisted solar water splitting continuously for ∼5 days with a solar-to-hydrogen conversion efficiency of ∼8.0%. Our discovery suggests that these transition metal oxide-based superlattices may serve as a unique structure modality for efficient bifunctional water splitting electrocatalysts with scale-up potentials. PMID:26496655

  6. Cross-linking connectivity in bone collagen fibrils: the COOH-terminal locus of free aldehyde

    NASA Technical Reports Server (NTRS)

    Otsubo, K.; Katz, E. P.; Mechanic, G. L.; Yamauchi, M.

    1992-01-01

    Quantitative analyses of the chemical state of the 16c residue of the alpha 1 chain of bone collagen were performed on samples from fetal (4-6-month embryo) and mature (2-3 year old) bovine animals. All of this residue could be accounted for in terms of three chemical states, in relative amounts which depended upon the age of the animal. Most of the residue was incorporated into either bifunctional or trifunctional cross-links. Some of it, however, was present as free aldehyde, and the content increased with maturation. This was established by isolating and characterizing the aldehyde-containing peptides generated by tryptic digestion of NaB3H4-reduced mature bone collagen. We have concluded that the connectivity of COOH-terminal cross-linking in bone collagen fibrils changes with maturation in the following way: at first, each 16c residue in each of the two alpha 1 chains of the collagen molecule is incorporated into a sheet-like pattern of intermolecular iminium cross-links, which stabilizes the young, nonmineralized fibril as a whole. In time, some of these labile cross-links maturate into pyridinoline while others dissociate back to their precursor form. The latter is likely due to changes in the molecular packing brought about by the mineralization of the collagen fibrils. The resultant reduction in cross-linking connectivity may provide a mechanism for enhancing certain mechanical characteristics of the skeleton of a mature animal.

  7. Crosslinking biopolymers for biomedical applications.

    PubMed

    Reddy, Narendra; Reddy, Roopa; Jiang, Qiuran

    2015-06-01

    Biomaterials made from proteins, polysaccharides, and synthetic biopolymers are preferred but lack the mechanical properties and stability in aqueous environments necessary for medical applications. Crosslinking improves the properties of the biomaterials, but most crosslinkers either cause undesirable changes to the functionality of the biopolymers or result in cytotoxicity. Glutaraldehyde, the most widely used crosslinking agent, is difficult to handle and contradictory views have been presented on the cytotoxicity of glutaraldehyde-crosslinked materials. Recently, poly(carboxylic acids) that can crosslink in both dry and wet conditions have been shown to provide the desired improvements in tensile properties, increase in stability under aqueous conditions, and also promote cell attachment and proliferation. Green chemicals and newer crosslinking approaches are necessary to obtain biopolymeric materials with properties desired for medical applications. PMID:25887334

  8. F-actin is intermolecularly crosslinked by N,N'-p-phenylenedimaleimide through lysine-191 and cysteine-374.

    PubMed

    Elzinga, M; Phelan, J J

    1984-11-01

    The bifunctional reagent N,N'-p-phenylenedimaleimide (PDM) is being used in an attempt to measure distances between specific side chains in adjacent monomers within F-actin. [14C]PDM was synthesized and was used to crosslink F-actin. Uncrosslinked actin was removed by gel filtration, and, from an arginine-specific tryptic digest of the covalently crosslinked dimers and higher oligomers, one radioactive crosslinked peptide was obtained in high yield. Amino acid composition and sequence analysis indicated that it comprises residues 184-196 of one monomer and 373-375 of an adjacent actin molecule, bridged by PDM through Cys-374 and Lys-191. Thus, these groups are shown to be 1.2-1.4 nm apart in adjacent actin monomers in F-actin. This information may be crucial in establishing the orientation of actin monomers within F-actin. PMID:6436818

  9. The Use of Glass Substrates with Bi-Functional Silanes for Designing Micropatterned Cell-Secreted Cytokine Immunoassays

    PubMed Central

    Seo, Jeong Hyun; Chen, Li-Jung; Verkhoturov, Stanislav V.; Schweikert, Emile A.; Revzin, Alexander

    2011-01-01

    It is often desirable to sequester cells in specific locations on the surface and to integrate sensing elements next to the cells. In the present study, surfaces were fabricated so as to position cytokine sensing domains inside non-fouling poly(ethylene glycol) (PEG) hydrogel microwells. Our aim was to increase sensitivity of micropatterned cytokine immunoassays through covalent attachment of biorecognition molecules. To achieve this, glass substrates were functionalized with a binary mixture of acrylate- and thiol-terminated methoxysilanes. During subsequent hydrogel photopatterning step acrylate moieties served to anchor hydrogel microwells to glass substrates. Importantly, glass attachment sites within the microwells contained thiol groups that could be activated with a hetero-bifunctional cross-linker for covalent immobilization of proteins. After incubation with fluorescently-labeled avidin, microwells fabricated on a mixed acryl/thiol silane layer emitted ~6 times more fluorescence compared to microwells fabricated on an acryl silane alone. This result highlighted the advantages of covalent attachment of avidin inside the microwells. To create cytokine immunoassays, micropatterned surfaces were incubated with biotinylated IFN-γ or TNF-α antibodies (Abs). Micropatterned immunoassays prepared in this manner were sensitive down to 1 ng/ml or 60 pM IFN-γ. To further prove utility of this bionterface design, macrophages were seeded into 30 µm diameter microwells fabricated on either bi-functional (acryl/thiol) or monofunctional silane layers. Both types of microwells were coated with avidin and biotin-anti-TNF-α prior to cell seeding. Short mitogenic activation followed by immunostaining for TNF-α revealed that microwells created on bi-functional silane layer had 3 times higher signal due to macrophage-secreted TNF-α compared to microwells fabricated on mono-functional silane. The rational design of cytokine-sensing surfaces described here will be leveraged

  10. Bifunctional Phosphorus Dendrimers and Their Properties.

    PubMed

    Caminade, Anne-Marie; Majoral, Jean-Pierre

    2016-01-01

    Dendrimers are hyperbranched and monodisperse macromolecules, generally considered as a special class of polymers, but synthesized step-by-step. Most dendrimers have a uniform structure, with a single type of terminal function. However, it is often desirable to have at least two different functional groups. This review will discuss the case of bifunctional phosphorus-containing dendrimers, and the consequences for their properties. Besides the terminal functions, dendritic structures may have also a function at the core, or linked off-center to the core, or at the core of dendrons (dendritic wedges). Association of two dendrons having different terminal functions leads to Janus dendrimers (two faces). The internal structure can also possess functional groups on one layer, or linked to one layer, or on several layers. Finally, there are several ways to have two types of terminal functions, besides the case of Janus dendrimers: either each terminal function bears two functions sequentially, or two different functions are linked to each terminal branching point. Examples of each type of structure will be given in this review, as well as practical uses of such sophisticated structures in the fields of fluorescence, catalysis, nanomaterials and biology. PMID:27120586

  11. Photoaffinity labeling and photoaffinity cross-linking of phosphofructokinase-1 from Saccharomyces cerevisiae by 8-azidoadeninenucleotides.

    PubMed

    Knoche, M; Mönnich, K; Schäfer, H J; Kopperschläger, G

    2001-01-15

    Phosphofructokinase-1 from Saccharomyces cerevisiae is composed of four alpha- and four beta-subunits, each of them carrying catalytic and regulatory bindings sites for MgATP. In this paper, various photoaffinity labels, such as 8-azidoadenosine 5'-triphosphate, 8-azido-1,N6-ethenoadenosine 5'-triphosphate, and 8-N3-3'(2')-O-biotinyl-8-azidoadenosine 5'-triphosphate have been used to study their interaction with the enzyme in the dark and during irradiation. All nucleotidetriphosphates function as phosphate donor forming fructose 1,6-bisphosphate from fructose 6-phosphate. However, the kinetic analysis revealed distinctly differences between them. Photolabeling causes a decrease in enzyme activity to a similar extent, and ATP acts as competitive effector to inactivation. Three bifunctional diazidodiadeninedinucleotides (8-diN3AP4A, monoepsilon-8-diN3AP4A, and diepsilon-8-diN3AP4A) were applied for studying the spatial arrangement of the nucleotide binding sites. No cross-linking of the subunits was obtained by irradiation of the enzyme with 8-diN3AP4A. Photolabeling with diepsilon-8-diN3AP4A resulted in the formation of two alpha-beta cross-links with different mobilities in the SDS-polyacrylamide gel electrophoresis, while monoepsilon-8-diN3AP4A yielded only one alpha-beta cross-link. Because an interfacial location of the catalytic sites between two subunits is less likely, we suggest that the formation of cross-linked subunits may be the result of specific interactions of the bifunctional photolabels with regulatory sites at the interface of both subunits. PMID:11368011

  12. Epoxy Cross-Linked Collagen and Collagen-Laminin Peptide Hydrogels as Corneal Substitutes

    PubMed Central

    Koh, Li Buay; Islam, Mohammad Mirazul; Mitra, Debbie; Noel, Christopher W.; Merrett, Kimberley; Odorcic, Silvia; Fagerholm, Per; Jackson, William. Bruce; Liedberg, Bo; Phopase, Jaywant; Griffith, May

    2013-01-01

    A bi-functional epoxy-based cross-linker, 1,4-Butanediol diglycidyl ether (BDDGE), was investigated in the fabrication of collagen based corneal substitutes. Two synthetic strategies were explored in the preparation of the cross-linked collagen scaffolds. The lysine residues of Type 1 porcine collagen were directly cross-linked using l,4-Butanediol diglycidyl ether (BDDGE) under basic conditions at pH 11. Alternatively, under conventional methodology, using both BDDGE and 1-Ethyl-3-(3-dimethyl aminopropyl) carbodiimide (EDC)/N-hydroxysuccinimide (NHS) as cross-linkers, hydrogels were fabricated under acidic conditions. In this latter strategy, Cu(BF4)2·XH2O was used to catalyze the formation of secondary amine bonds. To date, we have demonstrated that both methods of chemical cross-linking improved the elasticity and tensile strength of the collagen implants. Differential scanning calorimetry and biocompatibility studies indicate comparable, and in some cases, enhanced properties compared to that of the EDC/NHS controls. In vitro studies showed that human corneal epithelial cells and neuronal progenitor cell lines proliferated on these hydrogels. In addition, improvement of cell proliferation on the surfaces of the materials was observed when neurite promoting laminin epitope, IKVAV, and adhesion peptide, YIGSR, were incorporated. However, the elasticity decreased with peptide incorporation and will require further optimization. Nevertheless, we have shown that epoxy cross-linkers should be further explored in the fabrication of collagen-based hydrogels, as alternatives to or in conjunction with carbodiimide cross-linkers. PMID:24956085

  13. Laser welding and collagen crosslinks

    SciTech Connect

    Reiser, K.M.; Last, J.A.; Small, W. IV; Maitland, D.J.; Heredia, N.J.; Da Silva, L.B.; Matthews, D.L.

    1997-02-20

    Strength and stability of laser-welded tissue may be influenced, in part, by effects of laser exposure on collagen crosslinking. We therefore studied effects of diode laser exposure (805 nm, 1-8 watts, 30 seconds) + indocyanine green dye (ICG) on calf tail tendon collagen crosslinks. Effect of ICG dye alone on crosslink content prior to laser exposure was investigated; unexpectedly, we found that ICG-treated tissue had significantly increased DHLNL and OHP, but not HLNL. Laser exposure after ICG application reduced elevated DHLNL and OHP crosslink content down to their native levels. The monohydroxylated crosslink HLNL was inversely correlated with laser output (p<0.01 by linear regression analysis). DHLNL content was highly correlated with content of its maturational product, OHP, suggesting that precursor-product relations are maintained. We conclude that: (1)ICG alone induces DHLNL and OHP crosslink formation; (2)subsequent laser exposure reduces the ICG-induced crosslinks down to native levels; (3)excessive diode laser exposure destroys normally occurring HLNL crosslinks.

  14. DNA Photolithography with Cinnamate Crosslinkers

    NASA Technical Reports Server (NTRS)

    Feng, Lang (Inventor); Chaikin, Paul Michael (Inventor)

    2016-01-01

    The present invention relates generally to cinnamate crosslinkers. Specifically, the present invention relates to gels, biochips, and functionalized surfaces useful as probes, in assays, in gels, and for drug delivery, and methods of making the same using a newly-discovered crosslinking configuration.

  15. Formation of Deoxyguanosine Cross-links from Calf Thymus DNA Treated with Acrolein and 4-Hydroxy-2-nonenal

    PubMed Central

    Kozekov, Ivan D.; Turesky, Robert J.; Alas, Guillermo R.; Harris, Constance M.; Harris, Thomas M.; Rizzo, Carmelo J.

    2010-01-01

    Acrolein (AC) and 4-hydroxy-2-nonenal (HNE) are α,β-unsaturated aldehyde (enal) endogenous bis-electrophiles that arise from the oxidation of polyunsaturated fatty acids. AC is also found in high concentrations in cigarette smoke and automobile exhaust. These reactive enals covalently modify nucleic acids, to form exocyclic adducts, where the three-carbon hydroxypropano unit bridges the N1 and N2 -positions of deoxyguanosine (dG). The bifunctional nature of these enals enables them to undergo reaction with a second nucleophilic group and form DNA cross-links. These cross-linked enal adducts are likely to contribute to the genotoxic effects of both AC and HNE. We have developed a sensitive mass spectrometric method to detect cross-linked adducts of these enals in calf thymus DNA (CT DNA) treated with AC or HNE. The AC and HNE cross-linked adducts were measured by the stable isotope dilution method, employing a linear quadrupole ion trap mass spectrometer and consecutive reaction monitoring at the MS3 or MS4 scan stage. The lower limit of quantification of the cross-linked adducts is ~1 adduct per 108 DNA bases, when 50 µg of DNA is assayed. The cross-linked adducts occur at levels that are ~1–2% of the levels of the monomeric 1,N2-dG adducts in CT DNA treated with either enal. PMID:20964440

  16. Interdomain communications in bifunctional enzymes: how are different activities coordinated?

    PubMed

    Nagradova, Natalya

    2003-08-01

    Although bifunctional enzymes containing two different active centers located within separate domains are quite common in living systems, the significance of this bifunctionality is not always clear, and the molecular mechanisms of site-site interactions in such complex systems have come under the scrutiny of science only in recent years. This review summarizes recent data on the mechanisms of communication between active centers in bifunctional enzymes. Three types of enzymes are considered: (1) those catalyzing consecutive reactions of a metabolic pathway and exhibiting substrate channeling (glutamate synthase and imidazole glycerol phosphate synthase), (2) those catalyzing consecutive reactions without substrate channeling (lysine-ketoglutarate reductase/saccharopine dehydrogenase), and (3) those catalyzing opposed reactions (6-phosphofructo-2-kinase/fructose-2,6-bisphosphatase). The functional role of interdomain communications is briefly discussed. PMID:14609201

  17. Strategies for the preparation of bifunctional gadolinium(III) chelators

    PubMed Central

    Frullano, Luca; Caravan, Peter

    2012-01-01

    The development of gadolinium chelators that can be easily and readily linked to various substrates is of primary importance for the development high relaxation efficiency and/or targeted magnetic resonance imaging (MRI) contrast agents. Over the last 25 years a large number of bifunctional chelators have been prepared. For the most part, these compounds are based on ligands that are already used in clinically approved contrast agents. More recently, new bifunctional chelators have been reported based on complexes that show a more potent relaxation effect, faster complexation kinetics and in some cases simpler synthetic procedures. This review provides an overview of the synthetic strategies used for the preparation of bifunctional chelators for MRI applications. PMID:22375102

  18. Structure of a DNA Repair Substrate Containing an Alkyl Interstrand Crosslink at 1.65 Å Resolution†‡

    PubMed Central

    Swenson, Matthew C.; Paranawithana, Shanthi R.; Miller, Paul S.; Kielkopf, Clara L.

    2008-01-01

    Chemotherapeutic alkylating agents, such as bifunctional nitrogen mustards and cisplatins, generate interstrand DNA crosslinks that inhibit cell proliferation by arresting DNA transcription and replication. A synthetic N4C-ethyl-N4C interstrand crosslink between opposing cytidines mimics the DNA damage produced by this class of clinically important compounds, and can be synthesized in large quantities to study the repair, physical properties, and structures of these DNA adducts. The X-ray structure of a DNA duplex d(CCAAC*GTTGG)2 containing a synthetic N4C-ethyl-N4C interstrand crosslink between the cytosines of the central CpG step (*) has been determined at 1.65 Å resolution. This structure reveals that the ethyl crosslink in the CpG major groove does not significantly disrupt the B-form DNA helix. Comparison of the N4C-ethyl-N 4C crosslinked structure with the structure of an uncrosslinked oligonucleotide of the same sequence reveals that the crosslink selectively stabilizes a pre-existing alternative conformation. The conformation preferred by the crosslinked DNA is constrained by the geometry of the ethyl group bridging the cytosine amines. Characteristics of the crosslinked CpG step include subtle differences in the roll of the base pairs, optimized Watson-Crick hydrogen bonds, and loss of a divalent cation binding site. Given that the N4C-ethyl-N4C crosslink stabilizes a pre-existing conformation of the CpG step, this synthetically accessible substrate presents an ideal model system for studying the genomic effects of covalently coupling the DNA strands, independent of gross alterations in DNA structure. PMID:17375936

  19. Novel bifunctional natriuretic peptides as potential therapeutics.

    PubMed

    Dickey, Deborah M; Burnett, John C; Potter, Lincoln R

    2008-12-12

    Synthetic atrial natriuretic peptide (carperitide) and B-type natriuretic peptide (BNP; nesiritide) are used to treat congestive heart failure. However, despite beneficial cardiac unloading properties, reductions in renal perfusion pressures limit their clinical effectiveness. Recently, CD-NP, a chimeric peptide composed of C-type natriuretic peptide (CNP) fused to the C-terminal tail of Dendroaspis natriuretic peptide (DNP), was shown to be more glomerular filtration rate-enhancing than BNP in dogs. However, the molecular basis for the increased responsiveness was not determined. Here, we show that the DNP tail has a striking effect on CNP, converting it from a non-agonist to a partial agonist of natriuretic peptide receptor (NPR)-A while maintaining the ability to activate NPR-B. This effect is specific for human receptors because CD-NP was only a slightly better activator of rat NPR-A due to the promiscuous nature of CNP in this species. Interesting, the DNP tail alone had no effect on any NPR even though it is effective in vivo. To further increase the potency of CD-NP for NPR-A, we converted two different triplet sequences within the CNP ring to their corresponding residues in BNP. Both variants demonstrated increased affinity and full agonist activity for NPR-A, whereas one was as potent as any NPR-A activator known. In contrast to a previous report, we found that DNP binds the natriuretic peptide clearance receptor (NPR-C). However, none of the chimeric peptides bound NPR-C with significantly higher affinity than endogenous ligands. We suggest that bifunctional chimeric peptides represent a new generation of natriuretic peptide therapeutics. PMID:18940797

  20. Novel Bifunctional Natriuretic Peptides as Potential Therapeutics*

    PubMed Central

    Dickey, Deborah M.; Burnett, John C.; Potter, Lincoln R.

    2008-01-01

    Synthetic atrial natriuretic peptide (carperitide) and B-type natriuretic peptide (BNP; nesiritide) are used to treat congestive heart failure. However, despite beneficial cardiac unloading properties, reductions in renal perfusion pressures limit their clinical effectiveness. Recently, CD-NP, a chimeric peptide composed of C-type natriuretic peptide (CNP) fused to the C-terminal tail of Dendroaspis natriuretic peptide (DNP), was shown to be more glomerular filtration rate-enhancing than BNP in dogs. However, the molecular basis for the increased responsiveness was not determined. Here, we show that the DNP tail has a striking effect on CNP, converting it from a non-agonist to a partial agonist of natriuretic peptide receptor (NPR)-A while maintaining the ability to activate NPR-B. This effect is specific for human receptors because CD-NP was only a slightly better activator of rat NPR-A due to the promiscuous nature of CNP in this species. Interesting, the DNP tail alone had no effect on any NPR even though it is effective in vivo. To further increase the potency of CD-NP for NPR-A, we converted two different triplet sequences within the CNP ring to their corresponding residues in BNP. Both variants demonstrated increased affinity and full agonist activity for NPR-A, whereas one was as potent as any NPR-A activator known. In contrast to a previous report, we found that DNP binds the natriuretic peptide clearance receptor (NPR-C). However, none of the chimeric peptides bound NPR-C with significantly higher affinity than endogenous ligands. We suggest that bifunctional chimeric peptides represent a new generation of natriuretic peptide therapeutics. PMID:18940797

  1. Bifunctional Chelates Optimized for Molecular MRI

    PubMed Central

    2015-01-01

    Important requirements for exogenous dyes or contrast agents in magnetic resonance imaging (MRI) include an effective concentration of paramagnetic or superparamagnetic ions at the target to be imaged. We report the concise synthesis and characterization of several new enantiopure bifunctional derivatives of (α1R,α4R,α7R,α10R)-α1,α4,α7,α10-tetramethyl-1,4,7,10-tetraazacyclododecane-1,4,7,10-tetraacetic acid (DOTMA) (and their 1,4,7,10-tetraazacyclododecane-1,4,7,10-tetraacetic acid (DOTA) analogues as controls) that can be covalently attached to a contrast agent delivery system using either click or peptide coupling chemistry. Gd complexes of these derivatives can be attached to delivery systems while maintaining optimal water residence time for increased molecular imaging sensitivity. Long chain biotin (LC-biotin) derivatives of the Eu(III) and Gd(III) chelates associated with avidin are used to demonstrate higher efficiencies. Variable-temperature relaxometry, 17O NMR, and nuclear magnetic resonance dispersion (NMRD) spectroscopy used on the complexes and biotin–avidin adducts measure the influence of water residence time and rotational correlation time on constrained and unconstrained systems. The Gd(III)-DOTMA derivative has a shorter water residence time than the Gd(III)-DOTA derivative. Compared to the constrained Gd(III)-DOTA derivatives, the rotationally constrained Gd(III)-DOTMA derivative has ∼40% higher relaxivity at 37 °C, which could increase its sensitivity as an MRI agent as well as reduce the dose of the targeting agent. PMID:24933389

  2. Function and Localization Dynamics of Bifunctional Penicillin-Binding Proteins in Caulobacter crescentus

    PubMed Central

    Strobel, Wolfgang; Möll, Andrea; Kiekebusch, Daniela; Klein, Kathrin E.

    2014-01-01

    The peptidoglycan cell wall of bacteria is a complex macromolecule composed of glycan strands that are cross-linked by short peptide bridges. Its biosynthesis involves a conserved group of enzymes, the bifunctional penicillin-binding proteins (bPBPs), which contain both a transglycosylase and a transpeptidase domain, thus being able to elongate the glycan strands and, at the same time, generate the peptide cross-links. The stalked model bacterium Caulobacter crescentus possesses five bPBP paralogs, named Pbp1A, PbpC, PbpX, PbpY, and PbpZ, whose function is still incompletely understood. In this study, we show that any of these proteins except for PbpZ is sufficient for growth and normal morphogenesis when expressed at native or elevated levels, whereas inactivation of all five paralogs is lethal. Growth analyses indicate a central role of PbpX in the resistance of C. crescentus against the noncanonical amino acid d-alanine. Moreover, we show that PbpX and PbpY localize to the cell division site. Their recruitment to the divisome is dependent on the essential cell division protein FtsN and likely involves interactions with FtsL and the putative peptidoglycan hydrolase DipM. The same interaction pattern is observed for Pbp1A and PbpC, although these proteins do not accumulate at midcell. Our findings demonstrate that the bPBPs of C. crescentus are, to a large extent, redundant and have retained the ability to interact with the peptidoglycan biosynthetic machineries responsible for cell elongation, cytokinesis, and stalk growth. Nevertheless, they may preferentially act in specific peptidoglycan biosynthetic complexes, thereby facilitating the independent regulation of distinct growth processes. PMID:24532768

  3. Bifunctional mesoporous silicas with clearly distinguished localization of grafted groups

    NASA Astrophysics Data System (ADS)

    Roik, N. V.; Belyakova, L. A.

    2013-12-01

    Bifunctional mesoporous silicas with clearly distinguished localization of grafted groups on the surface of particles and inside their pores were obtained by means of sol-gel synthesis with postsynthetic vapor-phase treatment in vacuum. It was found that the synthesized materials have the hexagonally ordered porous structure typical of MCM-41 type silica.

  4. Crosslinking of agarose bioplastic using citric acid.

    PubMed

    Awadhiya, Ankur; Kumar, David; Verma, Vivek

    2016-10-20

    We report chemical crosslinking of agarose bioplastic using citric acid. Crosslinking was confirmed using Fourier transform infrared (FTIR) spectroscopy. The effects of crosslinking on the tensile strength, swelling, thermal stability, and degradability of the bioplastic were studied in detail. The tensile strength of the bioplastic films increased from 25.1MPa for control films up to a maximum of 52.7MPa for citric acid crosslinked films. At 37°C, the amount of water absorbed by crosslinked agarose bioplastic was only 11.5% of the amount absorbed by non-crosslinked controls. Thermogravimetric results showed that the crosslinked samples retain greater mass at high temperature (>450°C) than control samples. Moreover, while the crosslinked films were completely degradable, the rate of degradation was lower compared to non-crosslinked controls. PMID:27474543

  5. A protein crosslinking assay for measuring cell surface expression of glutamate receptor subunits in the rodent brain after in vivo treatments

    PubMed Central

    Boudreau, Amy C.; Milovanovic, Mike; Conrad, Kelly L.; Nelson, Christopher; Ferrario, Carrie R.; Wolf, Marina E.

    2012-01-01

    Trafficking of neurotransmitter receptors between intracellular and cell surface compartments is important for regulating neurotransmission. We developed a method for determining if an in vivo treatment has altered receptor distribution in a particular region of rodent brain. After the treatment, brain slices are rapidly prepared from the region of interest. Then cell surface-expressed receptors are covalently crosslinked to nearby proteins using the membrane-impermeable, bifunctional crosslinker bis(sulfosuccinimidyl)suberate (BS3). This increases the apparent molecular weight of surface receptors, while intracellular receptors are not modified. Thus, surface and intracellular receptor pools can be separated and quantified using SDS-PAGE and immunoblotting. This method is particularly useful for analyzing AMPA receptor subunits, offering advantages in accuracy, efficiency and cost compared to biotinylation. A disadvantage is that some antibodies no longer recognize their target protein after crosslinking. We have used this method to quantify changes in receptor distribution after acute and chronic exposure to psychomotor stimulants. PMID:22470150

  6. Electrochemical properties of interstrand cross-linked DNA duplexes labeled with Nile blue.

    PubMed

    Mie, Yasuhiro; Kowata, Keiko; Kojima, Naoshi; Komatsu, Yasuo

    2012-12-11

    DNA molecules have attracted considerable attention as functional materials in various fields such as electrochemical sensors with redox-labeled DNA. However, the recently developed interstrand cross-link (ICL) technique for double-stranded DNA can adequately modify the electronic properties inside the duplex. Hence, the electrochemical investigation of ICL-DNA helps us to understand the electron transfer of redox-labeled DNA at an electrode surface, which would develop useful sensors. In this study, the first insight into this matter is presented. We prepared 17-mer DNA duplexes incorporating Nile blue (NB-DNA) at one end as a redox marker and a disulfide tether at the other end for immobilization onto an electrode. The duplexes were covalently cross-linked by bifunctional cross-linkers that utilize either a propyl or naphthalene residue to replace a base pair. Their electrochemical responses at the electrode surface were compared to evaluate the effect of the ICL on the electron-transfer reactions of the redox-labeled DNA duplexes. A direct transfer of electrons between NB and the electrode was observed for a standard DNA, as previously reported, whereas interstrand cross-linked DNA (CL-DNA) strands showed a decrease in the direct electron-transfer pathway. This is expected to result from constraining the elastic bending/flexibility of the duplex caused by the covalent cross-links. Interestingly, the CL-DNA incorporating naphthalene residues exhibited additional voltammetric peaks derived from DNA-mediated electron transfer (through base π stacking), which was not observed in the mismatched CL-DNA. The present results indicate that the ICL significantly affects electron transfer in the redox-labeled DNA at the electrode and can be an important determinant for electrochemical signaling in addition to its role in stabilizing the duplex structure. PMID:23153070

  7. Glutathione production by recombinant Escherichia coli expressing bifunctional glutathione synthetase.

    PubMed

    Wang, Dezheng; Wang, Cheng; Wu, Hui; Li, Zhimin; Ye, Qin

    2016-01-01

    Glutathione (GSH) is an important bioactive substance applied widely in pharmaceutical and food industries. Due to the strong product inhibition in the GSH biosynthetic pathway, high levels of intracellular content, yield and productivity of GSH are difficult to achieve. Recently, a novel bifunctional GSH synthetase was identified to be less sensitive to GSH. A recombinant Escherichia coli strain expressing gshF encoding the bifunctional glutathione synthetase of Streptococcus thermophilus was constructed for GSH production. In this study, efficient GSH production using this engineered strain was investigated. The cultivation process was optimized by controlling dissolved oxygen (DO), amino acid addition and glucose feeding. 36.8 mM (11.3 g/L) GSH were formed at a productivity of 2.06 mM/h when the amino acid precursors (75 mM each) were added and glucose was supplied as the sole carbon and energy source. PMID:26586402

  8. Bifunctional organophosphorus liquid-liquid extraction reagents: development and applications

    SciTech Connect

    Schulz, W.W.; Navratil, J.D.

    1985-01-01

    American and Russian workers have evidenced great interest in the last decade in the potential application of certain neutral and acidic bifunctional organophosphorus compounds in solvent extraction processes. Triggering this interest is the ability of some carbamoylmethylenephosphorus (CMP) and carbamoylmethylenephosphine oxide (CMPO) compounds to extract trivalent actinides and lanthanides from strong HNO/sub 3/ (>1 M) solutions, a property which distinguishes them from monofunctional organophosphorus reagents. Investigators at several US Department of Energy laboratories have concentrated on synthesis of novel CMP and CMPO reagents and on reactions and mechanisms involved in extraction of metal ions from aqueous nitrate media; application of selected CMP and CMPO reagents in solvent extraction and supported liquid membrane recovery of metal values from nuclear waste solutions have been proposed. This paper, based upon a book now in preparation, provides a brief overview of the current status of the development and application of bifunctional organophosphorus extractants. 44 references, 4 tables.

  9. Bifunctional organophosphorus liquid-liquid extraction reagents: development and applications

    SciTech Connect

    Schulz, W.W.; Navratil, J.D.

    1984-03-13

    American and Russian workers have evidenced great interest in the last decade in the potential application of certain neutral and acidic bifunctional organophosphorus compounds in solvent extraction processes. Triggering this interest is the ability of some carbamoylmethylenephosphorus (CMP) and carbamoylmethylenephosphine oxide (CMPO) compounds to extract trivalent actinides and lanthanides from strong HNO/sub 3/ (>1M) solutions, a property which distinguishes them from monofunctional organophosphorus reagents. Investigators at several US Department of Energy laboratories have concentrated on synthesis of novel CMP and CMPO reagents and on reactions and mechanisms involved in extraction of metal ions from aqueous nitrate media; application of selected CMP and CMPO reagents in solvent extraction and supported liquid membrane recovery of metal values from nuclear waste solutions have been proposed. This paper, based upon a book now in preparation, provides a brief overview of the current status of the development and application of bifunctional organophosphorus extractants. 42 references, 4 tables.

  10. The aminoindanol core as a key scaffold in bifunctional organocatalysts

    PubMed Central

    G. Sonsona, Isaac

    2016-01-01

    Summary The 1,2-aminoindanol scaffold has been found to be very efficient, enhancing the enantioselectivity when present in organocatalysts. This may be explained by its ability to induce a bifunctional activation of the substrates involved in the reaction. Thus, it is easy to find hydrogen-bonding organocatalysts ((thio)ureas, squaramides, quinolinium thioamide, etc.) in the literature containing this favored structural core. They have been successfully employed in reactions such as Friedel–Crafts alkylation, Michael addition, Diels–Alder and aza-Henry reactions. However, the 1,2-aminoindanol core incorporated into proline derivatives has been scarcely explored. Herein, the most representative and illustrative examples are compiled and this review will be mainly focused on the cases where the aminoindanol moiety confers bifunctionality to the organocatalysts. PMID:27340443

  11. The aminoindanol core as a key scaffold in bifunctional organocatalysts.

    PubMed

    G Sonsona, Isaac; Marqués-López, Eugenia; Herrera, Raquel P

    2016-01-01

    The 1,2-aminoindanol scaffold has been found to be very efficient, enhancing the enantioselectivity when present in organocatalysts. This may be explained by its ability to induce a bifunctional activation of the substrates involved in the reaction. Thus, it is easy to find hydrogen-bonding organocatalysts ((thio)ureas, squaramides, quinolinium thioamide, etc.) in the literature containing this favored structural core. They have been successfully employed in reactions such as Friedel-Crafts alkylation, Michael addition, Diels-Alder and aza-Henry reactions. However, the 1,2-aminoindanol core incorporated into proline derivatives has been scarcely explored. Herein, the most representative and illustrative examples are compiled and this review will be mainly focused on the cases where the aminoindanol moiety confers bifunctionality to the organocatalysts. PMID:27340443

  12. Bifunctional air electrodes containing elemental iron powder charging additive

    DOEpatents

    Liu, Chia-tsun; Demczyk, Brian G.; Gongaware, Paul R.

    1982-01-01

    A bifunctional air electrode for use in electrochemical energy cells is made, comprising a hydrophilic layer and a hydrophobic layer, where the hydrophilic layer essentially comprises a hydrophilic composite which includes: (i) carbon; (ii) elemental iron particles having a particle size of between about 25 microns and about 700 microns diameter; (iii) an oxygen evolution material; (iv) a nonwetting agent; and (v) a catalyst, where at least one current collector is formed into said composite.

  13. Room Temperature Hydrosilylation of Silicon Nanocrystals with Bifunctional Terminal Alkenes

    PubMed Central

    Yu, Yixuan; Hessel, Colin M.; Bogart, Timothy; Panthani, Matthew G.; Rasch, Michael R.; Korgel, Brian A.

    2013-01-01

    H-terminated Si nanocrystals undergo room temperature hydrosilylation with bifunctional alkenes with distal polar moieties—ethyl-, methyl-ester or carboxylic acids—without the aid of light or added catalyst. The passivated Si nanocrystals exhibit bright photoluminescence (PL) and disperse in polar solvents, including water. We propose a reaction mechanism in which ester or carboxylic acid groups facilitate direct nucleophilic attack of the highly curved Si surface of the nanocrystals by the alkene. PMID:23312033

  14. Nanoscale intimacy in bifunctional catalysts for selective conversion of hydrocarbons.

    PubMed

    Zečević, Jovana; Vanbutsele, Gina; de Jong, Krijn P; Martens, Johan A

    2015-12-10

    The ability to control nanoscale features precisely is increasingly being exploited to develop and improve monofunctional catalysts. Striking effects might also be expected in the case of bifunctional catalysts, which are important in the hydrocracking of fossil and renewable hydrocarbon sources to provide high-quality diesel fuel. Such bifunctional hydrocracking catalysts contain metal sites and acid sites, and for more than 50 years the so-called intimacy criterion has dictated the maximum distance between the two types of site, beyond which catalytic activity decreases. A lack of synthesis and material-characterization methods with nanometre precision has long prevented in-depth exploration of the intimacy criterion, which has often been interpreted simply as 'the closer the better' for positioning metal and acid sites. Here we show for a bifunctional catalyst--comprising an intimate mixture of zeolite Y and alumina binder, and with platinum metal controllably deposited on either the zeolite or the binder--that closest proximity between metal and zeolite acid sites can be detrimental. Specifically, the selectivity when cracking large hydrocarbon feedstock molecules for high-quality diesel production is optimized with the catalyst that contains platinum on the binder, that is, with a nanoscale rather than closest intimacy of the metal and acid sites. Thus, cracking of the large and complex hydrocarbon molecules that are typically derived from alternative sources, such as gas-to-liquid technology, vegetable oil or algal oil, should benefit especially from bifunctional catalysts that avoid locating platinum on the zeolite (the traditionally assumed optimal location). More generally, we anticipate that the ability demonstrated here to spatially organize different active sites at the nanoscale will benefit the further development and optimization of the emerging generation of multifunctional catalysts. PMID:26659185

  15. Nanoscale intimacy in bifunctional catalysts for selective conversion of hydrocarbons

    NASA Astrophysics Data System (ADS)

    Zecevic, Jovana; Vanbutsele, Gina; de Jong, Krijn P.; Martens, Johan A.

    2015-12-01

    The ability to control nanoscale features precisely is increasingly being exploited to develop and improve monofunctional catalysts. Striking effects might also be expected in the case of bifunctional catalysts, which are important in the hydrocracking of fossil and renewable hydrocarbon sources to provide high-quality diesel fuel. Such bifunctional hydrocracking catalysts contain metal sites and acid sites, and for more than 50 years the so-called intimacy criterion has dictated the maximum distance between the two types of site, beyond which catalytic activity decreases. A lack of synthesis and material-characterization methods with nanometre precision has long prevented in-depth exploration of the intimacy criterion, which has often been interpreted simply as ‘the closer the better’ for positioning metal and acid sites. Here we show for a bifunctional catalyst—comprising an intimate mixture of zeolite Y and alumina binder, and with platinum metal controllably deposited on either the zeolite or the binder—that closest proximity between metal and zeolite acid sites can be detrimental. Specifically, the selectivity when cracking large hydrocarbon feedstock molecules for high-quality diesel production is optimized with the catalyst that contains platinum on the binder, that is, with a nanoscale rather than closest intimacy of the metal and acid sites. Thus, cracking of the large and complex hydrocarbon molecules that are typically derived from alternative sources, such as gas-to-liquid technology, vegetable oil or algal oil, should benefit especially from bifunctional catalysts that avoid locating platinum on the zeolite (the traditionally assumed optimal location). More generally, we anticipate that the ability demonstrated here to spatially organize different active sites at the nanoscale will benefit the further development and optimization of the emerging generation of multifunctional catalysts.

  16. Nanoscale intimacy in bifunctional catalysts for selective conversion of hydrocarbons

    PubMed Central

    Zečević, Jovana; Vanbutsele, Gina; de Jong, Krijn P.; Martens, Johan A.

    2016-01-01

    The ability to precisely control nanoscale features is increasingly exploited to develop and improve monofunctional catalysts1–4. Striking effects might also be expected in the case of bifunctional catalysts, which play an important role in hydrocracking of fossil and renewable hydrocarbon sources to provide high-quality diesel fuel5–7. Such bifunctional hydrocracking catalysts contain metal sites and acid sites, and for more than 50 years the so-called ‘intimacy criterion’8 has dictated the maximum distance between the two site types beyond which catalytic activity decreases. The lack of synthesis and material characterization methods with nanometer precision has long prevented in-depth exploration of the criterion, which has often been interpreted simply as ‘the closer the better’ for positioning metal and acid sites8–11. Here we show for a bifunctional catalyst, comprised of an intimate mixture of zeolite Y and alumina binder and with platinum (Pt) metal controllably deposited20,21 on either the zeolite or the binder, that close proximity between metal and zeolite acid sites can be detrimental: the selectivity when cracking large hydrocarbon feedstock molecules for high-quality diesel production is optimized with the catalyst that contains Pt on the binder, i.e. with a larger distance between metal and acid sites. Cracking of the large and complex hydrocarbon molecules typically derived from alternative sources such as gas-to-liquid technology, vegetable oil or algal oil6–7 should thus benefit especially from bifunctional catalysts that avoid locating Pt on the zeolite as the traditionally assumed optimal location. More generally, we anticipate that the ability to spatially organize different active sites at the nanoscale demonstrated here will benefit the further development and optimization of the newly emerging generation of multifunctional catalysts12–15. PMID:26659185

  17. (Bifunctional chelates of Rh-105, Au-199, and other metallic radionuclides as potential radiotherapeutic agents)

    SciTech Connect

    Not Available

    1991-01-01

    Progress during this period is reported under the following headings: Diethylenetriamine based and related bifunctional chelating agents and their complexation with Rh-105, Au-198, Pd-109, cu-67, In-111, and Co-57; studies of Pd-109, Rh-105 and Tc-99m with bifunctional chelates based on phenylenediamine; establishment of an appropriate protein assay method for conjugated proteins; studies of new bifunctional Bi, Tri and tetradentate amine oxime ligands with Rh-105; IgG and antibody B72.3 conjugation studies by HPLC Techniques with bifunctional metal chelates; and progress on ligand systems for Au(III).

  18. [Bifunctional chelates of Rh-105, Au-199, and other metallic radionuclides as potential radiotherapeutic agents

    SciTech Connect

    Not Available

    1991-12-31

    Progress during this period is reported under the following headings: Diethylenetriamine based and related bifunctional chelating agents and their complexation with Rh-105, Au-198, Pd-109, cu-67, In-111, and Co-57; studies of Pd-109, Rh-105 and Tc-99m with bifunctional chelates based on phenylenediamine; establishment of an appropriate protein assay method for conjugated proteins; studies of new bifunctional Bi, Tri and tetradentate amine oxime ligands with Rh-105; IgG and antibody B72.3 conjugation studies by HPLC Techniques with bifunctional metal chelates; and progress on ligand systems for Au(III).

  19. Shadow enhancers enable Hunchback bifunctionality in the Drosophila embryo

    PubMed Central

    Staller, Max V.; Vincent, Ben J.; Bragdon, Meghan D. J.; Lydiard-Martin, Tara; Wunderlich, Zeba; Estrada, Javier; DePace, Angela H.

    2015-01-01

    Hunchback (Hb) is a bifunctional transcription factor that activates and represses distinct enhancers. Here, we investigate the hypothesis that Hb can activate and repress the same enhancer. Computational models predicted that Hb bifunctionally regulates the even-skipped (eve) stripe 3+7 enhancer (eve3+7) in Drosophila blastoderm embryos. We measured and modeled eve expression at cellular resolution under multiple genetic perturbations and found that the eve3+7 enhancer could not explain endogenous eve stripe 7 behavior. Instead, we found that eve stripe 7 is controlled by two enhancers: the canonical eve3+7 and a sequence encompassing the minimal eve stripe 2 enhancer (eve2+7). Hb bifunctionally regulates eve stripe 7, but it executes these two activities on different pieces of regulatory DNA—it activates the eve2+7 enhancer and represses the eve3+7 enhancer. These two “shadow enhancers” use different regulatory logic to create the same pattern. PMID:25564665

  20. Protein folding: Turbo-charged crosslinking

    NASA Astrophysics Data System (ADS)

    Craik, David J.

    2012-08-01

    The efficient production of stable bioactive proteins often requires the selective formation of several disulfide crosslinks. Two recent studies have now shown that replacing cysteine with selenocysteine in the unfolded protein can autocatalyse the formation of the desired crosslinks.

  1. Degradable polyethylenimine derivate coupled to a bifunctional peptide R13 as a new gene-delivery vector

    PubMed Central

    Liu, Kehai; Wang, Xiaoyu; Fan, Wei; Zhu, Qing; Yang, Jingya; Gao, Jing; Gao, Shen

    2012-01-01

    Background To solve the efficiency versus cytotoxicity and tumor-targeting problems of polyethylenimine (PEI) used as a nonviral gene delivery vector, a degradable PEI derivate coupled to a bifunctional peptide R13 was developed. Methods First, we synthesized a degradable PEI derivate by crosslinking low-molecular-weight PEI with pluronic P123, then used tumor-targeting peptide arginine-glycine-aspartate-cysteine (RGDC), in conjunction with the cell-penetrating peptide Tat (49–57), to yield a bifunctional peptide RGDC-Tat (49–57) named R13, which can improve cell selection and increase cellular uptake, and, lastly, adopted R13 to modify the PEI derivates so as to prepare a new polymeric gene vector (P123-PEI-R13). The new gene vector was characterized in terms of its chemical structure and biophysical parameters. We also investigated the specificity, cytotoxicity, and gene transfection efficiency of this vector in αvβ3-positive human cervical carcinoma Hela cells and murine melanoma B16 cells in vitro. Results The vector showed controlled degradation, strong targeting specificity to αvβ3 receptor, and noncytotoxicity in Hela cells and B16 cells at higher doses, in contrast to PEI 25 KDa. The particle size of P123-PEI-R13/DNA complexes was around 100–250 nm, with proper zeta potential. The nanoparticles can protect plasmid DNA from being digested by DNase I at a concentration of 6 U DNase I/μg DNA. The nanoparticles were resistant to dissociation induced by 50% fetal bovine serum and 600 μg/mL sodium heparin. P123-PEI-R13 also revealed higher transfection efficiency in two cell lines as compared with PEI 25 KDa. Conclusion P123-PEI-R13 is a potential candidate as a safe and efficient gene-delivery carrier for gene therapy. PMID:22412301

  2. A bi-functional antibody-receptor domain fusion protein simultaneously targeting IGF-IR and VEGF for degradation

    PubMed Central

    Shen, Yang; Zeng, Lin; Novosyadlyy, Ruslan; Forest, Amelie; Zhu, Aiping; Korytko, Andrew; Zhang, Haifan; Eastman, Scott W; Topper, Michael; Hindi, Sagit; Covino, Nicole; Persaud, Kris; Kang, Yun; Burtrum, Douglas; Surguladze, David; Prewett, Marie; Chintharlapalli, Sudhakar; Wroblewski, Victor J; Shen, Juqun; Balderes, Paul; Zhu, Zhenping; Snavely, Marshall; Ludwig, Dale L

    2015-01-01

    Bi-specific antibodies (BsAbs), which can simultaneously block 2 tumor targets, have emerged as promising therapeutic alternatives to combinations of individual monoclonal antibodies. Here, we describe the engineering and development of a novel, human bi-functional antibody-receptor domain fusion molecule with ligand capture (bi-AbCap) through the fusion of the domain 2 of human vascular endothelial growth factor receptor 1 (VEGFR1) to an antibody directed against insulin-like growth factor – type I receptor (IGF-IR). The bi-AbCap possesses excellent stability and developability, and is the result of minimal engineering. Beyond potent neutralizing activities against IGF-IR and VEGF, the bi-AbCap is capable of cross-linking VEGF to IGF-IR, leading to co-internalization and degradation of both targets by tumor cells. In multiple mouse xenograft tumor models, the bi-AbCap improves anti-tumor activity over individual monotherapies. More importantly, it exhibits superior inhibition of tumor growth, compared with the combination of anti-IGF-IR and anti-VEGF therapies, via powerful blockade of both direct tumor cell growth and tumor angiogenesis. The unique “capture-for-degradation” mechanism of the bi-AbCap is informative for the design of next-generation bi-functional anti-cancer therapies directed against independent signaling pathways. The bi-AbCap design represents an alternative approach to the creation of dual-targeting antibody fusion molecules by taking advantage of natural receptor-ligand interactions. PMID:26073904

  3. A bi-functional antibody-receptor domain fusion protein simultaneously targeting IGF-IR and VEGF for degradation.

    PubMed

    Shen, Yang; Zeng, Lin; Novosyadlyy, Ruslan; Forest, Amelie; Zhu, Aiping; Korytko, Andrew; Zhang, Haifan; Eastman, Scott W; Topper, Michael; Hindi, Sagit; Covino, Nicole; Persaud, Kris; Kang, Yun; Burtrum, Douglas; Surguladze, David; Prewett, Marie; Chintharlapalli, Sudhakar; Wroblewski, Victor J; Shen, Juqun; Balderes, Paul; Zhu, Zhenping; Snavely, Marshall; Ludwig, Dale L

    2015-01-01

    Bi-specific antibodies (BsAbs), which can simultaneously block 2 tumor targets, have emerged as promising therapeutic alternatives to combinations of individual monoclonal antibodies. Here, we describe the engineering and development of a novel, human bi-functional antibody-receptor domain fusion molecule with ligand capture (bi-AbCap) through the fusion of the domain 2 of human vascular endothelial growth factor receptor 1 (VEGFR1) to an antibody directed against insulin-like growth factor - type I receptor (IGF-IR). The bi-AbCap possesses excellent stability and developability, and is the result of minimal engineering. Beyond potent neutralizing activities against IGF-IR and VEGF, the bi-AbCap is capable of cross-linking VEGF to IGF-IR, leading to co-internalization and degradation of both targets by tumor cells. In multiple mouse xenograft tumor models, the bi-AbCap improves anti-tumor activity over individual monotherapies. More importantly, it exhibits superior inhibition of tumor growth, compared with the combination of anti-IGF-IR and anti-VEGF therapies, via powerful blockade of both direct tumor cell growth and tumor angiogenesis. The unique "capture-for-degradation" mechanism of the bi-AbCap is informative for the design of next-generation bi-functional anti-cancer therapies directed against independent signaling pathways. The bi-AbCap design represents an alternative approach to the creation of dual-targeting antibody fusion molecules by taking advantage of natural receptor-ligand interactions. PMID:26073904

  4. Electrospinning formaldehyde cross-linked zein solutions

    Technology Transfer Automated Retrieval System (TEKTRAN)

    In order to develop zein fibers with improved physical properties and solvent resistance, formaldehyde was used as the cross-linking reagent before spinning. The cross-linking reaction was carried out in either acetic acid or ethanolic-HCl where the amount of cross-linking reagent was between 1 and...

  5. Identification of neighbouring protein pairs in the rat liver 40-S ribosomal subunits cross-linked with dimethyl suberimidate.

    PubMed

    Terao, K; Uchiumi, T; Kobayashi, Y; Ogata, K

    1980-01-24

    (1) The 40-S ribosomal subunits of rat liver were treated with a bifunctional cross-linking reagent, dimethyl suberimidate. Cross-linked protein-protein dimers were separated by two-dimensional acrylamide gel electrophoresis. The stained cross-linked complexes within the gel were radioiodinated without the elution of proteins from the gel and were cloven into the original monomeric protein constituents by ammonolysis. The proteins in each dimer were finally identified by two-dimensional acrylamide gel electrophoresis of the cloven monomeric proteins, followed by radioautography of the stained gel. (2) The molecular weights of cross-linked complexes were determined by SDS-polyacrylamide gel electrophoresis and were compared with those of their constituent proteins. (3) The following dimers were proposed from these results: S3-S12 (S3 or S3a-S11), S4-S12 (S3b-S11, S5-S7 (S4-S6), S5-S22 (S4-S23 or S24), S6-S8 (S5-S7), S8-S16 (S7-S18), S17-S21 (S16--S19) and S22A-S22B (S23-S24), designated according to our numbering system [1]. The designations according to the proposed uniform nomenclature [2] are described in parentheses. PMID:7353033

  6. Property peculiarities of the atelocollagen-hyaluronan conjugates crosslinked with a short chain di-oxirane compound.

    PubMed

    Maier, Vasilica; Lefter, Cristina M; Maier, Stelian S; Butnaru, Maria; Danu, Maricel; Ibanescu, Constanta; Popa, Marcel; Desbrieres, Jacques

    2014-09-01

    Minimal amounts of a short-chain bifunctional crosslinker of about 1.3 nm length, the 1,4-butanediol-diglycidyl ether (BDDGE), were used to generate atelocollagen-hyaluronan conjugates in hydrogel state. Two a priori constraints were considered in recipe/procedure developing: (i) working in nondenaturing conditions, and (ii) ensuring a low cytotoxicity of the final product. Both atelocollagen (aK) and hyaluronan (NaHyal) were accurately purified to reduce their molecular-weight dispersity, in order to ensure the reproducibility of hydrogels characteristics. 1:5 aK:NaHyal weight ratios and 1:2.5 to 1:5 α-NH2:BDDGE molar ratios were found to be the most favorable recipe prescriptions that allow the obtaining of rheo-mechanically stable hydrogels, able to be manipulated during cell culturing protocols. Experiments revealed two unexpected effects due to the crosslinking reactions mediated by a short-chain molecule: (i) the occurrence of two thresholds in the rheological behavior of the hydrogels, related with the amount of added crosslinker, and (ii) a quasi-denaturation side-effect induced over the protein component by large or in excess amounts of crosslinker. PMID:25063116

  7. REDUCTIVE ACTIVATION OF DIOXYGEN FOR DEGRADATION OF METHYL TERT-BUTYL ETHER BY BIFUNCTION

    EPA Science Inventory

    Bifunctional aluminum is prepared by sulfating aluminum metal with sulfuric acid. The use of bifunctional aluminum to degrade methyl tert-butyl ether (MTBE) in the presence of dioxygen has been examined using batch systems. Primary degradation products were tert-butyl alcohol, ...

  8. Stepwise assembly of a cross-linked free-standing nanoparticle sheet with controllable shape

    NASA Astrophysics Data System (ADS)

    Zhang, Hui; Liu, Mei; Zhou, Tian; Dong, Bin; Li, Christopher Y.

    2015-06-01

    In this paper, we report a free-standing thin lamella consisting of nanoparticles with controllable shape. A self-assembly technique is utilized to obtain this sheet in a step by step fashion with nanoparticles and polymer single crystals as the basic building blocks. Inside the thin lamella, nanoparticles are not only immobilized on the surface of a polymer single crystal, which functions as a template, but also interconnected by a bifunctional crosslinker, i.e. 1,6-hexane dithiol. As a consequence, the nanoparticle lamella is crosslinked and cannot be destructed by solvent and heat treatment. This fabrication strategy is generally applicable and can be applied to a variety of different nanoparticles with various properties, including catalytically active platinum nanoparticles, superparamagnetic iron oxide nanoparticles or luminescent quantum dots, and different types of polymer single crystals, such as hexagonal polycaprolactone and square-shaped polyethylene glycol ones. Based on the abundant properties originating from both nanoparticles and polymer single crystals, we have demonstrated that the resulting ensemble can function as recyclable catalytically active materials or magnetically responsive luminescent materials.In this paper, we report a free-standing thin lamella consisting of nanoparticles with controllable shape. A self-assembly technique is utilized to obtain this sheet in a step by step fashion with nanoparticles and polymer single crystals as the basic building blocks. Inside the thin lamella, nanoparticles are not only immobilized on the surface of a polymer single crystal, which functions as a template, but also interconnected by a bifunctional crosslinker, i.e. 1,6-hexane dithiol. As a consequence, the nanoparticle lamella is crosslinked and cannot be destructed by solvent and heat treatment. This fabrication strategy is generally applicable and can be applied to a variety of different nanoparticles with various properties, including

  9. Bifunctional Phage-Based Pretargeted Imaging of Human Prostate Carcinoma Bifunctional Phage Based Pretargeted Imaging

    PubMed Central

    Newton-Northup, Jessica R.; Figueroa, Said D.; Quinn, Thomas P.; Deutscher, Susan L.

    2009-01-01

    Introduction Two-step and three-step pretargeting systems utilizing biotinylated prostate tumor-homing bacteriophage (phage) and 111In-radiolabeled- streptavidin or biotin were developed for use in cancer radioimaging. The in vivo selected prostate carcinoma-specific phage (G1) displaying up to five copies of the peptide IAGLATPGWSHWLAL, was the focus of the present study. Methods The ability of G1 phage to extravasate and target prostate tumor cells was investigated using immunohistochemistry. G1 phage were biotinylated, streptavidin was conjugated to diethylenetriaminepentaacetic acid (DTPA), and biotin was conjugated to 1,4,7,10-tetraazacyclododecane-1,4,7,10-tetraacetic acid (DOTA). Biodistribution studies and single photon emission computed tomography (SPECT)/CT imaging of xenografted PC-3 tumors via two-step pretargeted 111In-labeled streptavidin and three-step pretargeted 111In-labeled biotin were performed in SCID mice to determine the optimal pretargeting method. Results The ability of G1 phage to extravasate the vasculature and bind directly to human PC-3 prostate carcinoma tumor cells in vivo was demonstrated via immunocytochemical analysis. Comparative biodistribution studies of the two-step and three-step pretargeting strategies indicated increased PC-3 human prostate carcinoma tumor uptake in SCID mice of 4.34 ±0.26 %ID/g at 0.5 hours post-injection of 111In radiolabeled biotin (utilized in a three-step protocol) compared to that of 0.67 ±0.06 %ID/g at twenty four hour postinjection of 111In radiolabeled streptavidin (employed in a two-step protocol). In vivo SPECT/CT imaging of xenografted PC-3 tumors in SCID mice with the three-step pretargeting method was superior to that of the two-step pretargeting method, and, importantly, blocking studies demonstrated specificity of tumor uptake of 111In-labeled biotin in the three-step pretargeting scheme. Conclusion This study demonstrates the use of multivalent bifunctional phage in a three

  10. Constitutive Modeling of Crosslinked Nanotube Materials

    NASA Technical Reports Server (NTRS)

    Odegard, G. M.; Frankland, S. J. V.; Herzog, M. N.; Gates, T. S.; Fay, C. C.

    2004-01-01

    A non-linear, continuum-based constitutive model is developed for carbon nanotube materials in which bundles of aligned carbon nanotubes have varying amounts of crosslinks between the nanotubes. The model accounts for the non-linear elastic constitutive behavior of the material in terms of strain, and is developed using a thermodynamic energy approach. The model is used to examine the effect of the crosslinking on the overall mechanical properties of variations of the crosslinked carbon nanotube material with varying degrees of crosslinking. It is shown that the presence of the crosslinks has significant effects on the mechanical properties of the carbon nanotube materials. An increase in the transverse shear properties is observed when the nanotubes are crosslinked. However, this increase is accompanied by a decrease in axial mechanical properties of the nanotube material upon crosslinking.

  11. Localization of Membrane-Associated Proteins in Vesicular Stomatitis Virus by Use of Hydrophobic Membrane Probes and Cross-Linking Reagents

    PubMed Central

    Zakowski, Jack J.; Wagner, Robert R.

    1980-01-01

    The location of membrane-associated proteins of vesicular stomatitis virus was investigated by using two monofunctional and three bifunctional probes that differ in the degree to which they partition into membranes and in their specific group reactivity. Two hydrophobic aryl azide probes, [125I]5-iodonaphthyl-1-azide and [3H]pyrenesulfonylazide, readily partitioned into virion membrane and, when activated to nitrenes by UV irradiation, formed stable covalent adducts to membrane constituents. Both of these monofunctional probes labeled the glyco-protein G and matrix M proteins, but [125I]5-iodonaphthyl-1-azide also labeled the nucleocapsid N protein and an unidentified low-molecular-weight component. Protein labeling of intact virions was unaffected by the presence of cytochrome c or glutathione, but disruption of membrane by sodium dodecyl sulfate greatly enhanced the labeling of all viral proteins except G. Labeling of G protein was essentially restricted to the membrane-embedded, thermolysin-resistant tail fragment. Three bifunctional reagents, tartryl diazide, dimethylsuberimidate, and 4,4′-dithiobisphenylazide, were tested for their capacity to cross-link proteins to membrane phospholipids of virions grown in the presence of [3H]palmitate. Only G and M proteins of intact virions were labeled with 3H-phospholipid by these cross-linkers; the reactions were not affected by cytochrome c but were abolished by disruption of virus with sodium dodecyl sulfate. Dimethylsuberimidate, which reacts with free amino groups, cross-linked 3H-phospholipid to both G and M protein. In contrast, the hydrophilic tartryl diazide cross-linked phospholipid primarily to the M protein, whereas the hydrophobic 4,4′-dithiobisphenylazide cross-linked phospholipid primarily to the intrinsic G protein. These data support the hypothesis that the G protein traverses the virion membrane and that the M protein is membrane associated but does not penetrate very deeply, if at all. PMID:6255216

  12. Invariants reveal multiple forms of robustness in bifunctional enzyme systems.

    PubMed

    Dexter, Joseph P; Dasgupta, Tathagata; Gunawardena, Jeremy

    2015-08-01

    Experimental and theoretical studies have suggested that bifunctional enzymes catalyzing opposing modification and demodification reactions can confer steady-state concentration robustness to their substrates. However, the types of robustness and the biochemical basis for them have remained elusive. Here we report a systematic study of the most general biochemical reaction network for a bifunctional enzyme acting on a substrate with one modification site, along with eleven sub-networks with more specialized biochemical assumptions. We exploit ideas from computational algebraic geometry, introduced in previous work, to find a polynomial expression (an invariant) between the steady state concentrations of the modified and unmodified substrate for each network. We use these invariants to identify five classes of robust behavior: robust upper bounds on concentration, robust two-sided bounds on concentration ratio, hybrid robustness, absolute concentration robustness (ACR), and robust concentration ratio. This analysis demonstrates that robustness can take a variety of forms and that the type of robustness is sensitive to many biochemical details, with small changes in biochemistry leading to very different steady-state behaviors. In particular, we find that the widely-studied ACR requires highly specialized assumptions in addition to bifunctionality. An unexpected result is that the robust bounds derived from invariants are strictly tighter than those derived by ad hoc manipulation of the underlying differential equations, confirming the value of invariants as a tool to gain insight into biochemical reaction networks. Furthermore, invariants yield multiple experimentally testable predictions and illuminate new strategies for inferring enzymatic mechanisms from steady-state measurements. PMID:26021467

  13. Cupreines and cupreidines: an established class of bifunctional cinchona organocatalysts.

    PubMed

    Bryant, Laura A; Fanelli, Rossana; Cobb, Alexander J A

    2016-01-01

    Cinchona alkaloids with a free 6'-OH functionality are being increasingly used within asymmetric organocatalysis. This fascinating class of bifunctional catalyst offers a genuine alternative to the more commonly used thiourea systems and because of the different spacing between the functional groups, can control enantioselectivity where other organocatalysts have failed. In the main, this review covers the highlights from the last five years and attempts to show the diversity of reactions that these systems can control. It is hoped that chemists developing asymmetric methodologies will see the value in adding these easily accessible, but underused organocatalysts to their screens. PMID:27340439

  14. Cupreines and cupreidines: an established class of bifunctional cinchona organocatalysts

    PubMed Central

    Bryant, Laura A; Fanelli, Rossana

    2016-01-01

    Summary Cinchona alkaloids with a free 6'-OH functionality are being increasingly used within asymmetric organocatalysis. This fascinating class of bifunctional catalyst offers a genuine alternative to the more commonly used thiourea systems and because of the different spacing between the functional groups, can control enantioselectivity where other organocatalysts have failed. In the main, this review covers the highlights from the last five years and attempts to show the diversity of reactions that these systems can control. It is hoped that chemists developing asymmetric methodologies will see the value in adding these easily accessible, but underused organocatalysts to their screens. PMID:27340439

  15. Divergent evolution of a bifunctional de novo protein.

    PubMed

    Smith, Betsy A; Mularz, Ann E; Hecht, Michael H

    2015-02-01

    Primordial proteins, the evolutionary ancestors of modern sequences, are presumed to have been minimally active and nonspecific. Following eons of selective pressure, these early progenitors evolved into highly active and specific proteins. While evolutionary trajectories from poorly active and multifunctional generalists toward highly active specialists likely occurred many times in evolutionary history, such pathways are difficult to reconstruct in natural systems, where primordial sequences are lost to time. To test the hypothesis that selection for enhanced activity leads to a loss of promiscuity, we evolved a de novo designed bifunctional protein. The parental protein, denoted Syn-IF, was chosen from a library of binary patterned 4-helix bundles. Syn-IF was shown previously to rescue two different auxotrophic strains of E. coli: ΔilvA and Δfes. These two strains contain deletions for proteins with very different biochemical functions; IlvA is involved in isoleucine biosynthesis, while Fes is involved in iron assimilation. In two separate experiments, Syn-IF, was evolved for faster rescue of either ΔilvA or Δfes. Following multiple rounds of mutagenesis, two new proteins were selected, each capable of rescuing the selected function significantly faster than the parental protein. In each case, the evolved protein also lost the ability to rescue the unselected function. In both evolutionary trajectories, the original bifunctional generalist was evolved into a monofunctional specialist with enhanced activity. PMID:25420677

  16. Amino Acid-Derived Bifunctional Phosphines for Enantioselective Transformations.

    PubMed

    Wang, Tianli; Han, Xiaoyu; Zhong, Fangrui; Yao, Weijun; Lu, Yixin

    2016-07-19

    Even though seminal reports on phosphine catalysis appeared in the 1960s, in the last few decades of the past century trivalent phosphines were viewed primarily as useful ligands for transition-metal-mediated processes. The 1990s saw revived interest in using phosphines in organic catalysis, but the key advances in asymmetric phosphine catalysis have all come within the past decade. The uniqueness of phosphine catalysis can be attributed to the high nucleophilicity of the phosphorus atom. In typical phosphine-catalyzed reactions, nucleophilic attacks of the phosphorus atom on electron-deficient multiple bonds create different reactive ylide-type intermediates. When such structurally diverse zwitterionic species react with a variety of suitable substrates, new reaction patterns are often discovered and a diverse array of reactions can be developed. In recent years, substantial progress has been made in the field of asymmetric phosphine catalysis; many new reactions have been discovered, and numerous enantioselective processes have been reported. However, we felt that powerful and versatile phosphine catalysts that can work for a wide range of asymmetric reactions are still lacking. We therefore set our goal to develop a family of easily derived phosphine catalysts that are efficient in asymmetric induction for a broad range of phosphine-mediated transformations. This Account describes our efforts in the past few years on the development of amino acid-based bifunctional phosphines and their applications to enantioselective processes. Building upon our previous success in primary-amine-mediated enamine catalysis, we first established that bifunctional phosphines could be readily prepared from amino acids. In most of our studies, we chose threonine as the key backbone for catalyst development, and threonine-based monoamino acid or dipeptide bifunctional phosphines have displayed remarkable stereochemical control. We began our investigations by demonstrating the

  17. Novel Bifunctional Quinolonyl Diketo Acid Derivatives as HIV-1 Integrase Inhibitors: Design, Synthesis, Biological Activities and Mechanism of Action

    PubMed Central

    Di Santo, Roberto; Costi, Roberta; Roux, Alessandra; Artico, Marino; Lavecchia, Antonio; Marinelli, Luciana; Novellino, Ettore; Palmisano, Lucia; Andreotti, Mauro; Amici, Roberta; Galluzzo, Clementina Maria; Nencioni, Lucia; Palamara, Anna Teresa; Pommier, Yves; Marchand, Christophe

    2008-01-01

    The virally encoded integrase protein is an essential enzyme in the life cycle of the HIV-1 virus and represents an attractive and validated target in the development of therapeutics against HIV infection. Drugs that selectively inhibit this enzyme, when used in combination with inhibitors of reverse transcriptase and protease, are believed to be highly effective in suppressing the viral replication. Among the HIV-1 integrase inhibitors, the β-diketo acids (DKAs) represent a major lead for anti-HIV-1drug development. In this study, novel bifunctional quinolonyl diketo acid derivatives were designed, synthesized and tested for their inhibitory ability against HIV-1 integrase. The compounds are potent inhibitors of integrase activity. Particularly, derivative 8 is a potent IN inhibitor for both steps of the reaction (3′-processing and strand transfer) and exhibits both high antiviral activity against HIV-1 infected cells and low cytotoxicity. Molecular modeling studies provide a plausible mechanism of action, which is consistent with ligand SARs and enzyme photo-crosslinking experiments. PMID:16539381

  18. Viscoelastic behavior of polymers undergoing crosslinking reactions.

    NASA Technical Reports Server (NTRS)

    Moacanin, J.; Aklonis, J. J.

    1971-01-01

    Previously a method was developed for predicting the viscoelastic response of polymers undergoing scission reactions. These results are now extended to include crosslinking reactions. As for scission, at any given time the character of the network chains is determined by the instantaneous crosslink density. For scission all chains were assumed to carry the same stress; for crosslinking, however, the stress is distributed between the 'new' and 'old' chains. Equations for calculating the creep response of a system which experiences a step increase in crosslink density are derived.

  19. Fabrication and Characterization of Cross-Linked Organic Thin Films with Nonlinear Mass Densities.

    PubMed

    Rashed, Md A; Laokroekkiat, Salinthip; Hara, Mitsuo; Nagano, Shusaku; Nagao, Yuki

    2016-06-14

    The preparation of urea (bonded) cross-linked multilayer thin films by sequential deposition of bifunctional and tetrafunctional molecular building blocks is demonstrated. Multilayer growth as a function of deposition cycles was inspected using UV-vis absorption spectroscopy. From infrared results, three characteristic infrared bands of amide I, amide II, and asymmetric νa(N-C-N) stretching confirmed the formation of polyurea networks by alternate dipping into solutions of amine and isocyanate functionality monomers. The deconvoluted component of the C 1s and N 1s spectra obtained by X-ray photoelectron spectroscopy shows clear evidence of stable polyurea networks. The enhancement of structural periodicity with film growth was demonstrated by grazing-incidence small-angle X-ray scattering measurements. The thin film near the substrate surface seems to have an amorphous structure. However, molecular ordering improves in the surface normal direction of the substrate with a certain number of deposited layers. Constant mass density was not observed with deposition cycles. The mass density increased up to 16% within deposited layers from proximate layers to those extending away from the substrate surface. This difference in the packing density might derive from the different degrees of cross-linking among layers proximate to the substrate surface and extending away from the substrate surface. PMID:27175975

  20. Bifunctional monomers having terminal oxime and cyano or amidine groups

    NASA Technical Reports Server (NTRS)

    Rosser, R. W.; Shalhoub, I. M.; Kwongs, H. (Inventor)

    1981-01-01

    The preparation of crosslinked 1,2,4-oxadiazole elastomers is described. The technique involves thermally condensing (1) a monomer having the formula H2N(HON)C-R-Q, wherein Q is a triazine ring-forming groups such as nitrile or amidine or a mixture of such group with amidoxime, or (2) a mixture of the same monomer with R(C(NOH)NH2)2, with R in these formulas standing for a bivalent organic radical. In the monomer charge, the overall proportions of amidoxime groups to triazine ring-forming groups varies depending on the extent of crosslinking desired in the final polymer.

  1. Radiation induced estane polymer crosslinking

    SciTech Connect

    Fletcher, M.; Foster, P.

    1997-12-01

    The exposure of polymeric materials to radiation has been known to induce the effects of crosslinking and degradation. The crosslinking phenomena comes about when two long chain polymers become linked together by a primary bond that extends the chain and increases the viscosity, molecular weight and the elastic modules of the polymer. This process has been observed in relatively short periods of time with fairly high doses of radiation, on the order of several megarads/hour. This paper address low dose exposure over long periods of time to determine what the radiation effects are on the polymeric binder material in PBX 9501. An experimental sample of binder material without explosives will be placed into a thermal and radiation field produced from a W-48 put mod 0. Another sample will be placed in a thermal environment without the radiation. The following is the test plan that was submitted to the Pantex process. The data presented here will be from the first few weeks of exposure and this test will be continued over the next few years. Subsequent data will hopefully be presented in the next compatibility and aging conference.

  2. Antibody-Drug Conjugates (ADCs) Derived from Interchain Cysteine Cross-Linking Demonstrate Improved Homogeneity and Other Pharmacological Properties over Conventional Heterogeneous ADCs.

    PubMed

    Behrens, Christopher R; Ha, Edward H; Chinn, Lawrence L; Bowers, Simeon; Probst, Gary; Fitch-Bruhns, Maureen; Monteon, Jorge; Valdiosera, Amanda; Bermudez, Abel; Liao-Chan, Sindy; Wong, Tiffany; Melnick, Jonathan; Theunissen, Jan-Willem; Flory, Mark R; Houser, Derrick; Venstrom, Kristy; Levashova, Zoia; Sauer, Paul; Migone, Thi-Sau; van der Horst, Edward H; Halcomb, Randall L; Jackson, David Y

    2015-11-01

    Conventional antibody-drug conjugates (ADCs) are heterogeneous mixtures of chemically distinct molecules that vary in both drugs/antibody (DAR) and conjugation sites. Suboptimal properties of heterogeneous ADCs have led to new site-specific conjugation methods for improving ADC homogeneity. Most site-specific methods require extensive antibody engineering to identify optimal conjugation sites and introduce unique functional groups for conjugation with appropriately modified linkers. Alternative nonrecombinant methods have emerged in which bifunctional linkers are utilized to cross-link antibody interchain cysteines and afford ADCs containing four drugs/antibody. Although these methods have been shown to improve ADC homogeneity and stability in vitro, their effect on the pharmacological properties of ADCs in vivo is unknown. In order to determine the relative impact of interchain cysteine cross-linking on the therapeutic window and other properties of ADCs in vivo, we synthesized a derivative of the known ADC payload, MC-MMAF, that contains a bifunctional dibromomaleimide (DBM) linker instead of a conventional maleimide (MC) linker. The DBM-MMAF derivative was conjugated to trastuzumab and a novel anti-CD98 antibody to afford ADCs containing predominantly four drugs/antibody. The pharmacological properties of the resulting cross-linked ADCs were compared with analogous heterogeneous ADCs derived from conventional linkers. The results demonstrate that DBM linkers can be applied directly to native antibodies, without antibody engineering, to yield highly homogeneous ADCs via cysteine cross-linking. The resulting ADCs demonstrate improved pharmacokinetics, superior efficacy, and reduced toxicity in vivo compared to analogous conventional heterogeneous ADCs. PMID:26393951

  3. Preparation of molecularly imprinted polymeric fibers using a single bifunctional monomer for the solid-phase microextraction of parabens from environmental solid samples.

    PubMed

    Díaz-Álvarez, Myriam; Smith, Stephen P; Spivak, David A; Martín-Esteban, Antonio

    2016-02-01

    In this study, molecularly imprinted polymer fibers for solid-phase microextraction have been prepared with a single bifunctional monomer, N,O-bismethacryloyl ethanolamine using the so-called "one monomer molecularly imprinted polymers" method, replacing the conventional combination of functional monomer and cross-linker to form high fidelity binding sites. For comparison, imprinted fibers were prepared following the conventional approach based on ethylene glycol dimethacrylate as cross-linker and methacrylic acid as monomer. The recognition performance of the new fibers was evaluated in the solid-phase microextraction of parabens, and from this study it was concluded that they provided superior performance over conventionally formulated fibers. Ultimately, real-world environmental testing on spiked solid samples was successful by the molecularly imprinted solid-phase microextraction of samples, and the relative recoveries obtained at enrichment levels of 10 ng/g of parabens were within 78-109% for soil and 83-109% for sediments with a relative standard deviation <15% (n = 3). PMID:26582435

  4. Cu(I) stabilizing crosslinked polyethyleneimine.

    PubMed

    Movahedi, Alireza; Lundin, Angelica; Kann, Nina; Nydén, Magnus; Moth-Poulsen, Kasper

    2015-07-28

    Polyethyleneimine (PEI) is known for its metal-coordinating properties and in its crosslinked form has applications in different areas ranging from drug delivery to waste water treatment and recovery of trace metals. With the aim to regulate the coordination environment of Cu(I) and Cu(II) ions in marine coatings, we have prepared a triazole cross-linking agent with 'soft' coordination that can crosslink PEI via indirect reductive amination. We have shown that this triazole crosslinker not only increases the Cu(II) absorption capacity of the crosslinked PEI in comparison to the traditionally used glutaraldehyde-crosslinked PEI (PEI-GA), but also allows the crosslinked polymer network to stabilize the Cu(I) oxidation state more effectively. The Cu(II) uptake and Cu(I) stabilization of the polymer have been determined by elemental analysis and UV-vis spectroscopy. It was found that the triazole-crosslinked polymer (PEI-TA) could coordinate up to 12 wt% of Cu(II) before and 6 wt% Cu(II) after imine reduction. PMID:26104912

  5. Chemical cross-linking of Chlamydia trachomatis.

    PubMed Central

    Birkelund, S; Lundemose, A G; Christiansen, G

    1988-01-01

    Purified elementary bodies (EBs) of Chlamydia trachomatis serovar L2 were analyzed by chemical cross-linking with disuccinimidyl selenodipropionate. The effect of the cross-linking was analyzed by immunoblotting sodium dodecyl sulfate-polyacrylamide gel electrophoresis-separated components which were reacted with monoclonal antibodies against major outer membrane protein (MOMP) and lipopolysaccharide (LPS). It was shown that in EBs, MOMP was cross-linked to the LPS component of the outer membrane. Migration analysis of the cross-linked components showed that with extensive cross-linking, most of the MOMP became cross-linked to LPS, changing the migration rate from 40 to 42.5 kilodaltons. A small fraction of MOMP associated with LPS was shown to be present in bands with migration rates of 100 and 110 kilodaltons. No association of MOMP or LPS to other proteins, or to dimer or multimer forms of MOMP without LPS, was observed. A totally different membrane structure must be present in reticulate bodies, since there, MOMP was so heavily cross-linked that it did not enter the polyacrylamide gel and thus became impossible to analyze. Furthermore, the monoclonal antibody, which reacted with LPS associated with MOMP in the cross-linked EBs, did not react with reticulate bodies. Images PMID:2449399

  6. Bifunctional combined aptamer for simultaneous separation and detection of thrombin.

    PubMed

    Bing, Tao; Liu, Xiangjun; Cheng, Xiaohong; Cao, Zehui; Shangguan, Dihua

    2010-02-15

    Here we report on the construction and evaluation of a bifunctional combined aptamer (BCA) that consists of a DNA streptavidin-binding aptamer (SBA), a DNA thrombin-binding aptamer (TBA) and a fluorophore. The BCA adopts a new conformation that is very different from simply linking the conformations of the two individual aptamers together, so that it does not bind to streptavidin in the absence of thrombin. Binding of this novel DNA aptamer to streptavidin is triggered by the thrombin binding and depends on the concentration of thrombin. Meanwhile, fluorescence from the streptavidin captured BCA reflects the quantity of the target molecule in the sample. This aptamer combination strategy based on the SBA holds good potential for applications in simultaneous detection and separation of targets of aptamers or certain DNA and RNA targets. PMID:19959350

  7. Enantioselective tandem reaction over a site-isolated bifunctional catalyst.

    PubMed

    Xu, Jianyou; Cheng, Tanyu; Zhang, Kun; Wang, Ziyun; Liu, Guohua

    2016-05-21

    Construction of a site-isolated heterogeneous catalyst to realize the compatibility of bimetallic complexes for a feasible tandem reaction is a significant challenge in heterogeneous asymmetric catalysis. Herein, taking advantage of yolk-shell-structured mesoporous silica, we assemble an active site-isolated bifunctional catalyst through assembly of organopalladium-functionality into silicate channels as an outer shell and chiral organoruthenium-functionality onto silicate yolk as an inner core, realizing the one-pot enantioselective tandem reaction from Pd-catalyzed Sonogashira coupling to Ru-catalyzed asymmetric transfer hydrogenation. As presented in this study, this tandem Sonogashira coupling-asymmetric transfer hydrogenation of haloacetophenones and arylacetylenes affords various chiral conjugated alkynols with high yields and up to 99% enantioselectivity. Moreover, a catalyst can also be recovered easily and recycled repeatedly, making it an interesting feature in a practical organic transformation. PMID:27063335

  8. Bifunctional magnetic-fluorescent nanoparticles: synthesis, characterization, and cell imaging.

    PubMed

    Lu, Yanjiao; Zheng, Yang; You, Shusen; Wang, Feng; Gao, Zhuo; Shen, Jie; Yang, Wantai; Yin, Meizhen

    2015-03-11

    A new type of bifunctional magnetic-fluorescent Fe3O4@SiO2-PDI-PAA/Ca(2+) nanoparticles has been prepared by coating PDI-cored star polymers (PDI-PAA) onto the surface of Fe3O4@SiO2 core-shell nanostructures. The morphology and properties of the composite nanoparticles are investigated by transmission electron microscopy, ultraviolet-visible spectrometry, fluorescence spectrometry, and vibrating sample magnetometry. The composite nanoparticles display a strong red emission and superparamagnetic behavior at room temperature. The cell viability and uptake assays reveal good biocompatibility of these hybrid nanoparticles. Hence, the composite nanoparticles are of potential to be further explored as therapeutic vector in biomedical field. PMID:25691125

  9. BIFUNCTIONAL ALUMINUN: A PERMEABLE BARRIER MATERIAL FOR THE DEGRADATION OF MTBE

    EPA Science Inventory

    Bifunctional aluminum is an innovative remedial material for the treatment of gasoline oxygenates in permeable reactive barriers (PRBs). PRBs represent a promising environmental technology for remediation of groundwater contamination. Although zero-valent metals (ZVM) have been...

  10. Bifunctional chelating agent for the design and development of site specific radiopharmaceuticals and biomolecule conjugation strategy

    DOEpatents

    Katti, Kattesh V.; Prabhu, Kandikere R.; Gali, Hariprasad; Pillarsetty, Nagavara Kishore; Volkert, Wynn A.

    2003-10-21

    There is provided a method of labeling a biomolecule with a transition metal or radiometal in a site specific manner to produce a diagnostic or therapeutic pharmaceutical compound by synthesizing a P.sub.2 N.sub.2 -bifunctional chelating agent intermediate, complexing the intermediate with a radio metal or a transition metal, and covalently linking the resulting metal-complexed bifunctional chelating agent with a biomolecule in a site specific manner. Also provided is a method of synthesizing the --PR.sub.2 containing biomolecules by synthesizing a P.sub.2 N.sub.2 -bifunctional chelating agent intermediate, complexing the intermediate with a radiometal or a transition metal, and covalently linking the resulting radio metal-complexed bifunctional chelating agent with a biomolecule in a site specific manner. There is provided a therapeutic or diagnostic agent comprising a --PR.sub.2 containing biomolecule.

  11. Bifunctional chelates of RH-105 and AU199 as potential radiotherapeutic agents

    SciTech Connect

    Droege, P.

    1997-03-01

    Research is presented on new bifunctional chelating ligand systems with stability on the macroscopic and radiochemical levels. The synthesis of the following complexes are described: rhodium 105, palladium 109, and gold 198.

  12. Synergistic Interaction within Bifunctional Ruthenium Nanoparticle/SILP Catalysts for the Selective Hydrodeoxygenation of Phenols.

    PubMed

    Luska, Kylie L; Migowski, Pedro; El Sayed, Sami; Leitner, Walter

    2015-12-21

    Ruthenium nanoparticles immobilized on acid-functionalized supported ionic liquid phases (Ru NPs@SILPs) act as efficient bifunctional catalysts in the hydrodeoxygenation of phenolic substrates under batch and continuous flow conditions. A synergistic interaction between the metal sites and acid groups within the bifunctional catalyst leads to enhanced catalytic activities for the overall transformation as compared to the individual steps catalyzed by the separate catalytic functionalities. PMID:26545408

  13. Detection and isolation of nucleic acid sequences using a bifunctional hybridization probe

    DOEpatents

    Lucas, Joe N.; Straume, Tore; Bogen, Kenneth T.

    2000-01-01

    A method for detecting and isolating a target sequence in a sample of nucleic acids is provided using a bifunctional hybridization probe capable of hybridizing to the target sequence that includes a detectable marker and a first complexing agent capable of forming a binding pair with a second complexing agent. A kit is also provided for detecting a target sequence in a sample of nucleic acids using a bifunctional hybridization probe according to this method.

  14. Crosslinked Matrix-free Nanocomposites

    NASA Astrophysics Data System (ADS)

    Dach, Benjamin; Rengifo, Hernan; Turro, Nicholas; Koberstein, Jeffrey

    2010-03-01

    Matrix-free polymer-silica nanocomposites are formed by crosslinking polymer coated nanoparticles via the `click' reaction. The `click' reaction is also known as H"uisgen 1, 3-dipolar cycloaddition of terminal alkyne and azide functional groups to give 1, 2, 3-triazoles. Silica nanoparticles are functionalized with alkyne and azide moieties. Heterobifunctional α,φ-trimethylsilane-alkyne,azide-poly(styrene) (TMS-PS-N3) and α,φ-trimethylsilane-alkyne,azide--poly(tert-butyl acrylate) (TMS-PtBA-N3) are then covalently bound to the surfaces of the nanoparticles via the `click' reaction. The bare and modified nanoparticles are analyzed by diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS). The thermal, morphological, and mechanical properties of the systems are investigated by thermogravimetric analysis (TGA), transmission electron microscopy (TEM), and dynamic rheology, respectively. .

  15. New in situ crosslinking chemistries for hydrogelation

    NASA Astrophysics Data System (ADS)

    Roberts, Meredith Colleen

    Over the last half century, hydrogels have found immense value as biomaterials in a vast number of biomedical and pharmaceutical applications. One subset of hydrogels receiving increased attention is in situ forming gels. Gelling by either bioresponsive self-assembly or mixing of binary crosslinking systems, these technologies are useful in minimally invasive applications as well as drug delivery systems in which the sol-to-gel transition aids the formulation's performance. Thus far, the field of in situ crosslinking hydrogels has received limited attention in the development of new crosslinking chemistries. Moreover, not only does the chemical nature of the crosslinking moieties allow these systems to perform in situ, but they contribute dramatically to the mechanical properties of the hydrogel networks. For example, reversible crosslinks with finite lifetimes generate dynamic viscoelastic gels with time-dependent properties, whereas irreversible crosslinks form highly elastic networks. The aim of this dissertation is to explore two new covalent chemistries for their ability to crosslink hydrogels in situ under physiological conditions. First, reversible phenylboronate-salicylhydroxamate crosslinking was implemented in a binary, multivalent polymeric system. These gels formed rapidly and generated hydrogel networks with frequency-dependent dynamic rheological properties. Analysis of the composition-structure-property relationships of these hydrogels---specifically considering the effects of pH, degree of polymer functionality, charge of the polymer backbone and polymer concentration on dynamic theological properties---was performed. These gels demonstrate diverse mechanical properties, due to adjustments in the binding equilibrium of the pH-sensitive crosslinks, and thus have the potential to perform in a range of dynamic or bioresponsive applications. Second, irreversible catalyst-free "click" chemistry was employed in the hydrogelation of multivalent azide

  16. Enhancing DNA Crystal Durability through Chemical Crosslinking.

    PubMed

    Zhang, Diana; Paukstelis, Paul J

    2016-06-16

    Three-dimensional (3D) DNA crystals have been envisioned as a powerful tool for the positional control of biological and non-biological arrays on the nanoscale. However, most DNA crystals contain short duplex regions that can result in low thermal stability. Additionally, because DNA is a polyanion, DNA crystals often require high cation concentrations to maintain their integrity. Here, we demonstrate that a DNA alkylating mustard, bis(2-chloroethyl)amine, can form interstrand crosslinks within a model 3D DNA crystal. The crosslinking procedure did not alter crystal X-ray diffraction properties, but it did significantly improve the overall stability of the crystals under a variety of conditions. Crosslinked crystals showed enhanced stability at elevated temperature and were stable at Mg(2+) concentrations as low as 1 mm. Remarkably, the crosslinked crystals showed significant resistance to DNase I treatment, while also having improved longevity in tissue culture mediums. Characterization of the crosslinked species suggest that there are multiple crosslinking sites, but that the most prevalent interstrand crosslink involves an unpaired 3'-terminal guanosine residue. The improved stability of these DNA crystals suggests that simple treatment with alkylating reagents might be sufficient to stabilize crystals and other DNA constructs for improved functionality in biological and non-biological applications. PMID:27108768

  17. Histone cross-linking by transglutaminase.

    PubMed

    Kim, Jae-Hong; Nam, Kang Hoon; Kwon, Oh-Seok; Kim, In Gyu; Bustin, Michael; Choy, Hyon E; Park, Sang Chul

    2002-05-24

    Transglutaminases irreversibly catalyze covalent cross-linking of proteins by forming isopeptide bonds between peptide-bound glutamine and lysine residues. Among several transglutaminases, tissue-type transglutaminase (tTGase) is most ubiquitously found in every type of cells and tissues in animals, but its natural substrate has yet to be identified. In an attempt to identify the natural substrate for tTGase, we examined in vitro if core histones were subject to cross-linking by tTGase. We found core histone subunits, H2A and H2B, were specifically cross-linked by tTGase. The cross-linking was between either one or both glutamines at C-terminal end of H2A (-VTIAQ104 GGVLPNTQ112 SVLLPKKTESSKSK-C' end) and the first and/or third lysine from C-terminal end of H2B (-AVESEGK116 AVTKYTSSK125-C' end). The cross-linking occurred only when these subunits were released from nucleosome but not when these were organized in nucleosome. Most interestingly, in chicken erythrocyte the cross-linked H2A-H2B was present in a significant amount. From these results, it can be proposed that tTGase-mediated cross-linking is an another form of core histone modification and it may play a role of chromatin condensation during erythrocyte differentiation. PMID:12054678

  18. Porous Cross-Linked Polyimide Networks

    NASA Technical Reports Server (NTRS)

    Meador, Mary Ann B. (Inventor); Guo, Haiquan (Inventor)

    2015-01-01

    Porous cross-linked polyimide networks are provided. The networks comprise an anhydride end-capped polyamic acid oligomer. The oligomer (i) comprises a repeating unit of a dianhydride and a diamine and terminal anhydride groups, (ii) has an average degree of polymerization of 10 to 50, (iii) has been cross-linked via a cross-linking agent, comprising three or more amine groups, at a balanced stoichiometry of the amine groups to the terminal anhydride groups, and (iv) has been chemically imidized to yield the porous cross-linked polyimide network. Also provided are porous cross-linked polyimide aerogels comprising a cross-linked and imidized anhydride end-capped polyamic acid oligomer, wherein the oligomer comprises a repeating unit of a dianhydride and a diamine, and the aerogel has a density of 0.10 to 0.333 g/cm.sup.3 and a Young's modulus of 1.7 to 102 MPa. Also provided are thin films comprising aerogels, and methods of making porous cross-linked polyimide networks.

  19. Extracellular glycation crosslinks: prospects for removal.

    PubMed

    Furber, John D

    2006-01-01

    Extracellular aging--accumulating molecular damage by glycation, oxidation, and crosslinking of long-lived extracellular proteins, mainly collagen and elastin--is a major cause of several important human aging pathologies. Crosslinking increases mechanical stiffness of blood vessels and urinary bladder. Crosslinking impairs the functioning of the kidney, heart, retina, and other tissues and organs. Glycation adducts trigger inflammatory signaling, provoking tissue damage and cancers. Crosslinking tightens up the extracellular matrix (ECM), hardening it against natural turnover processes. Known crosslink breakers (e.g., alagebrium, of the thiazolium halide family) are only partly effective because they break only a subset of AGE crosslink structures (sugar-derived alpha-diketone bridges). So far, no agent has been found that breaks the prevalent glucosepane and K2P crosslink structures. Enzymes that would be able to recognize and disassemble glycation products may be too big to migrate into the ECM and repair collagen or elastin in vivo. Two approaches to therapy development are presented here. ECM turnover enhancement would enhance natural processes to digest old ECM and replace it with new. It will be important to tune the collagen degradation to a rate slow enough to prevent dire side-effects, such as hemorrhage from leaky blood vessels as collagen molecules are removed and replaced. Glycation breaker discovery would use high-throughput screening and rational drug design to find molecules that are able to break glucosepane crosslinks and K2P crosslinks of extracellular proteins. Candidates would be further screened for selectivity and toxicity in order to avoid damage to other molecules. PMID:16706655

  20. Corneal Collagen Cross-Linking

    PubMed Central

    Jankov II, Mirko R.; Jovanovic, Vesna; Nikolic, Ljubisa; Lake, Jonathan C.; Kymionis, Georgos; Coskunseven, Efekan

    2010-01-01

    Corneal collagen cross-linking (CXL) with riboflavin and ultraviolet-A (UVA) is a new technique of corneal tissue strengthening by using riboflavin as a photosensitizer and UVA to increase the formation of intra and interfibrillar covalent bonds by photosensitized oxidation. Keratocyte apoptosis in the anterior segment of the corneal stroma all the way down to a depth of about 300 microns has been described and a demarcation line between the treated and untreated cornea has been clearly shown. It is important to ensure that the cytotoxic threshold for the endothelium has not been exceeded by strictly respecting the minimal corneal thickness. Confocal microscopy studies show that repopulation of keratocytes is already visible 1 month after the treatment, reaching its pre-operative quantity and quality in terms of functional morphology within 6 months after the treatment. The major indication for the use of CXL is to inhibit the progression of corneal ectasias, such as keratoconus and pellucid marginal degeneration. CXL may also be effective in the treatment and prophylaxis of iatrogenic keratectasia, resulting from excessively aggressive photoablation. This treatment has also been used to treat infectious corneal ulcers with apparent favorable results. Combination with other treatments, such as intracorneal ring segment implantation, limited topography-guided photoablation and conductive keratoplasty have been used with different levels of success. PMID:20543933

  1. The colibactin warhead crosslinks DNA

    NASA Astrophysics Data System (ADS)

    Vizcaino, Maria I.; Crawford, Jason M.

    2015-05-01

    Members of the human microbiota are increasingly being correlated to human health and disease states, but the majority of the underlying microbial metabolites that regulate host-microbe interactions remain largely unexplored. Select strains of Escherichia coli present in the human colon have been linked to the initiation of inflammation-induced colorectal cancer through an unknown small-molecule-mediated process. The responsible non-ribosomal peptide-polyketide hybrid pathway encodes ‘colibactin’, which belongs to a largely uncharacterized family of small molecules. Genotoxic small molecules from this pathway that are capable of initiating cancer formation have remained elusive due to their high instability. Guided by metabolomic analyses, here we employ a combination of NMR spectroscopy and bioinformatics-guided isotopic labelling studies to characterize the colibactin warhead, an unprecedented substituted spirobicyclic structure. The warhead crosslinks duplex DNA in vitro, providing direct experimental evidence for colibactin's DNA-damaging activity. The data support unexpected models for both colibactin biosynthesis and its mode of action.

  2. Solution structure of the reduced form of human peroxiredoxin-6 elucidated using zero-length chemical cross-linking and homology modelling.

    PubMed

    Rivera-Santiago, Roland F; Harper, Sandra L; Zhou, Suiping; Sriswasdi, Sira; Feinstein, Sheldon I; Fisher, Aron B; Speicher, David W

    2015-05-15

    Peroxiredoxin-6 (PRDX6) is an unusual member of the peroxiredoxin family of antioxidant enzymes that has only one evolutionarily conserved cysteine. It reduces oxidized lipids and reactive oxygen species (ROS) by oxidation of the active-site cysteine (Cys(47)) to a sulfenic acid, but the mechanism for conversion back to a thiol is not completely understood. Moreover, it has phospholipase A2 (PLA2) activity in addition to its peroxidase activity. Interestingly, some biochemical data are inconsistent with a known high-resolution crystal structure of the catalytic intermediate of the protein, and biophysical data indicate that the protein undergoes conformational changes that affect enzyme activity. In order to further elucidate the solution structure of this important enzyme, we used chemical cross-linking coupled with high-resolution MS (CX-MS), with an emphasis on zero-length cross-links. Distance constraints from high confidence cross-links were used in homology modelling experiments to determine a solution structure of the reduced form of the protein. This structure was further evaluated using chemical cross-links produced by several homo-bifunctional amine-reactive cross-linking reagents, which helped to confirm the solution structure. The results show that several regions of the reduced version of human PRDX6 are in a substantially different conformation from that shown for the crystal structure of the peroxidase catalytic intermediate. The differences between these two structures are likely to reflect catalysis-related conformational changes. These studies also demonstrate that CX-MS using zero-length cross-linking is a powerful strategy for probing protein conformational changes that is complementary to alternative methods such as crystallographic, NMR and biophysical studies. PMID:25748205

  3. Drilling fluid containing crosslinked polysaccharide derivative

    SciTech Connect

    Demott, D.N.; Kucera, C.H.

    1981-03-24

    A drilling fluid having extremely desirable physical properties which comprises an aqueous solution of a hydroxyalkyl polysaccharide derivative and a water soluble ionic aluminum crosslinking agent, preferably sodium aluminate.

  4. Highly cross-linked nanoporous polymers

    DOEpatents

    Steckle, Jr., Warren P.; Apen, Paul G.; Mitchell, Michael A.

    1997-01-01

    Condensation polymerization followed by a supercritical extraction step can be used to obtain highly cross-linked nanoporous polymers with high surface area, controlled pore sizes and rigid structural integrity. The invention polymers are useful for applications requiring separation membranes.

  5. Highly cross-linked nanoporous polymers

    DOEpatents

    Steckle, Jr., Warren P.; Apen, Paul G.; Mitchell, Michael A.

    1998-01-01

    Condensation polymerization followed by a supercritical extraction step can be used to obtain highly cross-linked nanoporous polymers with high surface area, controlled pore sizes and rigid structural integrity. The invention polymers are useful for applications requiring separation membranes.

  6. Surface Wave Velocity of Crosslinked Polyacrylate Gels

    NASA Astrophysics Data System (ADS)

    Matsuoka, Tatsuro; Kinouchi, Wataru; ShinobuKoda, ShinobuKoda; Nomura, Hiroyasu

    1999-05-01

    Surface wave velocities of crosslinked polyacrylate hydrogelswere measured as a function of water content with differentcompositions of sodium polyacrylate (NaPA) and polyacrylic acid (PAA).The water content and composition dependencies of the surface wavevelocity were discussed.

  7. X-Ray Crystallinity of Bleached and Crosslinked Cottons

    Technology Transfer Automated Retrieval System (TEKTRAN)

    An X-ray diffractometer was used to study the crystalline structure of cotton fibers after bleaching, crosslinking and a combination of bleaching and crosslinking treatments. Wet crosslinking was accomplished with formaldehyde (Form W) and dry crosslinking was carried out with either dimethyloldihyd...

  8. Crosslinked Polybenzimidazole Membrane For Gas Separation

    DOEpatents

    Jorgensen, Betty S.; Young, Jennifer S.; Espinoza, Brent F.

    2005-09-20

    A cross-linked, supported polybenzimidazole membrane for gas separation is prepared by layering a solution of polybenzimidazole (PBI) and a,a'dibromo-p-xylene onto a porous support and evaporating solvent. A supported membrane of cross-linked poly-2,2'-(m-phenylene)-5,5'-bibenzimidazole unexpectedly exhibits an enhanced gas permeability compared to the non-cross linked analog at temperatures over 265° C.

  9. Grafting functional antioxidants on highly crosslinked polyethylene

    NASA Astrophysics Data System (ADS)

    Al-Malaika, S.; Riasat, S.; Lewucha, C.

    2016-05-01

    The problem of interference of antioxidants, such as hindered phenols, with peroxide-initiated crosslinking of polyethylene was addressed through the use of functional (reactive) graftable antioxidants (g-AO). Reactive derivatives of hindered phenol and hindered amine antioxidants were synthesised, characterised and used to investigate their grafting reactions in high density polyethylene; both non-crosslinked (PE) and highly peroxide-crosslinked (PEXa). Assessment of the extent of in-situ grafting of the antioxidants, their retention after exhaustive solvent extraction in PE and PEXa, and the stabilising performance of the grafted antioxidants (g-AO) in the polymer were examined and benchmarked against conventionally stabilised crosslinked & non-crosslinked polyethylene. It was shown that the functional antioxidants graft to a high extent in PEXa, and that the level of interference of the g-AOs with the polymer crosslinking process was minimal compared to that of conventional antioxidants which bear the same antioxidant function. The much higher level of retention of the g-AOs in PEXa after exhaustive solvent extraction, compared to that of the corresponding conventional antioxidants, accounts for their superior long-term thermal stabilising performance under severe extractive conditions.

  10. Radical initiated polymerization in a bifunctional mixture via computer simulation

    NASA Astrophysics Data System (ADS)

    Diamond, Keri L.; Pandey, Ras B.; Thames, Shelby F.

    2004-06-01

    Computer simulations are performed to study the polymerization behavior in a mixture of bifunctional groups such as olefins (A) and acrylates (B) in an effective solvent (a coarse description for vegetable oil derived macromonomers (VOMMs) in solution) on a cubic lattice. A set of interactions between these units and solvent (S) constituents and their relative concentrations (pA, pB, and pS) are considered. Samples are equilibrated with Metropolis algorithm to model the perceived behavior of VOMMs. The covalent bonding between monomeric units is then implemented via reaction pathways initiated by stochastic motion of free radicals (a very small fraction). The rate of reaction shows decay patterns with the time steps (t) with power laws (i.e., Rabαt-r, r≅0.4-0.8), exponential decays (i.e., Rabαe-0.001t), and their combination. Growth of A-B bonding is studied as a function of polymer concentration p=pA+pB for four different model systems appropriate for VOMMs. The data from the free radical initiated simulations are compared to the original simulations with homopolymerization. While most of the data are consistent with experimental observations, the variations are found to be model dependent.

  11. Bioinspired Bifunctional Membrane for Efficient Clean Water Generation.

    PubMed

    Liu, Yang; Lou, Jinwei; Ni, Mengtian; Song, Chengyi; Wu, Jianbo; Dasgupta, Neil P; Tao, Peng; Shang, Wen; Deng, Tao

    2016-01-13

    Solving the problems of water pollution and water shortage is an urgent need for the sustainable development of modern society. Different approaches, including distillation, filtration, and photocatalytic degradation, have been developed for the purification of contaminated water and the generation of clean water. In this study, we explored a new approach that uses solar light for both water purification and clean water generation. A bifunctional membrane consisting of a top layer of TiO2 nanoparticles (NPs), a middle layer of Au NPs, and a bottom layer of anodized aluminum oxide (AAO) was designed and fabricated through multiple filtration processes. Such a design enables both TiO2 NP-based photocatalytic function and Au NP-based solar-driven plasmonic evaporation. With the integration of these two functions into a single membrane, both the purification of contaminated water through photocatalytic degradation and the generation of clean water through evaporation were demonstrated using simulated solar illumination. Such a demonstration should also help open up a new strategy for maximizing solar energy conversion and utilization. PMID:26646606

  12. Gold(I) catalysts with bifunctional P, N ligands.

    PubMed

    Wetzel, Corinna; Kunz, Peter C; Thiel, Indre; Spingler, Bernhard

    2011-08-15

    A series of phosphanes with imidazolyl substituents were prepared as hemilabile PN ligands. The corresponding gold(I) complexes were tested as bifunctional catalysts in the Markovnikov hydration of 1-octyne, as well as in the synthesis of propargylamines by the three component coupling reaction of piperidine, benzaldehyde, and phenylacetylene. While the activity in the hydration of 1-octyne was low, the complexes are potent catalysts for the three component coupling reaction. In homogeneous solution the conversions to the respective propargylamine were considerably higher than under aqueous biphasic conditions. The connectivity of the imidazolyl substituents to the phosphorus atom, their substitution pattern, as well as the number of heteroaromatic substituents have pronounced effects on the catalytic activity of the corresponding gold(I) complexes. Furthermore, formation of polymetallic species with Au(2), Au(3), and Au(4) units has been observed and the solid-state structures of the compounds [(5)(2)Au(3)Cl(2)]Cl and [(3c)(2)Au(4)Cl(2)]Cl(2) (3c = tris(2-isopropylimidazol-4(5)-yl phosphane, 5 = 2-tert-butylimidazol-4(5)-yldiphenyl phosphane) were determined. The gold(I) complexes of imidazol-2-yl phosphane ligands proved to be a novel source for bis(NHC)gold(I) complexes (NHC = N-heterocyclic carbene). PMID:21761834

  13. Identification of a Bifunctional Maize C- and O-Glucosyltransferase*

    PubMed Central

    Falcone Ferreyra, María Lorena; Rodriguez, Eduardo; Casas, María Isabel; Labadie, Guillermo; Grotewold, Erich; Casati, Paula

    2013-01-01

    Flavonoids accumulate in plant vacuoles usually as O-glycosylated derivatives, but several species can also synthesize flavonoid C-glycosides. Recently, we demonstrated that a flavanone 2-hydroxylase (ZmF2H1, CYP93G5) converts flavanones to the corresponding 2-hydroxy derivatives, which are expected to serve as substrates for C-glycosylation. Here, we isolated a cDNA encoding a UDP-dependent glycosyltransferase (UGT708A6), and its activity was characterized by in vitro and in vivo bioconversion assays. In vitro assays using 2-hydroxyflavanones as substrates and in vivo activity assays in yeast co-expressing ZmF2H1 and UGT708A6 show the formation of the flavones C-glycosides. UGT708A6 can also O-glycosylate flavanones in bioconversion assays in Escherichia coli as well as by in vitro assays with the purified recombinant protein. Thus, UGT708A6 is a bifunctional glycosyltransferase that can produce both C- and O-glycosidated flavonoids, a property not previously described for any other glycosyltransferase. PMID:24045947

  14. Bifunctional drugs for the treatment of asthma and chronic obstructive pulmonary disease.

    PubMed

    Page, Clive; Cazzola, Mario

    2014-08-01

    Over the last decade, there has been a steady increase in the use of fixed-dose combinations of drugs for the treatment of a range of diseases, including hypertension, cancer, AIDS, tuberculosis and other infectious diseases. It is now evident that patients with asthma or chronic obstructive pulmonary disease (COPD) can also benefit from the use of fixed-dose combinations, including combinations of a long-acting β2-agonist and an inhaled corticosteroid, and combinations of long-acting β2-agonists and long-acting muscarinic receptor antagonists. In fact, there are now a number of "triple-inhaler" fixed-dose combinations under development, with the first such triple combination having been approved in India. This use of combinations containing drugs with complementary pharmacological actions in the treatment of patients with asthma or COPD has also led to the discovery and development of drugs having two different primary pharmacological actions in the same molecule, which we have called "bifunctional drugs". In this review, we discuss the state of the art of these new bifunctional drugs as novel treatments for asthma and COPD that can be categorised as bifunctional bronchodilators, bifunctional bronchodilator/anti-inflammatory drugs and bifunctional anti-inflammatory drugs. PMID:24696121

  15. Perovskite-nitrogen-doped carbon nanotube composite as bifunctional catalysts for rechargeable lithium-air batteries.

    PubMed

    Park, Hey Woong; Lee, Dong Un; Park, Moon Gyu; Ahmed, Raihan; Seo, Min Ho; Nazar, Linda F; Chen, Zhongwei

    2015-03-01

    Developing an effective bifunctional catalyst is a significant issue, as rechargeable metal-air batteries are very attractive for future energy systems. In this study, a facile one-pot process is introduced to prepare an advanced bifunctional catalyst (op-LN) incorporating nitrogen-doped carbon nanotubes (NCNTs) into perovskite La0.5 Sr0.5 Co0.8 Fe0.2 O3 nanoparticles (LSCF-NPs). Confirmed by half-cell testing, op-LN exhibits synergistic effects of LSCF-NP and NCNT with excellent bifunctionality for both the oxygen reduction reaction and the oxygen evolution reaction. Furthermore, op-LN exhibits comparable performances in these reactions to Pt/C and Ir/C, respectively, which highlights its potential for use as a commercially viable bifunctional catalyst. Moreover, the results obtained by testing op-LN in a practical Li-air battery demonstrate improved and complementary charge/discharge performance compared to those of LSCF-NP and NCNT, and this confirms that simply prepared op-LN is a promising candidate as a highly effective bifunctional catalyst for rechargeable metal-air batteries. PMID:25684405

  16. A novel N-acetylglutamate synthase architecture revealed by the crystal structure of the bifunctional enzyme from Maricaulis maris.

    PubMed

    Shi, Dashuang; Li, Yongdong; Cabrera-Luque, Juan; Jin, Zhongmin; Yu, Xiaolin; Zhao, Gengxiang; Haskins, Nantaporn; Allewell, Norma M; Tuchman, Mendel

    2011-01-01

    Novel bifunctional N-acetylglutamate synthase/kinases (NAGS/K) that catalyze the first two steps of arginine biosynthesis and are homologous to vertebrate N-acetylglutamate synthase (NAGS), an essential cofactor-producing enzyme in the urea cycle, were identified in Maricaulis maris and several other bacteria. Arginine is an allosteric inhibitor of NAGS but not NAGK activity. The crystal structure of M. maris NAGS/K (mmNAGS/K) at 2.7 Å resolution indicates that it is a tetramer, in contrast to the hexameric structure of Neisseria gonorrhoeae NAGS. The quaternary structure of crystalline NAGS/K from Xanthomonas campestris (xcNAGS/K) is similar, and cross-linking experiments indicate that both mmNAGS/K and xcNAGS are tetramers in solution. Each subunit has an amino acid kinase (AAK) domain, which is likely responsible for N-acetylglutamate kinase (NAGK) activity and has a putative arginine binding site, and an N-acetyltransferase (NAT) domain that contains the putative NAGS active site. These structures and sequence comparisons suggest that the linker residue 291 may determine whether arginine acts as an allosteric inhibitor or activator in homologous enzymes in microorganisms and vertebrates. In addition, the angle of rotation between AAK and NAT domains varies among crystal forms and subunits within the tetramer. A rotation of 26° is sufficient to close the predicted AcCoA binding site, thus reducing enzymatic activity. Since mmNAGS/K has the highest degree of sequence homology to vertebrate NAGS of NAGS and NAGK enzymes whose structures have been determined, the mmNAGS/K structure was used to develop a structural model of human NAGS that is fully consistent with the functional effects of the 14 missense mutations that were identified in NAGS-deficient patients. PMID:22174908

  17. A Novel N-Acetylglutamate Synthase Architecture Revealed by the Crystal Structure of the Bifunctional Enzyme from Maricaulis maris

    PubMed Central

    Shi, Dashuang; Li, Yongdong; Cabrera-Luque, Juan; Jin, Zhongmin; Yu, Xiaolin; Zhao, Gengxiang; Haskins, Nantaporn; Allewell, Norma M.; Tuchman, Mendel

    2011-01-01

    Novel bifunctional N-acetylglutamate synthase/kinases (NAGS/K) that catalyze the first two steps of arginine biosynthesis and are homologous to vertebrate N-acetylglutamate synthase (NAGS), an essential cofactor-producing enzyme in the urea cycle, were identified in Maricaulis maris and several other bacteria. Arginine is an allosteric inhibitor of NAGS but not NAGK activity. The crystal structure of M. maris NAGS/K (mmNAGS/K) at 2.7 Å resolution indicates that it is a tetramer, in contrast to the hexameric structure of Neisseria gonorrhoeae NAGS. The quaternary structure of crystalline NAGS/K from Xanthomonas campestris (xcNAGS/K) is similar, and cross-linking experiments indicate that both mmNAGS/K and xcNAGS are tetramers in solution. Each subunit has an amino acid kinase (AAK) domain, which is likely responsible for N-acetylglutamate kinase (NAGK) activity and has a putative arginine binding site, and an N-acetyltransferase (NAT) domain that contains the putative NAGS active site. These structures and sequence comparisons suggest that the linker residue 291 may determine whether arginine acts as an allosteric inhibitor or activator in homologous enzymes in microorganisms and vertebrates. In addition, the angle of rotation between AAK and NAT domains varies among crystal forms and subunits within the tetramer. A rotation of 26° is sufficient to close the predicted AcCoA binding site, thus reducing enzymatic activity. Since mmNAGS/K has the highest degree of sequence homology to vertebrate NAGS of NAGS and NAGK enzymes whose structures have been determined, the mmNAGS/K structure was used to develop a structural model of human NAGS that is fully consistent with the functional effects of the 14 missense mutations that were identified in NAGS-deficient patients. PMID:22174908

  18. EDTA-Cross-Linked β-Cyclodextrin: An Environmentally Friendly Bifunctional Adsorbent for Simultaneous Adsorption of Metals and Cationic Dyes.

    PubMed

    Zhao, Feiping; Repo, Eveliina; Yin, Dulin; Meng, Yong; Jafari, Shila; Sillanpää, Mika

    2015-09-01

    The discharge of metals and dyes poses a serious threat to public health and the environment. What is worse, these two hazardous pollutants are often found to coexist in industrial wastewaters, making the treatment more challenging. Herein, we report an EDTA-cross-linked β-cyclodextrin (EDTA-β-CD) bifunctional adsorbent, which was fabricated by an easy and green approach through the polycondensation reaction of β-cyclodextrin with EDTA as a cross-linker, for simultaneous adsorption of metals and dyes. In this setting, cyclodextrin cavities are expected to capture dye molecules through the formation of inclusion complexes and EDTA units as the adsorption sites for metals. The adsorbent was characterized by FT-IR, elemental analysis, SEM, EDX, ζ-potential, and TGA. In a monocomponent system, the adsorption behaviors showed a monolayer adsorption capacity of 1.241 and 1.106 mmol g(-1) for Cu(II) and Cd(II), respectively, and a heterogeneous adsorption capacity of 0.262, 0.169, and 0.280 mmol g(-1) for Methylene Blue, Safranin O, and Crystal Violet, respectively. Interestingly, the Cu(II)-dye binary experiments showed adsorption enhancement of Cu(II), but no significant effect on dyes. The simultaneous adsorption mechanism was further confirmed by FT-IR, thermodynamic study, and elemental mapping. Overall, its facile and green fabrication, efficient sorption performance, and excellent reusability indicate that EDTA-β-CD has potential for practical applications in integrative and efficient treatment of coexistenting toxic pollutants. PMID:26237660

  19. A Novel N-Acetylglutamate Synthase Architecture Revealed by the Crystal Structure of the Bifunctional Enzyme from Maricaulis maris

    SciTech Connect

    Shi, Dashuang; Li, Yongdong; Cabrera-Luque, Juan; Jin, Zhongmin; Yu, Xiaolin; Zhao, Gengxiang; Haskins, Nantaporn; Allewell, Norma M.; Tuchman, Mendel

    2012-05-24

    Novel bifunctional N-acetylglutamate synthase/kinases (NAGS/K) that catalyze the first two steps of arginine biosynthesis and are homologous to vertebrate N-acetylglutamate synthase (NAGS), an essential cofactor-producing enzyme in the urea cycle, were identified in Maricaulis maris and several other bacteria. Arginine is an allosteric inhibitor of NAGS but not NAGK activity. The crystal structure of M. maris NAGS/K (mmNAGS/K) at 2.7 {angstrom} resolution indicates that it is a tetramer, in contrast to the hexameric structure of Neisseria gonorrhoeae NAGS. The quaternary structure of crystalline NAGS/K from Xanthomonas campestris (xcNAGS/K) is similar, and cross-linking experiments indicate that both mmNAGS/K and xcNAGS are tetramers in solution. Each subunit has an amino acid kinase (AAK) domain, which is likely responsible for N-acetylglutamate kinase (NAGK) activity and has a putative arginine binding site, and an N-acetyltransferase (NAT) domain that contains the putative NAGS active site. These structures and sequence comparisons suggest that the linker residue 291 may determine whether arginine acts as an allosteric inhibitor or activator in homologous enzymes in microorganisms and vertebrates. In addition, the angle of rotation between AAK and NAT domains varies among crystal forms and subunits within the tetramer. A rotation of 26{sup o} is sufficient to close the predicted AcCoA binding site, thus reducing enzymatic activity. Since mmNAGS/K has the highest degree of sequence homology to vertebrate NAGS of NAGS and NAGK enzymes whose structures have been determined, the mmNAGS/K structure was used to develop a structural model of human NAGS that is fully consistent with the functional effects of the 14 missense mutations that were identified in NAGS-deficient patients.

  20. Crosslinked poly(vinylbenzyl chloride) with a macromolecular crosslinker for anion exchange membrane fuel cells

    NASA Astrophysics Data System (ADS)

    Lu, Wangting; Shao, Zhi-Gang; Zhang, Geng; Zhao, Yun; Yi, Baolian

    2014-02-01

    A new material based on crosslinked poly(vinylbenzyl chloride) (PVBC) with a macromolecular crosslinker is synthesized and employed as the membrane for anion exchange membrane fuel cells (AEMFCs). PVBC is used as the hydroxide conducting polymers, while poly(vinyl acetal) (PVAc) containing dimethylamino groups plays the role as macromolecular crosslinker and the supporting matrix simultaneously. Fourier transform infrared (FT-IR) absorption spectra and X-ray photoelectron (XPS) spectra prove successful crosslinking between PVBC and PVAc. The crosslinked membrane shows hydroxide conductivity larger than 0.01 S cm-1 at room temperature, and the swelling by water at elevated temperature is suppressed. The H2/O2 AEMFC using the crosslinked membrane shows a peak power density (Pmax) of 124.7 mW cm-2 at 40 °C, and the decrease of the open circuit voltage (OCV) of the fuel cell is negligible under continuous OCV conditions for 120 h. All the results indicate that the crosslinking with a macromolecular crosslinker may be a promising strategy to fabricate anion exchange membrane for the application in the AEMFCs.

  1. Enhanced Bifunctional Oxygen Catalysis in Strained LaNiO3 Perovskites.

    PubMed

    Petrie, Jonathan R; Cooper, Valentino R; Freeland, John W; Meyer, Tricia L; Zhang, Zhiyong; Lutterman, Daniel A; Lee, Ho Nyung

    2016-03-01

    Strain is known to greatly influence low-temperature oxygen electrocatalysis on noble metal films, leading to significant enhancements in bifunctional activity essential for fuel cells and metal-air batteries. However, its catalytic impact on transition-metal oxide thin films, such as perovskites, is not widely understood. Here, we epitaxially strain the conducting perovskite LaNiO3 to systematically determine its influence on both the oxygen reduction and oxygen evolution reaction. Uniquely, we found that compressive strain could significantly enhance both reactions, yielding a bifunctional catalyst that surpasses the performance of noble metals such as Pt. We attribute the improved bifunctionality to strain-induced splitting of the eg orbitals, which can customize orbital asymmetry at the surface. Analogous to strain-induced shifts in the d-band center of noble metals relative to the Fermi level, such splitting can dramatically affect catalytic activity in this perovskite and other potentially more active oxides. PMID:26866808

  2. Electrochemical Investigation of Interaction between a Bifunctional Probe and GG Mismatch Duplex.

    PubMed

    Li, Jiao; He, Hanping; Peng, Xiaoqian; Huang, Min; Zhang, Xiuhua; Wang, Shengfu

    2015-01-01

    A bifunctional probe (FecNC), containing a recognition part and an electrochemical active center, was applied to electrochemical detection of GG mismatch duplexes. The preparation of gold electrodes modified by mismatch and complementatry duplexes was characterized by electrochemical impedance spectroscopy (EIS) and optimized for better detection in terms of self-assembly time, hybridization time, and incubation time. The interaction between FecNC and DNA duplexes modified on the surface of a gold electrode was explored by square wave voltammetry (SWV) and EIS. The results showed that the DNA duplexes with GG mismatch on the surface of a gold electrode was easily detected by the largest electrochemical signal of the bifunctional probe because of its selective binding to GG mismatches. The bifunctional probe could offer a simple, effective electrochemical detection of GG mismatches, and theoretical bases for development of electrochemical biosensors. Further, the method would be favorable for diagnosis of genetic diseases. PMID:26165289

  3. Nickel sulfide microsphere film on Ni foam as an efficient bifunctional electrocatalyst for overall water splitting.

    PubMed

    Zhu, Wenxin; Yue, Xiaoyue; Zhang, Wentao; Yu, Shaoxuan; Zhang, Yuhuan; Wang, Jing; Wang, Jianlong

    2016-01-25

    Developing low-cost, efficient, and bifunctional electrocatalysts for both the hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) is an appealing yet challenging task. Herein, for the first time, a NiS microsphere film was grown in situ on Ni foam (NiS/Ni foam) via a sulfurization reaction as an efficient bifunctional electrocatalyst for overall water splitting with superior activity and good durability. This NiS/Ni foam electrode delivers 20 mA cm(-2) at an overpotential of 158 mV for the HER and 50 mA cm(-2) at an overpotential of 335 mV for the OER in 1.0 M KOH. This bifunctional electrode also enables a high-efficiency alkaline water electrolyzer with 10 mA cm(-2) at a cell voltage of only 1.64 V, which could be promising in water splitting devices for large-scale hydrogen production. PMID:26661579

  4. Synthesis, characterization and catalytic activity of acid-base bifunctional materials through protection of amino groups

    SciTech Connect

    Shao, Yanqiu; Liu, Heng; Yu, Xiaofang; Guan, Jingqi; Kan, Qiubin

    2012-03-15

    Graphical abstract: Acid-base bifunctional mesoporous material SO{sub 3}H-SBA-15-NH{sub 2} was successfully synthesized under low acidic medium through protection of amino groups. Highlights: Black-Right-Pointing-Pointer The acid-base bifunctional material SO{sub 3}H-SBA-15-NH{sub 2} was successfully synthesized through protection of amino groups. Black-Right-Pointing-Pointer The obtained bifunctional material was tested for aldol condensation. Black-Right-Pointing-Pointer The SO{sub 3}H-SBA-15-NH{sub 2} catalyst containing amine and sulfonic acid groups exhibited excellent acid-basic properties. -- Abstract: Acid-base bifunctional mesoporous material SO{sub 3}H-SBA-15-NH{sub 2} was successfully synthesized under low acidic medium through protection of amino groups. X-ray diffraction (XRD), N{sub 2} adsorption-desorption, transmission electron micrographs (TEM), back titration, {sup 13}C magic-angle spinning (MAS) NMR and {sup 29}Si magic-angle spinning (MAS) NMR were employed to characterize the synthesized materials. The obtained bifunctional material was tested for aldol condensation reaction between acetone and 4-nitrobenzaldehyde. Compared with monofunctional catalysts of SO{sub 3}H-SBA-15 and SBA-15-NH{sub 2}, the bifunctional sample of SO{sub 3}H-SBA-15-NH{sub 2} containing amine and sulfonic acid groups exhibited excellent acid-basic properties, which make it possess high activity for the aldol condensation.

  5. Cross-linking Chemistry of Squid Beak*

    PubMed Central

    Miserez, Ali; Rubin, Daniel; Waite, J. Herbert

    2010-01-01

    In stark contrast to most aggressive predators, Dosidicus gigas (jumbo squids) do not use minerals in their powerful mouthparts known as beaks. Their beaks instead consist of a highly sclerotized chitinous composite with incremental hydration from the tip to the base. We previously reported l-3,4-dihydroxyphenylalanine (dopa)-histidine (dopa-His) as an important covalent cross-link providing mechanical strengthening to the beak material. Here, we present a more complete characterization of the sclerotization chemistry and describe additional cross-links from D. gigas beak. All cross-links presented in this report share common building blocks, a family of di-, tri-, and tetra-histidine-catecholic adducts, that were separated by affinity chromatography and high performance liquid chromatography (HPLC) and identified by tandem mass spectroscopy and proton nuclear magnetic resonance (1H NMR). The data provide additional insights into the unusually high cross-link density found in mature beaks. Furthermore, we propose both a low molecular weight catechol, and peptidyl-dopa, to be sclerotization agents of squid beak. This appears to represent a new strategy for forming hard tissue in animals. The interplay between covalent cross-linking and dehydration on the graded properties of the beaks is discussed. PMID:20870720

  6. Cross-linking chemistry of squid beak.

    PubMed

    Miserez, Ali; Rubin, Daniel; Waite, J Herbert

    2010-12-01

    In stark contrast to most aggressive predators, Dosidicus gigas (jumbo squids) do not use minerals in their powerful mouthparts known as beaks. Their beaks instead consist of a highly sclerotized chitinous composite with incremental hydration from the tip to the base. We previously reported l-3,4-dihydroxyphenylalanine (dopa)-histidine (dopa-His) as an important covalent cross-link providing mechanical strengthening to the beak material. Here, we present a more complete characterization of the sclerotization chemistry and describe additional cross-links from D. gigas beak. All cross-links presented in this report share common building blocks, a family of di-, tri-, and tetra-histidine-catecholic adducts, that were separated by affinity chromatography and high performance liquid chromatography (HPLC) and identified by tandem mass spectroscopy and proton nuclear magnetic resonance ((1)H NMR). The data provide additional insights into the unusually high cross-link density found in mature beaks. Furthermore, we propose both a low molecular weight catechol, and peptidyl-dopa, to be sclerotization agents of squid beak. This appears to represent a new strategy for forming hard tissue in animals. The interplay between covalent cross-linking and dehydration on the graded properties of the beaks is discussed. PMID:20870720

  7. Reaction Current Phenomenon in Bifunctional Catalytic Metal-Semiconductor Nanostructures

    NASA Astrophysics Data System (ADS)

    Hashemian, Mohammad Amin

    Energy transfer processes accompany every elementary step of catalytic chemical processes on material surface including molecular adsorption and dissociation on atoms, interactions between intermediates, and desorption of reaction products from the catalyst surface. Therefore, detailed understanding of these processes on the molecular level is of great fundamental and practical interest in energy-related applications of nanomaterials. Two main mechanisms of energy transfer from adsorbed particles to a surface are known: (i) adiabatic via excitation of quantized lattice vibrations (phonons) and (ii) non-adiabatic via electronic excitations (electron/hole pairs). Electronic excitations play a key role in nanocatalysis, and it was recently shown that they can be efficiently detected and studied using Schottky-type catalytic nanostructures in the form of measureable electrical currents (chemicurrents) in an external electrical circuit. These nanostructures typically contain an electrically continuous nanocathode layers made of a catalytic metal deposited on a semiconductor substrate. The goal of this research is to study the direct observations of hot electron currents (chemicurrents) in catalytic Schottky structures, using a continuous mesh-like Pt nanofilm grown onto a mesoporous TiO2 substrate. Such devices showed qualitatively different and more diverse signal properties, compared to the earlier devices using smooth substrates, which could only be explained on the basis of bifunctionality. In particular, it was necessary to suggest that different stages of the reaction are occurring on both phases of the catalytic structure. Analysis of the signal behavior also led to discovery of a formerly unknown (very slow) mode of the oxyhydrogen reaction on the Pt/TiO2(por) system occurring at room temperature. This slow mode was producing surprisingly large stationary chemicurrents in the range 10--50 microA/cm2. Results of the chemicurrent measurements for the bifunctional

  8. Bifunctional aldehyde/alcohol dehydrogenase (ADHE) in chlorophyte algal mitochondria.

    PubMed

    Atteia, Ariane; van Lis, Robert; Mendoza-Hernández, Guillermo; Henze, Katrin; Martin, William; Riveros-Rosas, Hector; González-Halphen, Diego

    2003-09-01

    Protein profiles of mitochondria isolated from the heterotrophic chlorophyte Polytomella sp. grown on ethanol at pH 6.0 and pH 3.7 were analyzed by Blue Native and denaturing polyacrylamide gel electrophoresis. Steady-state levels of oxidative phosphorylation complexes were influenced by external pH. Levels of an abundant, soluble, mitochondrial protein of 85 kDa and its corresponding mRNA increased at pH 6.0 relative to pH 3.7. N-terminal and internal sequencing of the 85 kDa mitochondrial protein together with the corresponding cDNA identified it as a bifunctional aldehyde/alcohol dehydrogenase (ADHE) with strong similarity to homologues from eubacteria and amitochondriate protists. A mitochondrial targeting sequence of 27 amino acids precedes the N-terminus of the mature mitochondrial protein. A gene encoding an ADHE homologue was also identified in the genome of Chlamydomonas reinhardtii, a photosynthetic relative of Polytomella. ADHE reveals a complex picture of sequence similarity among homologues. The lack of ADHE from archaebacteria indicates a eubacterial origin for the eukaryotic enzyme. Among eukaryotes, ADHE has hitherto been characteristic of anaerobes since it is essential to cytosolic energy metabolism of amitochondriate protists such as Giardia intestinalis and Entamoeba histolytica. Its abundance and expression pattern suggest an important role for ADHE in mitochondrial metabolism of Polytomella under the conditions studied. The current data are compatible with the view that Polytomella ADHE could be involved either in ethanol production or assimilation, or both, depending upon environmental conditions. Presence of ADHE in an oxygen-respiring algal mitochondrion and co-expression at ambient oxygen levels with respiratory chain components is unexpected with respect to the view that eukaryotes acquired ADHE genes specifically as an adaptation to an anaerobic lifestyle. PMID:14756315

  9. Physical properties of bifunctional BST/LSMO nanocomposites

    SciTech Connect

    Beltran-Huarac, Juan Morell, Gerardo; Martinez, Ricardo

    2014-02-28

    We report the fabrication of bifunctional nanocomposites consisting of ferroelectric Ba{sub 0.7}Sr{sub 0.3}TiO{sub 3} (BST) and ferromagnetic La{sub 0.67}Sr{sub 0.33}MnO{sub 3} (LSMO) at different concentrations via a high-temperature solid state route. The structural, dielectric, electrical, magnetodielectric (MD), magnetoelectric (ME) and magnetic properties of BST/LSMO nanocomposites were systematically investigated over a wide range of temperatures and frequencies. The X-Ray Diffraction analyses reveal the nanocrystalline nature of the heterostructures, wherein both perovskite phases co-exist. No parasitic phases were observed. The study of the dielectric properties shows that the nanocomposites exhibit relaxor ferroelectric character, with ferroelectric-paraelectric phase transition temperatures around 287–292 K that do not follow the Curie-Weiss law. The electrical measurements indicate that ac conductivities of the nanocomposites follow the Jonscher's universal power law, with activation energies of 0.42–0.63 eV based on Arrhenius-type behavior at high temperatures. The nanocomposites exhibit well-defined ferromagnetic hysteresis loops at room temperature (RT). The MD and ME measurements at RT indicate that BST/LSMO exhibits a nonlinear ME effect at low frequencies, with a threshold near 0.5 T. The magnetocapacitance (MC{sub p}) measurements evidence a quadratic dependence on magnetic field, further confirming the multiferroic nature of BST/LSMO. The order of MC{sub p} was found to be ∼7% per Tesla. The analysis of the MC{sub p} measurements indicates that one of the BST/LSMO compositions studied can be considered as a new multiferroic compound.

  10. Bifunctional Ligands Allow Deliberate Extrinsic Reprogramming of the Glucocorticoid Receptor

    PubMed Central

    Højfeldt, Jonas W.; Cruz-Rodríguez, Osvaldo; Imaeda, Yasuhiro; Van Dyke, Aaron R.; Carolan, James P.; Mapp, Anna K.

    2014-01-01

    Therapies based on conventional nuclear receptor ligands are extremely powerful, yet their broad and long-term use is often hindered by undesired side effects that are often part of the receptor's biological function. Selective control of nuclear receptors such as the glucocorticoid receptor (GR) using conventional ligands has proven particularly challenging. Because they act solely in an allosteric manner, conventional ligands are constrained to act via cofactors that can intrinsically partner with the receptor. Furthermore, effective means to rationally encode a bias for specific coregulators are generally lacking. Using the (GR) as a framework, we demonstrate here a versatile approach, based on bifunctional ligands, that extends the regulatory repertoire of GR in a deliberate and controlled manner. By linking the macrolide FK506 to a conventional agonist (dexamethasone) or antagonist (RU-486), we demonstrate that it is possible to bridge the intact receptor to either positively or negatively acting coregulatory proteins bearing an FK506 binding protein domain. Using this strategy, we show that extrinsic recruitment of a strong activation function can enhance the efficacy of the full agonist dexamethasone and reverse the antagonist character of RU-486 at an endogenous locus. Notably, the extrinsic recruitment of histone deacetylase-1 reduces the ability of GR to activate transcription from a canonical GR response element while preserving ligand-mediated repression of nuclear factor-κB. By providing novel ways for the receptor to engage specific coregulators, this unique ligand design approach has the potential to yield both novel tools for GR study and more selective therapeutics. PMID:24422633

  11. Janus nanobelts: fabrication, structure and enhanced magnetic-fluorescent bifunctional performance

    NASA Astrophysics Data System (ADS)

    Ma, Qianli; Yu, Wensheng; Dong, Xiangting; Wang, Jinxian; Liu, Guixia

    2014-02-01

    A new nanostructure of magnetic-fluorescent bifunctional Janus nanobelts with Fe3O4/PMMA as one half and Tb(BA)3phen/PMMA as the other half has been successfully fabricated by a specially designed parallel spinneret electrospinning technology. The morphology and properties of the final products were investigated in detail by X-ray diffractometry (XRD), scanning electron microscopy (SEM), energy dispersive spectrometry (EDS), biological microscopy (BM), vibrating sample magnetometry (VSM) and fluorescence spectroscopy. The results revealed that the [Fe3O4/PMMA]//[Tb(BA)3phen/PMMA] magnetic-fluorescent bifunctional Janus nanobelts possess superior magnetic and fluorescent properties due to their special nanostructure. Compared with Fe3O4/Tb(BA)3phen/PMMA composite nanobelts, the magnetic-fluorescent bifunctional Janus nanobelts provided better performance. The new magnetic-fluorescent bifunctional Janus nanobelts have potential applications in novel nano-bio-label materials, drug target delivery materials and future nanodevices due to their excellent magnetic-fluorescent properties, flexibility and insolubility. Moreover, the construction technique for the Janus nanobelts is of universal significance for the fabrication of other multifunctional Janus nanobelts.A new nanostructure of magnetic-fluorescent bifunctional Janus nanobelts with Fe3O4/PMMA as one half and Tb(BA)3phen/PMMA as the other half has been successfully fabricated by a specially designed parallel spinneret electrospinning technology. The morphology and properties of the final products were investigated in detail by X-ray diffractometry (XRD), scanning electron microscopy (SEM), energy dispersive spectrometry (EDS), biological microscopy (BM), vibrating sample magnetometry (VSM) and fluorescence spectroscopy. The results revealed that the [Fe3O4/PMMA]//[Tb(BA)3phen/PMMA] magnetic-fluorescent bifunctional Janus nanobelts possess superior magnetic and fluorescent properties due to their special

  12. Structural basis for bifunctional peptide recognition at human δ-opioid receptor.

    PubMed

    Fenalti, Gustavo; Zatsepin, Nadia A; Betti, Cecilia; Giguere, Patrick; Han, Gye Won; Ishchenko, Andrii; Liu, Wei; Guillemyn, Karel; Zhang, Haitao; James, Daniel; Wang, Dingjie; Weierstall, Uwe; Spence, John C H; Boutet, Sébastien; Messerschmidt, Marc; Williams, Garth J; Gati, Cornelius; Yefanov, Oleksandr M; White, Thomas A; Oberthuer, Dominik; Metz, Markus; Yoon, Chun Hong; Barty, Anton; Chapman, Henry N; Basu, Shibom; Coe, Jesse; Conrad, Chelsie E; Fromme, Raimund; Fromme, Petra; Tourwé, Dirk; Schiller, Peter W; Roth, Bryan L; Ballet, Steven; Katritch, Vsevolod; Stevens, Raymond C; Cherezov, Vadim

    2015-03-01

    Bifunctional μ- and δ-opioid receptor (OR) ligands are potential therapeutic alternatives, with diminished side effects, to alkaloid opiate analgesics. We solved the structure of human δ-OR bound to the bifunctional δ-OR antagonist and μ-OR agonist tetrapeptide H-Dmt-Tic-Phe-Phe-NH2 (DIPP-NH2) by serial femtosecond crystallography, revealing a cis-peptide bond between H-Dmt and Tic. The observed receptor-peptide interactions are critical for understanding of the pharmacological profiles of opioid peptides and for development of improved analgesics. PMID:25686086

  13. Structural basis for bifunctional peptide recognition at human δ-opioid receptor

    DOE PAGESBeta

    Fenalti, Gustavo; Zatsepin, Nadia A.; Betti, Cecilia; Giguere, Patrick; Han, Gye Won; Ishchenko, Andrii; Liu, Wei; Guillemyn, Karel; Zhang, Haitao; James, Daniel; et al

    2015-02-16

    Bi-functional μ- and δ- opioid receptor (OR) ligands are potential therapeutic alternatives to alkaloid opiate analgesics with diminished side effects. We solved the structure of human δ-OR bound to the bi-functional δ-OR antagonist and μ-OR agonist tetrapeptide H-Dmt-Tic-Phe-Phe-NH2 (DIPP-NH2) by serial femtosecond crystallography, revealing a cis-peptide bond between H-Dmt and Tic. In summary, the observed receptor-peptide interactions are critical to understand the pharmacological profiles of opioid peptides, and to develop improved analgesics.

  14. Structural basis for bifunctional peptide recognition at human δ-opioid receptor

    SciTech Connect

    Fenalti, Gustavo; Zatsepin, Nadia A.; Betti, Cecilia; Giguere, Patrick; Han, Gye Won; Ishchenko, Andrii; Liu, Wei; Guillemyn, Karel; Zhang, Haitao; James, Daniel; Wang, Dingjie; Weierstall, Uwe; Spence, John C. H.; Boutet, Sébastien; Messerschmidt, Marc; Williams, Garth J.; Gati, Cornelius; Yefanov, Oleksandr M.; White, Thomas A.; Oberthuer, Dominik; Metz, Markus; Yoon, Chun Hong; Barty, Anton; Chapman, Henry N.; Basu, Shibom; Coe, Jesse; Conrad, Chelsie E.; Fromme, Raimund; Fromme, Petra; Tourwé, Dirk; Schiller, Peter W.; Roth, Bryan L.; Ballet, Steven; Katritch, Vsevolod; Stevens, Raymond C.; Cherezov, Vadim

    2015-02-16

    Bi-functional μ- and δ- opioid receptor (OR) ligands are potential therapeutic alternatives to alkaloid opiate analgesics with diminished side effects. We solved the structure of human δ-OR bound to the bi-functional δ-OR antagonist and μ-OR agonist tetrapeptide H-Dmt-Tic-Phe-Phe-NH2 (DIPP-NH2) by serial femtosecond crystallography, revealing a cis-peptide bond between H-Dmt and Tic. In summary, the observed receptor-peptide interactions are critical to understand the pharmacological profiles of opioid peptides, and to develop improved analgesics.

  15. Effect of Cross-Linking on the Structure and Growth of Polymer Films Prepared by Interfacial Polymerization.

    PubMed

    Berezkin, Anatoly V; Kudryavtsev, Yaroslav V

    2015-11-10

    Interfacial polymerization of tri- and bifunctional monomers (A3B2 polymerization) is investigated by dissipative particle dynamics to reveal an effect of cross-linking on the reaction kinetics and structure of the growing polymer film. Regardless of the comonomer reactivity and miscibility, the kinetics in an initially bilayer melt passes from the reaction to diffusion control. Within the crossover period, branched macromolecules undergo gelation, which drastically changes the scenario of the polymerization process. Comparison with the previously studied linear interfacial polymerization (Berezkin, A. V.; Kudryavtsev, Y. V. Linear Interfacial Polymerization: Theory and Simulations with Dissipative Particle Dynamics J. Chem. Phys. 2014, 141, 194906) shows similar conversion rates but very different product characteristics. Cross-linked polymer films are markedly heterogeneous in density, their average polymerization degree grows with the comonomer miscibility, and end groups are mostly trapped deeply in the film core. Products of linear interfacial polymerization demonstrate opposite trends as they are spontaneously homogenized by a convective flow of macromolecules expelled from the reactive zone to the film periphery, which we call the reactive extrusion effect and which is hampered in branched polymerization. Influence of the comonomer architecture on the polymer film characteristics could be used in various practical applications of interfacial polymerization, such as fabrication of membranes, micro- and nanocapsules and 3D printing. PMID:26471239

  16. Crosslinked polyethylene foams, via EB radiation

    NASA Astrophysics Data System (ADS)

    Cardoso, E. C. L.; Lugão, A. B.; Andrade E. Silva, L. G.

    1998-06-01

    Polyethylene foams, produced by radio-induced crosslinking, show a smooth and homogeneous surface, when compared to chemical crosslinking method using peroxide as crosslinking agent. This process fosters excellent adhesive and printability properties. Besides that, closed cells, intrinsic to theses foams, imparts opitmum mechanical, shocks and insulation resistance, indicating these foams to some markets segments as: automotive and transport; buoyancy, flotation and marine: building and insulation: packaging: domestic sports and leisure goods. We were in search of an ideal foam, by adding 5 to 15% of blowing agent in LDPE. A series of preliminary trials defined 203° C as the right blowing agent decomposition temperature. At a 22.7 kGy/dose ratio, the lowest dose for providing an efficient foam was 30 kGy, for a formulation comprising 10% of azodicarbonamide in LDPE, within a 10 minutes foaming time.

  17. Development of a Crosslink Channel Simulator

    NASA Technical Reports Server (NTRS)

    Hunt, Chris; Smith, Carl; Burns, Rich

    2004-01-01

    Distributed Spacecraft missions are an integral part of current and future plans for NASA and other space agencies. Many of these multi-vehicle missions involve utilizing the array of spacecraft as a single, instrument requiring communication via crosslinks to achieve mission goals. NASA s Goddard Space Flight Center (GSFC) is developing the Formation Flying Test Bed (FFTB) to provide a hardware-in-the-loop simulation environment to support mission concept development and system trades with a primary focus on Guidance, Navigation, and Control (GN&C) challenges associated with spacecraft flying. The goal of the FFTB is to reduce mission risk by assisting in mission planning and analysis, provide a technology development platform that allows algorithms to be developed for mission functions such as precision formation navigation and control and time synchronization. The FFTB will provide a medium in which the various crosslink transponders being used in multi-vehicle missions can be integrated for development and test; an integral part of the FFTB is the Crosslink Channel Simulator (CCS). The CCS is placed into the communications channel between the crosslinks under test, and is used to simulate on-mission effects to the communications channel such as vehicle maneuvers, relative vehicle motion, or antenna misalignment. The CCS is based on the Starlight software programmable platform developed at General Dynamics Decision Systems and provides the CCS with the ability to be modified on the fly to adapt to new crosslink formats or mission parameters. This paper briefly describes the Formation Flying Test Bed and its potential uses. It then provides details on the current and future development of the Crosslink Channel Simulator and its capabilities.

  18. Shell-crosslinked knedel-like nanoparticles induce lower immunotoxicity than their non-crosslinked analogs

    PubMed Central

    Elsabahy, Mahmoud; Samarajeewa, Sandani; Raymond, Jeffery E.; Clark, Corrie; Wooley, Karen L.

    2013-01-01

    The development of stable nanoparticles that can withstand the changing conditions experienced in a biological setting and also be of low toxicity and immunogenicity is of particular importance to address the problems associated with currently utilized nanotechnology-based therapeutics and diagnostics. The use of crosslinked nanoparticles continues to receive special impetus, due to their robust structure and high kinetic stability, and they have recently been shown to induce lower cytotoxicity than their non-crosslinked micellar counterparts. In the current study, poly(acrylamidoethylamine)-block-poly(DL-lactide) (PAEA90-b-PDLLA40) copolymers were synthesized, self-assembled in water to yield nanoscopic polymeric micelles, and the effects of decorating the micellar surface with poly(ethylene glycol) (i.e. PEGylation) and crosslinking the PAEA layer to varying extents on the physicochemical characteristics, cytotoxicity and immunotoxicity of the nanoparticles were studied. Herein, we report for the first time that crosslinking can efficiently reduce the immunotoxicity of polymeric nanomaterials. In addition, increasing the degree of crosslinking further reduced the accessibility of biomolecules to the core of the nanoparticles and decreased their cytotoxicity and immunotoxicity. It is also highlighted that crosslinking can be more efficient than PEGylation in reducing the immunotoxicity of nanomaterials. Shell-crosslinking of block copolymer micelles, therefore, is expected to advance their clinical development beyond the earlier known effects, and to broaden the implications in the field of nanomedicine. PMID:24187610

  19. Microrheology of highly crosslinked microtubule networks is dominated by force-induced crosslinker unbinding

    PubMed Central

    Yang, Yali; Bai, Mo; Klug, William S.; Levine, Alex J.

    2012-01-01

    We determine the time- and force-dependent viscoelastic responses of reconstituted networks of microtubules that have been strongly crosslinked by biotin-streptavidin bonds. To measure the microscale viscoelasticity of such networks, we use a magnetic tweezers device to apply localized forces. At short time scales, the networks respond nonlinearly to applied force, with stiffening at small forces, followed by a reduction in the stiffening response at high forces, which we attribute to the force-induced unbinding of crosslinks. At long time scales, force-induced bond unbinding leads to local network rearrangement and significant bead creep. Interestingly, the network retains its elastic modulus even under conditions of significant plastic flow, suggesting that crosslinker breakage is balanced by the formation of new bonds. To better understand this effect, we developed a finite element model of such a stiff filament network with labile crosslinkers obeying force-dependent Bell model unbinding dynamics. The coexistence of dissipation, due to bond breakage, and the elastic recovery of the network is possible because each filament has many crosslinkers. Recovery can occur as long as a sufficient number of the original crosslinkers are preserved under the loading period. When these remaining original crosslinkers are broken, plastic flow results. PMID:23577042

  20. Cross-Linking Studies of Lysozyme Nucleation

    NASA Technical Reports Server (NTRS)

    Forsythe, Elizabeth; Pusey, Marc

    2000-01-01

    Tetragonal chicken egg white crystals consist of 4(sub 3) helices running in alternating directions, the helix rows having a two fold symmetry with each other. The unit cell consists of one complete tetrameric turn from each of two adjacent helices (an octamer). PBC analysis indicates that the helix intermolecular bonds are the strongest in the crystal, therefore likely formed first. AFM analysis of the (110) surface shows only complete helices, no half steps or bisected helices being found, while AFM line scans to measure the growth step increments show that they are multiples of the 4(sub 3) helix tetramer dimensions. This supports our thesis that the growth units are in fact multiples of the four molecule 4(sub 3) helix unit, the "average" growth unit size for the (110) face being an octamer (two turns about the helix) and the (101) growth unit averaging about the size of a hexamer. In an effort to better understand the species involved in the crystal nucleation and growth process, we have initiated an experimental program to study the species formed in solution compared to what is found in the crystal through covalent cross-linking studies. These experiments use the heterobifunctional cross-linking agent aminoethyl-4-azidonitroanaline (AEANA). An aliphatic amine at one end is covalently attached to the protein by a carbodiimide-mediated reaction, and a photo reactive group at the other can be used to initiate crosslinking. Modifications to the parent structure can be used to alter the distance between the two reactive groups and thus the cross-linking agents "reach". In practice, the cross-linking agent is first coupled to the asp101 side chain through the amine group. Asp101 lies within the active site cleft, and previous work with fluorescent probes had shown that derivatives at this site still crystallize in the tetragonal space group. This was also found to be the case with the AEANA derivative, which gave red tetragonal crystals. The protein now has a

  1. Hybridization triggered cross-linking of deoxyoligonucleotides.

    PubMed Central

    Webb, T R; Matteucci, M D

    1986-01-01

    This paper reports details of the synthesis of oligodeoxynucleotides containing the modified base 5-methyl-N4,N4-ethanocytosine (Ce). The 9-fluorenylmethoxycarbonyl group is used as a protecting group for the exocyclic amines of dA and dC. This group can be removed rapidly under very mild conditions. Oligomers containing the Ce base form a cross-link when hybridized to their complementary deoxyoligonucleotides. Some of the scope and limitations of these cross-link forming oligonucleotides are reported. Images PMID:3774542

  2. Probing PrPSc structure using chemical cross-linking and mass spectrometry: evidence of the proximity of Gly90 amino termini in the PrP 27-30 aggregate.

    PubMed

    Onisko, Bruce; Fernández, Esteban Guitián; Freire, María Louro; Schwarz, Anja; Baier, Michael; Camiña, Félix; García, Javier Rodríguez; Rodríguez-Segade Villamarín, Santiago; Requena, Jesús R

    2005-08-01

    Elucidation of the structure of PrP(Sc) continues to be one of the most important and difficult challenges in prion research. This task, essential for gaining an understanding of the basis of prion infectivity, has been hampered by the insoluble, aggregated nature of this molecule. We used a combination of chemical cross-linking, proteolytic digestion, and mass spectrometry (MALDI-TOF and nanoLC-ESI-QqTOF), in an attempt to gain structural information about PrP 27-30 purified from the brains of Syrian hamsters infected with scrapie. The rationale of this approach is to identify pairs of specific amino acid residues that are close enough to each other to react with a bifunctional reagent of a given chain length. We cross-linked PrP 27-30 with the amino-specific reagent bis(sulfosuccinimidyl) suberate (BS(3)), obtaining dimers, trimers, and higher-order oligomers that were separated by SDS-PAGE. In-gel digestion followed by mass spectrometric analysis showed that BS(3) reacted preferentially with Gly90. A cross-link involving two Gly90 amino termini was found in cross-linked PrP 27-30 dimers, but not in intramolecularly cross-linked monomers or control samples. This observation indicates the spatial proximity of Gly90 amino termini in PrP 27-30 fibrils. The Gly90-Gly90 cross-link is consistent with a recent model of PrP 27-30, based on electron crystallographic data, featuring a fiber composed of stacked trimers of PrP monomers; specifically, it is compatible with cross-linking of monomers stacked vertically along the fiber axis but not those adjacent to each other horizontally in the trimeric building block. Our results constitute the first measured distance constraint in PrP(Sc). PMID:16042387

  3. Ionic Polymer Microspheres Bearing a Co(III) -Salen Moiety as a Bifunctional Heterogeneous Catalyst for the Efficient Cycloaddition of CO2 and Epoxides.

    PubMed

    Leng, Yan; Lu, Dan; Zhang, Chenjun; Jiang, Pingping; Zhang, Weijie; Wang, Jun

    2016-06-01

    We report a unique strategy to obtain the bifunctional heterogeneous catalyst TBB-Bpy@Salen-Co (TBB=1,2,4,5-tetrakis(bromomethyl)benzene, Bpy=4,4'-bipyridine, Salen-Co=N,N'-bis({4-dimethylamino}salicylidene)ethylenediamino cobalt(III) acetate) by combining a cross-linked ionic polymer with a Co(III) -salen Schiff base. The catalyst showed extra high activity for CO2 fixation under mild, solvent-free reaction conditions with no requirement for a co-catalyst. The synthesized catalyst possessed distinctive spherical structural features, abundant halogen Br(-) anions with good leaving group ability, and accessible Lewis acidic Co metal centers. These unique features, together with the synergistic role of the Co and Br(-) functional sites, allowed TBB-Bpy@Salen-Co to exhibit enhanced catalytic conversion of CO2 into cyclic carbonates relative to the corresponding monofunctional analogues. This catalyst can be easily recovered and recycled five times without significant leaching of Co or loss of activity. Moreover, based on our experimental results and previous work, a synergistic cycloaddition reaction mechanism was proposed. PMID:27116117

  4. A bifunctional chiral [2]catenane based on 1,1'-binaphthyl-phosphates.

    PubMed

    Mitra, R; Thiele, M; Octa-Smolin, F; Letzel, M C; Niemeyer, J

    2016-05-21

    A novel [2]catenane was synthesised by ring-closing metathesis from a Ca-bisphosphate template. The resulting interlocked structure features two chiral 1,1'-binaphthyl-phosphates, leading to a bifunctional catenane structure. Initial binding studies point at the applicability of such mechanically interlocked bisphosphates as artificial receptors for dicationic guest molecules. PMID:27058367

  5. Bifunctional phosphoramidite reagents for the introduction of histidyl and dihistidyl residues into oligonucleotides.

    PubMed

    Smith, T H; LaTour, J V; Bochkariov, D; Chaga, G; Nelson, P S

    1999-01-01

    The synthesis and characterization of reagents for the incorporation of histidyl residues into oligonucleotides by automated chemical synthesis is described. Automated oligonucleotide synthesis utilizing a bifunctional reagent for the incorporation of a dihistidyl residue into oligonucleotides is described. Oligonucleotides incorporating one to three dihistidyl residues were prepared and characterized. The interaction of these oligonucleotides with a metal chelating IMAC matrix was explored. PMID:10411463

  6. Porous MoO2 Nanosheets as Non-noble Bifunctional Electrocatalysts for Overall Water Splitting.

    PubMed

    Jin, Yanshuo; Wang, Haotian; Li, Junjie; Yue, Xin; Han, Yujie; Shen, Pei Kang; Cui, Yi

    2016-05-01

    A porous MoO2 nanosheet as an active and stable bifunctional electrocatalyst for overall water splitting, is presented. It needs a cell voltage of only about 1.53 V to achieve a current density of 10 mA cm(-2) and maintains its activity for at least 24 h in a two-electrode configuration. PMID:26996884

  7. Sensitivity and robustness in covalent modification cycles with a bifunctional converter enzyme.

    PubMed

    Straube, Ronny

    2013-10-15

    Regulation by covalent modification is a common mechanism to transmit signals in biological systems. The modifying reactions are catalyzed either by two distinct converter enzymes or by a single bifunctional enzyme (which may employ either one or two catalytic sites for its opposing activities). The reason for this diversification is unclear, but contemporary theoretical models predict that systems with distinct converter enzymes can exhibit enhanced sensitivity to input signals whereas bifunctional enzymes with two catalytic sites are believed to generate robustness against variations in system's components. However, experiments indicate that bifunctional enzymes can also exhibit enhanced sensitivity due to the zero-order effect, raising the question whether both phenomena could be understood within a common mechanistic model. Here, I argue that this is, indeed, the case. Specifically, I show that bifunctional enzymes with two catalytic sites can exhibit both ultrasensitivity and concentration robustness, depending on the kinetic operating regime of the enzyme's opposing activities. The model predictions are discussed in the context of experimental observations of ultrasensitivity and concentration robustness in the uridylylation cycle of the PII protein, and in the phosphorylation cycle of the isocitrate dehydrogenase, respectively. PMID:24138868

  8. Asymmetric α-amination of β-keto esters using a guanidine–bisurea bifunctional organocatalyst

    PubMed Central

    Yamamoto, Yoshiharu

    2016-01-01

    Summary An asymmetric α-amination of β-keto esters with azodicarboxylate in the presence of a guanidine–bisurea bifunctional organocatalyst was investigated. The α-amination products were obtained in up to 99% yield with up to 94% ee. PMID:26977179

  9. Bifunctional N-heterocyclic carbene-catalyzed highly enantioselective synthesis of spirocyclic oxindolo-β-lactams.

    PubMed

    Zhang, Han-Ming; Gao, Zhong-Hua; Ye, Song

    2014-06-01

    The N-heterocyclic carbene-catalyzed Staudinger reaction of ketenes with isatin-derived ketimines was investigated. The bifunctional NHCs with a free hydroxyl group were demonstrated as efficient catalysts for the reaction, giving the corresponding spirocyclic oxindolo-β-lactams in high yields with excellent diastereo- and enantioselectivities. PMID:24856000

  10. Cross-linked structure of network evolution

    NASA Astrophysics Data System (ADS)

    Bassett, Danielle S.; Wymbs, Nicholas F.; Porter, Mason A.; Mucha, Peter J.; Grafton, Scott T.

    2014-03-01

    We study the temporal co-variation of network co-evolution via the cross-link structure of networks, for which we take advantage of the formalism of hypergraphs to map cross-link structures back to network nodes. We investigate two sets of temporal network data in detail. In a network of coupled nonlinear oscillators, hyperedges that consist of network edges with temporally co-varying weights uncover the driving co-evolution patterns of edge weight dynamics both within and between oscillator communities. In the human brain, networks that represent temporal changes in brain activity during learning exhibit early co-evolution that then settles down with practice. Subsequent decreases in hyperedge size are consistent with emergence of an autonomous subgraph whose dynamics no longer depends on other parts of the network. Our results on real and synthetic networks give a poignant demonstration of the ability of cross-link structure to uncover unexpected co-evolution attributes in both real and synthetic dynamical systems. This, in turn, illustrates the utility of analyzing cross-links for investigating the structure of temporal networks.

  11. Hydrogels with covalent and noncovalent crosslinks

    NASA Technical Reports Server (NTRS)

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

    2013-01-01

    A method for targeted delivery of therapeutic compounds from hydrogels is presented. The method involves administering to a cell a hydrogel in which a therapeutic compound is noncovalently bound to heparin. The hydrogel may contain covalent and non-covalent crosslinks.

  12. Preparation of DNA-crosslinked polyacrylamide hydrogels.

    PubMed

    Previtera, Michelle L; Langrana, Noshir A

    2014-01-01

    Mechanobiology is an emerging scientific area that addresses the critical role of physical cues in directing cell morphology and function. For example, the effect of tissue elasticity on cell function is a major area of mechanobiology research because tissue stiffness modulates with disease, development, and injury. Static tissue-mimicking materials, or materials that cannot alter stiffness once cells are plated, are predominately used to investigate the effects of tissue stiffness on cell functions. While information gathered from static studies is valuable, these studies are not indicative of the dynamic nature of the cellular microenvironment in vivo. To better address the effects of dynamic stiffness on cell function, we developed a DNA-crosslinked polyacrylamide hydrogel system (DNA gels). Unlike other dynamic substrates, DNA gels have the ability to decrease or increase in stiffness after fabrication without stimuli. DNA gels consist of DNA crosslinks that are polymerized into a polyacrylamide backbone. Adding and removing crosslinks via delivery of single-stranded DNA allows temporal, spatial, and reversible control of gel elasticity. We have shown in previous reports that dynamic modulation of DNA gel elasticity influences fibroblast and neuron behavior. In this report and video, we provide a schematic that describes the DNA gel crosslinking mechanisms and step-by-step instructions on the preparation DNA gels. PMID:25226067

  13. Age-related crosslink in skin collagen

    SciTech Connect

    Yamauchi, M.; Mechanic, G.

    1986-05-01

    A stable crosslinking amino acid was isolated from mature bovine skin collagen and its structure was identified as histidinohydroxylysinonorleucine (HHL) using fast atom bombardment mass spectrometry and /sup 1/H, /sup 13/C-NMR. This newly identified crosslink has a linkage between C-2 histidine and C-6 of lysine in the latter's portion of hydroxylysinonorleucine. Quantitative studies using various aged samples of cow and human skin collagen indicated that this acid-heat stable nonreducible compound was the major age-related crosslink. In case of cow skin collagen, for example, during early embryonic development (3 and 5 month old embryos) the content of HHL stayed less than 0.01 residue/mole of collagen, however from the middle of gestation period (7 month old embryo) through the maturation stage it showed rapid increase with age and reached approximately 0.5 residues/mole of collagen in the 3 year old animal. Small increments (up to 0.65 res/mole of collagen) were observed in the 9 year old cow. The amounts of the crosslink unlike pyridinoline do not decrease with aging. Similar patterns were observed in human skin collagen.

  14. Highly cross-linked nanoporous polymers

    DOEpatents

    Steckle, W.P. Jr.; Apen, P.G.; Mitchell, M.A.

    1998-01-20

    Condensation polymerization followed by a supercritical extraction step can be used to obtain highly cross-linked nanoporous polymers with high surface area, controlled pore sizes and rigid structural integrity. The invention polymers are useful for applications requiring separation membranes. 1 fig.

  15. Traceless cross-linker for photocleavable bioconjugation.

    PubMed

    Wang, Rong; Yan, Funing; Qiu, Dengli; Jeong, Jae-Sun; Jin, Qiaoling; Kim, Tae-Young; Chen, Liaohai

    2012-04-18

    Photoresponsive bioconjugation empowers the development of novel methods for drug discovery, disease diagnosis, and high-throughput screening, among others. In this paper, we report on the characteristics of a traceless photocleavable cross-linker, di-6-(3-succinimidyl carbonyloxymethyl-4-nitro-phenoxy)-hexanoic acid disulfide diethanol ester (SCNE). The traceless feature and the biocompatibility of this photocleavable cross-linking reagent were corroborated. Consequently, we demonstrated its application in reversible phage particle immobilization that could provide a platform for direct single-phage screening. We also applied it in protein-photoprinting, where SCNE acts as a "photo-eraser" to remove the cross-linked protein molecules at a desired region in a simple, clean, and light-controllable fashion. We further demonstrated the two-tier atomic force microscopic (AFM) method that uses SCNE to carry out two subsequent AFM tasks in situ. The approach allows guided protein delivery and subsequent high-resolution imaging at the same local area, thus opening up the possibility of monitoring protein functions in live cells. The results imply that SCNE is a versatile cross-linker that can be used for a wide range of applications where photocleavage ensures clean and remote-controllable release of biological molecules from a substrate. PMID:22432929

  16. Cross-linked structure of network evolution

    SciTech Connect

    Bassett, Danielle S.; Wymbs, Nicholas F.; Grafton, Scott T.; Porter, Mason A.; Mucha, Peter J.

    2014-03-15

    We study the temporal co-variation of network co-evolution via the cross-link structure of networks, for which we take advantage of the formalism of hypergraphs to map cross-link structures back to network nodes. We investigate two sets of temporal network data in detail. In a network of coupled nonlinear oscillators, hyperedges that consist of network edges with temporally co-varying weights uncover the driving co-evolution patterns of edge weight dynamics both within and between oscillator communities. In the human brain, networks that represent temporal changes in brain activity during learning exhibit early co-evolution that then settles down with practice. Subsequent decreases in hyperedge size are consistent with emergence of an autonomous subgraph whose dynamics no longer depends on other parts of the network. Our results on real and synthetic networks give a poignant demonstration of the ability of cross-link structure to uncover unexpected co-evolution attributes in both real and synthetic dynamical systems. This, in turn, illustrates the utility of analyzing cross-links for investigating the structure of temporal networks.

  17. Thermally crosslinked polymeric compositions and methods of making the same

    DOEpatents

    Koros, William John; Kratochvil, Adam Michal

    2014-03-04

    The various embodiments of the present disclosure relate generally to thermally crosslinked polymeric compositions and methods of making thermally crosslinked polymeric compositions. An embodiment of the present invention comprises a composition comprising: a first polymer comprising a first repeat unit, the first repeat unit comprising a carboxyl group, wherein the first polymer crosslinks to a second polymer formed from a second repeat unit, and wherein the first polymer crosslinks to the second polymer without formation of an ester group.

  18. CHARACTERIZATION OF CASEINS CROSSLINKED BY A NATURALLY OCCURRING CROSSLINKING AGENT-GENIPIN

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Increasing economic and environmental pressures demand more effective utilization of natural resources. Genipin, a naturally occurring crosslinking agent obtained from the fruit of Gardenia jasminoides, has recently attracted much attention due to its low cytotoxicity compared to traditional crossli...

  19. Kojak: Efficient analysis of chemically cross-linked protein complexes

    PubMed Central

    Hoopmann, Michael R.; Zelter, Alex; Johnson, Richard S.; Riffle, Michael; MacCoss, Michael J.; Davis, Trisha N.; Moritz, Robert L.

    2015-01-01

    Protein chemical cross-linking and mass spectrometry enable the analysis of protein-protein interactions and protein topologies, however complicated cross-linked peptide spectra require specialized algorithms to identify interacting sites. The Kojak cross-linking software application is a new, efficient approach to identify cross-linked peptides, enabling large-scale analysis of protein-protein interactions by chemical cross-linking techniques. The algorithm integrates spectral processing and scoring schemes adopted from traditional database search algorithms, and can identify cross-linked peptides using many different chemical cross-linkers, with or without heavy isotope labels. Kojak was used to analyze both novel and existing datasets, and was compared with existing cross-linking algorithms. The algorithm provided increased cross-link identifications over existing algorithms, and equally importantly, the results in a fraction of computational time. The Kojak algorithm is open-source, cross-platform, and freely available. This software provides both existing and new cross-linking researchers alike an effective way to derive additional cross-link identifications from new or existing datasets. For new users, it provides a simple analytical resource resulting in more cross-link identifications than other methods. PMID:25812159

  20. IMPROVED PHYSICAL PROPERTIES OF ZEIN USING GLYOXAL AS A CROSSLINKER

    Technology Transfer Automated Retrieval System (TEKTRAN)

    The effect of crosslinkers glyoxal, methylglyoxal and formaldehyde on physical properties of zein films was studied. Crosslinker concentrations varied from 0.3 to 6% by zein weight. Films crosslinked with glyoxal and formaldehyde showed a significant increase in tensile strength under certain pH c...

  1. A Single Molecular Diels-Alder Crosslinker for Achieving Recyclable Cross-Linked Polymers.

    PubMed

    Chen, Shengli; Wang, Fenfen; Peng, Yongjin; Chen, Tiehong; Wu, Qiang; Sun, Pingchuan

    2015-09-01

    A triol-functional crosslinker combining the thermoreversible properties of Diels-Alder (DA) adducts in one molecule is designed, synthesized, and used as an ideal substitute of a traditional crosslinker to prepare thermal recyclable cross-linked polyurethanes with excellent mechanical properties and recyclability in a very simple and efficient way. The recycle property of these materials achieved by the DA/retro-DA reaction at a suitable temperature is verified by differential scanning calorimetry and in situ variable temperature solid-state NMR experiments during the cyclic heating and cooling processes. The thermal recyclability and remending ability of the bulk polyurethanes is demonstrated by three polymer processing methods, including hot-press molding, injection molding, and solution casting. It is notable that all the recycled cross-linked polymers display nearly invariable elongation/stress at break compared to the as-synthesized samples. Further end-group functionalization of this single molecular DA crosslinker provides the potential in preparing a wide range of recyclable cross-linked polymers. PMID:26248230

  2. To Cross-Link or Not to Cross-Link? Cross-Linking Associated Foreign Body Response of Collagen-Based Devices

    PubMed Central

    Delgado, Luis M.; Bayon, Yves; Pandit, Abhay

    2015-01-01

    Collagen-based devices, in various physical conformations, are extensively used for tissue engineering and regenerative medicine applications. Given that the natural cross-linking pathway of collagen does not occur in vitro, chemical, physical, and biological cross-linking methods have been assessed over the years to control mechanical stability, degradation rate, and immunogenicity of the device upon implantation. Although in vitro data demonstrate that mechanical properties and degradation rate can be accurately controlled as a function of the cross-linking method utilized, preclinical and clinical data indicate that cross-linking methods employed may have adverse effects on host response, especially when potent cross-linking methods are employed. Experimental data suggest that more suitable cross-linking methods should be developed to achieve a balance between stability and functional remodeling. PMID:25517923

  3. Characterization of crosslinked artificial protein films

    NASA Astrophysics Data System (ADS)

    Nowatzki, Paul

    Genetically engineered artificial proteins are promising candidates for new biomaterials because their amino acid sequences can be precisely controlled. This work describes the characterization of crosslinked films of biomimetic artificial extracellular matrix (aECM) proteins with hybrid functions designed to meet materials needs in applications such as small diameter vascular grafts and corneal tissue implants. Elastin-derived polypeptides give the proteins flexibility, while RGD and CS5 peptide domains from fibronectin serve to adhere cells. Techniques were sought to crosslink aECM proteins in ways that resulted in tunable mechanical properties. Hexamethylene diisocyanate was used to crosslink aECM proteins into uniform, transparent, highly-extensible hydrogel films with low water contents characteristic of native elastin. Their elastic moduli, 0.1--1.1 MPa, depended on crosslinker concentration and aECM protein length, and spanned the observed range of elastin fibers. The suitability of biomaterials implants depends strongly on their susceptibility to proteolytic degradation in vivo. It was shown that small sequence changes in the elastin-like portion of aECM proteins were sufficient to decrease their rate of degradation by elastase sevenfold, illustrating a simple method to tune the protease sensitivity of designed proteins. The effects were seen in both soluble proteins and crosslinked films analyzed by measuring their decrease in elastic modulus during degradation. An aECM protein was examined for its effectiveness as a corneal onlay, i.e., a permanent contact lens. The protein was crosslinked into transparent, elastic, water-rich lenses and was implanted into rabbit corneas. The onlays were stable and well-tolerated, and full re-epithelialization occurred within 4-7 days. Histological examination revealed normal regenerating epithelial cell morphology on the anterior surface, good interfaces between the onlay and surrounding tissue, and only minimal

  4. Gelation of Copolymers Photo-crosslinked by Pendent Benzophenones

    NASA Astrophysics Data System (ADS)

    Christensen, Scott; Hayward, Ryan C.

    2012-02-01

    Copolymers containing pendent benzophenone (BP) groups provide a simple and powerful route to crosslinkable polymer films. While the solution state photo-chemistry of BP is well established, and crosslinking of polymers blended with BP has been studied in detail, the process of crosslinking by covalently attached BP has received comparatively little attention. We have prepared copolymers of BP with several different monomers, and studied gelation as a function of BP content and degree of photochemical conversion. Understanding the influence of polymer chemistry on crosslinking efficiency allows the appropriate choice of materials for nanostructured photo-crosslinkable polymer films and reactive polymer blends.

  5. Gelation of Copolymers Photo-crosslinked by Pendant Benzophenones

    NASA Astrophysics Data System (ADS)

    Christensen, Scott; Hayward, Ryan C.

    2011-03-01

    Copolymers containing pendant benzophenone (BP) groups provide a simple and powerful route to crosslinkable polymer films. While the solution state photo-chemistry of BP is well established, and crosslinking of polymers blended with BP has been studied in detail, the process of crosslinking by covalently attached BP has received comparatively little attention. We have prepared copolymers of BP with several different monomers, and studied gelation as a function of BP content and degree of photochemical conversion. We seek to understand the influence of polymer chemistry on crosslinking efficiency, to guide choices of materials for photo- crosslinkable polymer films and to provide a route for tailoring morphology in polymer blends.

  6. Propranolol hydrochloride release behaviour of crosslinked chitosan membranes.

    PubMed

    Thacharodi, D; Rao, K P

    1993-01-01

    Chitosan membranes of 20 microns thickness were prepared by a solvent evaporation technique and crosslinked with different concentrations of glutaraldehyde to obtain membranes of various degrees of crosslinking. These membranes were characterized by thermogravimetric (TG) analysis, differential scanning calorimetry (DSC) and tensile strength studies. The effect of crosslinking on the permeability of membranes to propranolol hydrochloride was evaluated by permeation studies conducted in static glass diffusion cells. A decrease in the thermal stability of chitosan membranes due to crosslinking was observed. The tensile strength of the membranes was improved by crosslinking. The introduction of crosslink points within the membrane reduced its permeability to propranolol hydrochloride as evidenced by decreased permeability and diffusion coefficients. Permeability studies revealed the operation of a pore mechanism in the transport of hydrophilic agents such as propranolol hydrochloride through chitosan and crosslinked chitosan membranes. PMID:7764115

  7. Desmosine-Inspired Cross-Linkers for Hyaluronan Hydrogels

    NASA Astrophysics Data System (ADS)

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

    2013-06-01

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

  8. Dynamics of Actively Driven Crosslinked Microtubule Networks

    NASA Astrophysics Data System (ADS)

    Yadav, Vikrant; Stanhope, Kasimira; Evans, Arthur A.; Ross, Jennifer L.

    We have designed a model experiment to explore dynamics of crosslinked active microtubule clusters crosslinked with MAP65. Microtubule clusters are allowed to settle on a slide coated with kinesin-1 molecular motors, which move microtubules. We systematically tune either concentration of cross linkers bound to microtubule (ρc) or the global concentration of microtubules (ρMT) . We quantified the shape of the cluster by measuring the standard deviation (σ) of the cluster outline. At low ρMTor ρc the network is in an expanding state. At higher ρMTor ρc expansion slows down, reaches zero at a critical density, and become negative indicating contraction. Further increase of ρMTor ρc halts any kind of dynamics. The ρMT-ρc phase space shows distinct regions of extensile, contractile and static regimes. We model these results using active hydrodynamic theory. Microtubules are modeled as active rods whereas effect of crosslinkers is modeled using a collision term that prefers anti-parallel alignment of microtubules. A linearized analysis of hydrodynamic equation predicts existence of density driven expanding, contracting, and static phases for microtubule clusters.

  9. Epoxy Crosslinked Silica Aerogels (X-Aerogels)

    NASA Technical Reports Server (NTRS)

    fabrizio, Eve; Ilhan, Faysal; Meador, Mary Ann; Johnston, Chris; Leventis, Nicholas

    2004-01-01

    NASA is interested in the development of strong lightweight materials for the dual role of thermal insulator and structural component for space vehicles; freeing more weight for useful payloads. Aerogels are very-low density materials (0.010 to 0.5 g/cc) that, due to high porosity (meso- and microporosity), can be, depending on the chemical nature of the network, ideal thermal insulators (thermal conductivity approx. 15 mW/mK). However, aerogels are extremely fragile. For practical application of aerogels, one must increase strength without compromising the physical properties attributed to low density. This has been achieved by templated growth of an epoxy polymer layer that crosslinks the "pearl necklace" network of nanoparticles: the framework of a typical silica aerogel. The requirement for conformal accumulation of the epoxy crosslinker is reaction both with the surface of silica and with itself. After cross-linking, the strength of a typical aerogel monolith increases by a factor of 200, in the expense of only a 2-fold increase in density. Strength is increased further by coupling residual unreacted epoxides with diamine.

  10. Covalent cross-linking of the bovine somatotropin dimer. Effects on growth-promoting, receptor-binding and immunological activities and preliminary characterization of the self-association.

    PubMed Central

    Fernández, H N; Delfino, J M

    1983-01-01

    Bovine somatotropin, at pH 8.5 in 0.02 M-Bicine [NN-bis-(2-hydroxyethyl)glycine]/0.09M-NaCl, showed by frontal analysis the characteristics of a rapid monomer-dimer equilibrium whose dissociation constant was estimated to be 6.6 X 10(-6)M. Reaction of the hormone with dimethyl suberimidate lead to covalent cross-linking of the dimeric species. Under the conditions chosen (0.4 mg of bifunctional imidate and 1 mg of protein/ml at room temperature for 1 h) the cross-linked dimers accounted for 26% of the total protein, and these were isolated by molecular sieving in 0.29M-NH3/0.12M-NaCl. Covalent stabilization greatly diminished the growth-promoting activity and the ability to interact with somatogenic sites in both rat liver in vivo and rabbit liver microsomal fractions. Evidence indicating a non-critical role for amino groups involved in the covalent cross-linking was provided by a nearly equivalent derivative obtained after reaction with 3,3'-dithiobispropionimidate, which had substantial hormonal activity upon cleavage of the disulphide links. Conversely, immunological reactivity as demonstrated by radioimmunoassay was not affected by cross-linking. Details of the least-squares procedure employed to evaluate the self-association equilibrium constant has been deposited as Supplement SUP 50115 (7 pages) with the British Library Lending Division, Boston Spa, Wetherby, West Yorkshire LS23 7BQ, U.K., from whom copies may be obtained on the terms indicated in Biochem.J. (1981) 193,5. Images Fig. 1. PMID:6303298

  11. A new injectable biphasic hydrogel based on partially hydrolyzed polyacrylamide and nano hydroxyapatite, crosslinked with chromium acetate, as scaffold for cartilage regeneration

    NASA Astrophysics Data System (ADS)

    Koushki, N.; Tavassoli, H.; Katbab, A. A.; Katbab, P.; Bonakdar, S.

    2015-05-01

    Polymer scaffolds are applied in the field of tissue engineering as three dimensional structures to organize cells and present stimuli to direct generation of a desired damaged tissue. In situ gelling scaffolds have attracted great attentions, as they are structurally similar to the extra cellular matrix (ECM). In the present work, attempts have been made to design and fabricate a new injectable and crosslinkable biphasic hydrogel based on partially hydrolyzed polyacrylamide (HPAM), chromium acetate as crosslink agent and nanocrystalline hydroxyapatite (nHAp) as reinforcing and bioactive agent for repair and regeneration of damaged cartilage. The distinct characteristic of HPAM is the presence of carboxylate anion groups on its backbone which allows to engineer the structure of the hydrogel for the desired bioactivity with appropriate cells differentiation towards both soft and hard (bone) tissues. The synthesized hydrogel exhibited bifunctional behavior which was derived by its biphasic structure in which one phase was loaded with nano hydroxyapatite to provide integration capability by subchondral bones and fix the hydrogel at cartilage defect without a need for suturing. The other phase differentiates the rabbit adipogenic mesenchymal stem cells (MSCs) towards soft tissue. Rheomechanical spectrometry (RMS) was employed to study the kinetic of the gelation including induction time and rate, as well as to measure the ultimate elastic modulus of the optimum crosslinked hydrogel. Surface tension measurement was also performed to tailor the surface characteristics of the gels. In vitro culturing of the cells inside the crosslinked hydrogel revealed high viability and high differentiation of the encapsulated rabbit stem cells, providing that the chromium acetate level was kept below 0.2 wt%. Based on the obtained results, the designed and fabricated biphasic hydrogel exhibited high potential as carrier for the stem cells for cartilage tissue engineering application

  12. Thioredoxin Cross-Linking by Nitrogen Mustard in Lung Epithelial Cells: Formation of Multimeric Thioredoxin/Thioredoxin Reductase Complexes and Inhibition of Disulfide Reduction.

    PubMed

    Jan, Yi-Hua; Heck, Diane E; Casillas, Robert P; Laskin, Debra L; Laskin, Jeffrey D

    2015-11-16

    The thioredoxin (Trx) system, which consists of Trx and thioredoxin reductase (TrxR), is a major cellular disulfide reduction system important in antioxidant defense. TrxR is a target of mechlorethamine (methylbis(2-chloroethyl)amine; HN2), a bifunctional alkylating agent that covalently binds to selenocysteine/cysteine residues in the redox centers of the enzyme, leading to inactivation and toxicity. Mammalian Trx contains two catalytic cysteines; herein, we determined if HN2 also targets Trx. HN2 caused a time- and concentration-dependent inhibition of purified Trx and Trx in A549 lung epithelial cells. Three Trx cross-linked protein complexes were identified in both cytosolic and nuclear fractions of HN2-treated cells. LC-MS/MS of these complexes identified both Trx and TrxR, indicating that HN2 cross-linked TrxR and Trx. This is supported by our findings of a significant decrease of Trx/TrxR complexes in cytosolic TrxR knockdown cells after HN2 treatment. Using purified recombinant enzymes, the formation of protein cross-links and enzyme inhibition were found to be redox status-dependent; reduced Trx was more sensitive to HN2 inactivation than the oxidized enzyme, and Trx/TrxR cross-links were only observed using reduced enzyme. These data suggest that HN2 directly targets catalytic cysteine residues in Trx resulting in enzyme inactivation and protein complex formation. LC-MS/MS confirmed that HN2 directly alkylated cysteine residues on Trx, including Cys32 and Cys35 in the redox center of the enzyme. Inhibition of the Trx system by HN2 can disrupt cellular thiol-disulfide balance, contributing to vesicant-induced lung toxicity. PMID:26451472

  13. Increasing round trip efficiency of hybrid Li-air battery with bifunctional catalysts

    SciTech Connect

    Huang, K; Li, YF; Xing, YC

    2013-07-30

    Previously it was shown that Pt as cathode catalyst ha's a large overpotential during charge in rechargeable hybrid Li-air battery with sulfuric acid catholyte. This article demonstrates that a bifunctional catalyst composed of Pt and IrO2 supported on carbon nanotubes can address this problem. The specially designed and synthesized bifunctional catalyst showed significant overpotential reduction and achieved a round trip energy efficiency of 81% after 10 cycles, higher than many achieved in aprotic Li-O-2 batteries. The hybrid Li-air battery was discharged and recharged for 20 cycles at 0.2 mA/cm(2), showing a fairly stable cell performance. A specific capacity of 306 mAh/g and a specific energy of 1110 Wh/kg were obtained for the hybrid Li-air battery in terms of acid weight. (c) 2013 Elsevier Ltd. All rights reserved.

  14. Synthesis of acid-base bifunctional mesoporous materials by oxidation and thermolysis

    SciTech Connect

    Yu, Xiaofang; Zou, Yongcun; Wu, Shujie; Liu, Heng; Guan, Jingqi; Kan, Qiubin

    2011-06-15

    Graphical abstract: A novel and efficient method has been developed for the synthesis of acid-base bifunctional catalyst. The obtained sample of SO{sub 3}H-MCM-41-NH{sub 2} containing amine and sulfonic acids exhibits excellent catalytic activity in aldol condensation reaction. Research highlights: {yields} Synthesize acid-base bifunctional mesoporous materials SO{sub 3}H-MCM-41-NH{sub 2}. {yields} Oxidation and then thermolysis to generate acidic site and basic site. {yields} Exhibit good catalytic performance in aldol condensation reaction between acetone and various aldehydes. -- Abstract: A novel and efficient method has been developed for the synthesis of acid-base bifunctional catalyst SO{sub 3}H-MCM-41-NH{sub 2}. This method was achieved by co-condensation of tetraethylorthosilicate (TEOS), 3-mercaptopropyltrimethoxysilane (MPTMS) and (3-triethoxysilylpropyl) carbamicacid-1-methylcyclohexylester (3TAME) in the presence of cetyltrimethylammonium bromide (CTAB), followed by oxidation and then thermolysis to generate acidic site and basic site. X-ray diffraction (XRD) and transmission electron micrographs (TEM) show that the resultant materials keep mesoporous structure. Thermogravimetric analysis (TGA), X-ray photoelectron spectra (XPS), back titration, solid-state {sup 13}C CP/MAS NMR and solid-state {sup 29}Si MAS NMR confirm that the organosiloxanes were condensed as a part of the silica framework. The bifunctional sample (SO{sub 3}H-MCM-41-NH{sub 2}) containing amine and sulfonic acids exhibits excellent acid-basic properties, which make it possess high activity in aldol condensation reaction between acetone and various aldehydes.

  15. Porous cobalt-based thin film as a bifunctional catalyst for hydrogen generation and oxygen generation.

    PubMed

    Yang, Yang; Fei, Huilong; Ruan, Gedeng; Tour, James M

    2015-05-27

    A mixed-phased Co-based catalyst composed of Co phosphide and Co phosphate is successfully fabricated for bifunctional water electrolysis. The highly porous morphology in this anodized film enables efficient catalytic activity toward water splitting in an extremely low loading mass. The mixed phases in the porous film afford an ability to generate both H2 and O2 in a single electrolyzer. PMID:25872881

  16. Highly enantioselective conjugate addition of malononitrile to 2-enoylpyridines with bifunctional organocatalyst.

    PubMed

    Molleti, Nagaraju; Rana, Nirmal K; Singh, Vinod K

    2012-09-01

    An efficient enantioselective conjugate addition of malononitrile to a range of β-substituted 2-enoylpyridines catalyzed by cinchona alkaloid-based bifunctional urea catalysts has been developed. Both enantiomers of the products could be achieved with the same level of enantioselectivity by using pseudoenantiomeric catalysts in up to 97% ee and in excellent yields. One of the enantioenriched products has been transformed to a highly functionalized piperidone derivative. PMID:22920458

  17. 3D Ordered Mesoporous Bifunctional Oxygen Catalyst for Electrically Rechargeable Zinc-Air Batteries.

    PubMed

    Park, Moon Gyu; Lee, Dong Un; Seo, Min Ho; Cano, Zachary Paul; Chen, Zhongwei

    2016-05-01

    To enhance energy efficiency and durability, a highly active and durable 3D ordered mesoporous cobalt oxide framework has been developed for rechargeable zinc-air batteries. The bifunctional air electrode consisting of 3DOM Co3 O4 having high active surface area and robust structure, results in superior charge and discharge battery voltages, and durable performance for electrically rechargeable zinc-air batteries. PMID:27043451

  18. L-Proline Derived Bifunctional Organocatalysts: Enantioselective Michael Addition of Dithiomalonates to trans-β-Nitroolefins.

    PubMed

    Jin, Hui; Kim, Seung Tae; Hwang, Geum-Sook; Ryu, Do Hyun

    2016-04-15

    A series of novel L-proline derived tertiary amine bifunctional organocatalysts 9 are reported, which were applied to the asymmetric Michael addition of dithiomalonates 2 to trans-β-nitroolefins 1. The reaction proceeded in high yields (up to 99%) with high enantioselectivities (up to 97% ee). The synthetic utility of this methodology was demonstrated in the short synthesis of (R)-phenibut in high yield. PMID:26989804

  19. Evolution of a bifunctional enzyme: 6-phosphofructo-2-kinase/fructose-2,6-bisphosphatase.

    PubMed Central

    Bazan, J F; Fletterick, R J; Pilkis, S J

    1989-01-01

    The bifunctional rat liver enzyme 6-phosphofructo-2-kinase/fructose-2,6-bisphosphatase (ATP:D-fructose-6-phosphate 2-phosphotransferase/D-fructose-2,6-bisphosphate 2-phosphohydrolase, EC 2.7.1.105/EC 3.1.3.46) is constructed of two independent catalytic domains. We present evidence that the kinase and bisphosphatase halves of the bifunctional enzyme are, respectively, structurally similar to the glycolytic enzymes 6-phosphofructo-1-kinase and phosphoglycerate mutase. Computer-assisted modeling of the C-terminal bisphosphatase domain reveals a hydrophobic core and active site residue constellation equivalent to the yeast mutase structure; structural differences map to length-variable, surface-located loops. Sequence patterns derived from the structural alignment of mutases and the bisphosphatase further detect a significant similarity to a family of acid phosphatases. The N-terminal kinase domain, in turn, is predicted to form a nucleotide-binding fold that is analogous to a segment of 6-phosphofructo-1-kinase, suggesting that these unrelated enzymes bind fructose 6-phosphate and ATP substrates in a similar geometry. This analysis indicates that the bifunctional enzyme is the likely product of gene fusion of kinase and mutase/phosphatase catalytic units. Images PMID:2557623

  20. Bifunctional Perovskite Oxide Catalysts for Oxygen Reduction and Evolution in Alkaline Media.

    PubMed

    Gupta, Shiva; Kellogg, William; Xu, Hui; Liu, Xien; Cho, Jaephil; Wu, Gang

    2016-01-01

    Oxygen electrocatalysis, namely of the oxygen reduction reaction (ORR) and the oxygen evolution reaction (OER), governs the performance of numerous electrochemical energy systems such as reversible fuel cells, metal-air batteries, and water electrolyzers. However, the sluggish kinetics of these two reactions and their dependency on expensive noble metal catalysts (e.g, Pt or Ir) prohibit the sustainable commercialization of these highly innovative and in-demand technologies. Bifunctional perovskite oxides have emerged as a new class of highly efficient non-precious metal catalysts (NPMC) for oxygen electrocatalysis in alkaline media. In this review, we discuss the state-of-the-art understanding of bifunctional properties of perovskites with regards to their OER/ORR activity in alkaline media and review the associated reaction mechanisms on the oxides surface and the related activity descriptors developed in the recent literature. We also summarize the present strategies to modify their electronic structure and to further improve their performance for the ORR/OER through highlighting the new concepts relating to the role of surface redox chemistry and oxygen deficiency of perovskite oxides for the ORR/OER activity. In addition, we provide a brief account of recently developed advanced perovskite-nanocarbon hybrid bifunctional catalysts with much improved performances. PMID:26247625

  1. Comparison of Dynamical Behaviors Between Monofunctional and Bifunctional Two-Component Signaling Modules

    NASA Astrophysics Data System (ADS)

    Yang, Xiyan; Wu, Yahao; Yuan, Zhanjiang

    2015-06-01

    Two-component signaling modules exist extensively in bacteria and microbes. These modules can be, based on their distinct network structures, divided into two types: the monofunctional system (denoted by MFS) where the sensor kinase (SK) modulates only phosphorylation of the response regulator (RR), and the bifunctional system (denoted by BFS) where the SK catalyzes both phosphorylation and dephosphorylation of the RR. Here, we analyze dynamical behaviors of these two systems based on stability theory, focusing on differences between them. The analysis of the deterministic behavior indicates that there is no difference between the two modules, that is, each system has the unique stable steady state. However, there are significant differences in stochastic behavior between them. Specifically, if the mean phosphorylated SK level is kept the same for the two modules, then the variance and the Fano factor for the phosphorylated RR in the BFS are always no less than those in the MFS, indicating that bifunctionality always enhances fluctuations. The correlation between the phosphorylated SK and the phosphorylated RR in the BFS is always positive mainly due to competition between system components, but this correlation in the MFS may be positive, almost zero, or negative, depending on the ratio between two rate constants. Our overall analysis indicates that differences between dynamical behaviors of monofunctional and bifunctional signaling modules are mainly in the stochastic rather than deterministic aspect.

  2. Development of Cobalt Hydroxide as a Bifunctional Catalyst for Oxygen Electrocatalysis in Alkaline Solution.

    PubMed

    Zhan, Yi; Du, Guojun; Yang, Shiliu; Xu, Chaohe; Lu, Meihua; Liu, Zhaolin; Lee, Jim Yang

    2015-06-17

    Co(OH)2 in the form of hexagonal nanoplates synthesized by a simple hydrothermal reaction has shown even greater activity than cobalt oxides (CoO and Co3O4) in oxygen reduction and oxygen evolution reactions (ORR and OER) under alkaline conditions. The bifunctionality for oxygen electrocatalysis as shown by the OER-ORR potential difference (ΔE) could be reduced to as low as 0.87 V, comparable to the state-of-the-art non-noble bifunctional catalysts, when the Co(OH)2 nanoplates were compounded with nitrogen-doped reduced graphene oxide (N-rGO). The good performance was attributed to the nanosizing of Co(OH)2 and the synergistic interaction between Co(OH)2 and N-rGO. A zinc-air cell assembled with a Co(OH)2-air electrode also showed a performance comparable to that of the state-of-the-art zinc-air cells. The combination of bifunctional activity and operational stability establishes Co(OH)2 as an effective low-cost alternative to the platinum group metal catalysts. PMID:25997179

  3. Enhanced Bifunctional Oxygen Catalysis in Strained LaNiO3 Perovskites

    DOE PAGESBeta

    Petrie, Jonathan R.; Cooper, Valentino R.; Freeland, John W.; Meyer, Tricia L.; Zhang, Zhiyong; Lutterman, Daniel A.; Lee, Ho Nyung

    2016-02-11

    Strain is known to greatly influence low-temperature oxygen electrocatalysis on noble metal films, leading to significant enhancements in bifunctional activity essential for fuel cells and metal-air batteries. Still, its catalytic impact on transition-metal oxide thin films, such as perovskites, is not widely understood. Here, we epitaxially strain the conducting perovskite LaNiO3 to systematically determine its influence on both the oxygen reduction and oxygen evolution reaction. Uniquely, we found that compressive strain could significantly enhance both reactions, yielding a bifunctional catalyst that surpasses the performance of noble metals such as Pt. We attribute the improved bifunctionality to strain-induced splitting of themore » eg orbitals, which can customize orbital asymmetry at the surface. Lastly, analogous to strain-induced shifts in the d-band center of noble metals relative to the Fermi level, such splitting can dramatically affect catalytic activity in this perovskite and other potentially more active oxides.« less

  4. (S)-5-(p-Nitrobenzyl)-PCTA, a Promising Bifunctional Ligand with Advantageous Metal Ion Complexation Kinetics

    PubMed Central

    Tircsó, Gyula; Benyó, Enikő Tircsóné; Suh, Eul Hyun; Jurek, Paul; Kiefer, Garry E.; Sherry, A. Dean; Kovács, Zoltán

    2009-01-01

    A bifunctional version of PCTA (3,6,9,15-tetraazabicyclo[9.3.1]pentadeca-1(15),11,13-triene-3,6,9,-triacetic acid) that exhibits fast complexation kinetics with the trivalent lanthanide(III) ions was synthesized in reasonable yields starting from N, N′, N″-tristosyl-(S)-2-(p-nitrobenzyl)-diethylenetriamine. pH-potentiometric studies showed that the basicities of p-nitrobenzyl-PCTA and the parent ligand PCTA were similar. The stability of M(NO2-Bn-PCTA) (M = Mg2+, Ca2+, Cu2+, Zn2+) complexes was similar to that of the corresponding PCTA complexes while the stability of Ln3+ complexes of the bifunctional ligand is somewhat lower than that of PCTA chelates. The rate of complex formation of Ln(NO2-Bn-PCTA) complexes was found to be quite similar to that of PCTA, a ligand known to exhibit the fastest formation rates among all lanthanide macrocyclic ligand complexes studied to date. The acid catalyzed decomplexation kinetic studies of the selected Ln(NO2-Bn-PCTA) complexes showed that the kinetic inertness of the complexes was comparable to that of Ln(DOTA) chelates making the bifunctional ligand NO2-Bn-PCTA suitable for labeling biological vectors with radioisotopes for nuclear medicine applications. PMID:19220012

  5. Investigation of Mg2+- and temperature-dependent folding of the hairpin ribozyme by photo-crosslinking: effects of photo-crosslinker tether length and chemistry.

    PubMed

    Borda, Emily J; Sigurdsson, Snorri Th

    2005-01-01

    We have used photo-crosslinking to investigate the structure and dynamics of four-way junction hairpin ribozyme constructs. Four phenylazide photo-crosslinkers were coupled to 2'-NH2-modified U+2 in the substrate and irradiated at different Mg2+ concentrations and temperatures. Consistent with the role of divalent metal ions in hairpin ribozyme folding, we observed more interdomain crosslinks in the presence of Mg2+ than in its absence. In general, we observed intradomain crosslinks to nucleotides 2-11 and interdomain crosslinks to the U1A binding loop. Crosslinks to A26 and G36 in domain B were also observed when crosslinking was carried out at -78 degrees C. In contrast to crosslinking results at higher temperatures (0, 25 and 37 degrees C), similar crosslinks were obtained in the presence and absence of Mg2+ at -78 degrees C, suggesting Mg2+ stabilizes a low-energy hairpin ribozyme conformation. We also evaluated the effects of photo-crosslinker structure and mechanism on crosslinks. First, most crosslinks were to unpaired nucleotides. Second, shorter and longer photo-crosslinkers formed crosslinks to intradomain locations nearer to and farther from photo-crosslinker modification, respectively. Finally, fluorine substitutions on the phenylazide ring did not change the locations of crosslinks, but rather decreased crosslinking efficiency. These findings have implications for the use of phenylazide photo-crosslinkers in structural studies of RNA. PMID:15722480

  6. Collagen cross-linking and resorption: effect of glutaraldehyde concentration.

    PubMed

    Roe, S C; Milthorpe, B K; Schindhelm, K

    1990-12-01

    Cross-linked collagen bioprostheses usually are designed to be inert and nonresorbable, resulting in fatigue and wear failure in high-stress environments. Eventual replacement of the implant, although minimizing strength loss during resorption, would result in a graft with reparative ability. Kangaroo tail tendon (KTT) partially cross-linked with glutaraldehyde (GA) was evaluated in vitro for resistance to bacterial collagenase digestion and in vivo for biocompatibility and resorbability in an intramuscular implant assay. Cross-linking was quantified by thermal denaturation studies. Incomplete cross-linking was achieved with concentrations of GA less than 0.1% (w/v). KTT cross-linked in greater than or equal to 0.05% GA were collagenase resistant being incompletely digested after 240 h. Cross-linking of KTT with low concentrations of GA resulted in partial collagenase resistance and slowed resorption. PMID:2126427

  7. Recovery system containing lanthanide-crosslinked polymers

    SciTech Connect

    Dovan, H.T.; Hutchins, R.D.

    1993-07-13

    A recovery system is described comprising: (a) a subterranean formation; (b) a well bore penetrating at least a portion of the subterranean formation; and (c) a composition capable of forming a gel present in at least a portion of the well bore, wherein the composition comprises: (i) a crosslinkable polymer (CP) selected from the group consisting of heteropolysaccharides obtained by the fermentation of starch-derived sugar, ammonium salts, and alkali metal salts; (ii) a lanthanide; and (iii) an ingredient selected from the group consisting of gel breakers, sequestering agents, proppants for use in hydraulically fracturing, particulate agents for forming a gravel pack, and base precursors selected from the group consisting of ammonium slats, urea, thiourea, and mixtures of these. A second recovery system is described in which the gel composition comprises: (i) a CP selected from the group consisting of acrylic acid-acrylamide copolymers, acrylic acid-methacrylamide copolymers, polyacrylamides, polymethacrylamides, partially hydrolyzed polyacrylamides, partially hydrolyzed polymethacrylamides, polyvinyl alcohol, polyvinyl acetate, polyvinyl pyrrolidone, polyalkyleneoxides, lignosulfonates, ammonium salts, alkali metal salts, and alkaline earth salts of lignosulfonates; and (ii) a crosslinking agent selected from the group consisting of lanthanides, sequestered lanthanides, and mixtures thereof. A third system is described in which the gel composition comprises: (i) a CP, hydroxyethylcellulose; and (ii) a crosslinking agent selected from the group consisting of lanthanides, sequestered lanthanides, and mixtures thereof. A fourth system is described in which the gel composition comprises: (i) a CP selected from the group consisting of polyvinyl alcohol, polyvinyl acetate, polyvinyl pyrrolidone, polyalkyleneoxides, lignosulfonates, ammonium salts, alkali metal salts, and alkaline earth salts of lignosulfonates; and (ii) a lanthanide.

  8. Contraction of cross-linked actomyosin bundles

    NASA Astrophysics Data System (ADS)

    Yoshinaga, Natsuhiko; Marcq, Philippe

    2012-08-01

    Cross-linked actomyosin bundles retract when severed in vivo by laser ablation, or when isolated from the cell and micromanipulated in vitro in the presence of ATP. We identify the timescale for contraction as a viscoelastic time τ, where the viscosity is due to (internal) protein friction. We obtain an estimate of the order of magnitude of the contraction time τ ≈ 10-100 s, consistent with available experimental data for circumferential microfilament bundles and stress fibers. Our results are supported by an exactly solvable, hydrodynamic model of a retracting bundle as a cylinder of isotropic, active matter, from which the order of magnitude of the active stress is estimated.

  9. Hydroxyl functionalized thermosensitive microgels with quadratic crosslinking density distribution.

    PubMed

    Elmas, Begum; Tuncel, Murvet; Senel, Serap; Patir, S; Tuncel, Ali

    2007-09-01

    N-isopropylacrylamide (NIPA) based uniform thermosensitive microgels were synthesized by dispersion polymerization by using relatively hydrophilic crosslinking agents with hydroxyl functionality. Glycerol dimethacrylate (GDMA), pentaerythritol triacrylate (PETA) and pentaerythritol propoxylate triacrylate (PEPTA) were used as crosslinking agents with different hydrophilicities. A protocol was first proposed to determine the crosslinking density distribution in the thermosensitive microgel particles by confocal laser scanning microscopy (CLSM). The microgels were fluorescently labeled by using hydroxyl group of the crosslinking agent. The CLSM observations performed with the microgels synthesized by three different crosslinking agents showed that the crosslinking density exhibited a quadratic decrease with the increasing radial distance in the spherical microgel particles. This structure led to the formation of more loose gel structure on the particle surface with respect to the center. Then the use of hydrophilic crosslinking agents in the dispersion polymerization of NIPA made possible the synthesis of thermosensitive microgels carrying long, flexible and chemically derivatizable (i.e., hydroxyl functionalized) fringes on the surface by a single-stage dispersion polymerization. The microgels with all crosslinking agents exhibited volume phase transition with the increasing temperature. The microgel obtained by the most hydrophilic crosslinking agent, GDMA exhibited higher hydrodynamic diameters in the fully swollen form at low temperatures than those obtained by PETA and PEPTA. Higher hydrodynamic size decrease from fully swollen form to the fully shrunken form was also observed with the same microgel. PMID:17532327

  10. Crosslinking of aromatic polyamides via pendant propargyl groups

    NASA Technical Reports Server (NTRS)

    St.clair, A. K.; St.clair, T. L.; Barrick, J. D.; Campbell, F. J.

    1980-01-01

    Methods for crosslinking N-methyl substituted aromatic polyamides were investigated in an effort to improve the applicability of these polymers as matrix resins for Kavlar trademark fiber composites. High molecular weight polymers were prepared from isophthaloyl dichloride and 4,4'- bis(methylamino)diphenylmethane with varying proportions of the N,N'bispropargyl diamine incorporated as a crosslinking agent. The propargylcontaining diamines were crosslinked thermally and characterized by infrared spectroscopy, differential scanning calorimetry, and thermogravimetric analysis. Attempts were also made to crosslink polyamide films by exposure to ultraviolet light, electron beam, and gamma radiation.

  11. A PI 4. 6 peroxidase that specifically crosslinks extensin precursors

    SciTech Connect

    Upham, B.L; Alizadeh, H.; Ryan, K.J.; Lamport, D.T.A. )

    1991-05-01

    The primary cell wall is a microcomposite of cellulose, pectin, hemicellulose and protein. The warp-weft model of the primary cell wall hypothesize that extensin monomers are intermolecularly crosslinked orthogonal to the cellulose microfibril thus mechanically coupling the major load-bearing polymer: cellulose. Media of tomato cell cultures contains heat labile, peroxide dependent crosslinking activity, as determined by the rate of decrease in monomer concentration analyzed via Superose-6. Isoelectric focusing of tomato cell culture media indicated crosslinking was predominantly in the acidic peroxidase fraction (pI4.6). This peroxidase was partially purified by ultracentrifugation, DEAE-Trisacryl and HPLC-DEAE chromatography techniques resulting in a 90 fold purification and 45% yield. A second acidic peroxidase eluted from the HPLC-DEAE column had 25% of the crosslinking activity of the pI 4.6 peroxidase. Purified basic peroxidase had only 0.7% of the activity of the pI 4.6 peroxidase. The specific activity of the pI 4.6 peroxidase was 5,473 mg extensin crosslinked/min/mg peroxidase. The pI 4.6 peroxidase crosslinked the following extensins: tomato I and II, carrot, Ginkgo II and did not crosslink Ginkgo I, Douglas Fir, Maize, Asparagus I and II, and sugarbeet extensins as well as bovine serum albumin. Comparison of motifs common to extensins that are crosslinked by the pI 4.6 peroxidase may help identify the crosslink domain(s) of extension.

  12. Cross-linked polyelectrolyte for direct methanol fuel cells applications based on a novel sulfonated cross-linker

    NASA Astrophysics Data System (ADS)

    Li, Mingyu; Zhang, Gang; Xu, Shuai; Zhao, Chengji; Han, Miaomiao; Zhang, Liyuan; Jiang, Hao; Liu, Zhongguo; Na, Hui

    2014-06-01

    A novel type of cross-linked proton exchange membrane of lower methanol permeation and high proton conductivity is prepared, based on a newly synthesized sulfonated cross-linker: carboxyl terminated benzimidazole trimer bearing sulfonic acid groups (s-BI). Compared to membranes cross-linked with non-sulfonated cross-linker (BI), SPEEK/s-BI-n membranes show higher IEC values and proton conductivities. Meanwhile, oxidative stability and mechanical property of SPEEK/s-BI-n membranes are obviously improved. Among SPEEK/s-BI-n membranes, SPEEK/s-BI-2 exhibits high proton conductivity, low swelling ratio (0.122 S cm-1 and 15.2% at 60 °C, respectively) and low methanol permeability coefficient. These results imply that the cross-linked membranes prepared with the newly sulfonated cross-linker are promising for the direct methanol fuel cells (DMFCs) application.

  13. Organization of Subunits in the Membrane Domain of the Bovine F-ATPase Revealed by Covalent Cross-linking*

    PubMed Central

    Lee, Jennifer; Ding, ShuJing; Walpole, Thomas B.; Holding, Andrew N.; Montgomery, Martin G.; Fearnley, Ian M.; Walker, John E.

    2015-01-01

    The F-ATPase in bovine mitochondria is a membrane-bound complex of about 30 subunits of 18 different kinds. Currently, ∼85% of its structure is known. The enzyme has a membrane extrinsic catalytic domain, and a membrane intrinsic domain where the turning of the enzyme's rotor is generated from the transmembrane proton-motive force. The domains are linked by central and peripheral stalks. The central stalk and a hydrophobic ring of c-subunits in the membrane domain constitute the enzyme's rotor. The external surface of the catalytic domain and membrane subunit a are linked by the peripheral stalk, holding them static relative to the rotor. The membrane domain contains six additional subunits named ATP8, e, f, g, DAPIT (diabetes-associated protein in insulin-sensitive tissues), and 6.8PL (6.8-kDa proteolipid), each with a single predicted transmembrane α-helix, but their orientation and topography are unknown. Mutations in ATP8 uncouple the enzyme and interfere with its assembly, but its roles and the roles of the other five subunits are largely unknown. We have reacted accessible amino groups in the enzyme with bifunctional cross-linking agents and identified the linked residues. Cross-links involving the supernumerary subunits, where the structures are not known, show that the C terminus of ATP8 extends ∼70 Å from the membrane into the peripheral stalk and that the N termini of the other supernumerary subunits are on the same side of the membrane, probably in the mitochondrial matrix. These experiments contribute significantly toward building up a complete structural picture of the F-ATPase. PMID:25851905

  14. Constraining the Lateral Helix of Respiratory Complex I by Cross-linking Does Not Impair Enzyme Activity or Proton Translocation.

    PubMed

    Zhu, Shaotong; Vik, Steven B

    2015-08-21

    Complex I (NADH:ubiquinone oxidoreductase) is a multisubunit, membrane-bound enzyme of the respiratory chain. The energy from NADH oxidation in the peripheral region of the enzyme is used to drive proton translocation across the membrane. One of the integral membrane subunits, nuoL in Escherichia coli, has an unusual lateral helix of ∼75 residues that lies parallel to the membrane surface and has been proposed to play a mechanical role as a piston during proton translocation (Efremov, R. G., Baradaran, R., and Sazanov, L. A. (2010) Nature 465, 441-445). To test this hypothesis we have introduced 11 pairs of cysteine residues into Complex I; in each pair one is in the lateral helix, and the other is in a nearby region of subunit N, M, or L. The double mutants were treated with Cu(2+) ions or with bi-functional methanethiosulfonate reagents to catalyze cross-link formation in membrane vesicles. The yields of cross-linked products were typically 50-90%, as judged by immunoblotting, but in no case did the activity of Complex I decrease by >10-20%, as indicated by deamino-NADH oxidase activity or rates of proton translocation. In contrast, several pairs of cysteine residues introduced at other interfaces of N:M and M:L subunits led to significant loss of activity, in particular, in the region of residue Glu-144 of subunit M. The results do not support the hypothesis that the lateral helix of subunit L functions like a piston, but rather, they suggest that conformational changes might be transmitted more directly through the functional residues of the proton translocation apparatus. PMID:26134569

  15. Self-crosslinking for dimensionally stable and solvent-resistant quaternary phosphonium based hydroxide exchange membranes

    SciTech Connect

    Gu, S; Cai, R; Yan, YS

    2011-01-01

    A simple self-crosslinking strategy, without the needs of a separate crosslinker or a catalyst, is reported here. The crosslinking drastically lowers the water swelling ratio (e.g., 5-10 folds reduction) and provides excellent solvent-resistance. The self-crosslinked membrane (DCL: 5.3%) shows the highest IEC-normalized hydroxide conductivity among all crosslinked HEMs reported.

  16. Corneal Collagen Cross-Linking Outcomes: Review

    PubMed Central

    Jankov II, Mirko R; Jovanovic, Vesna; Delevic, Sladjana; Coskunseven, Efekan

    2011-01-01

    Keratoconus is a condition characterized by biomechanical instability of the cornea, presenting in a progressive, asymmetric and bilateral way. Corneal collagen cross-linking with riboflavin and UVA (CXL) is a new technique of corneal tissue strengthening that combines the use of riboflavin as a photo sensitizer and UVA irradiation. The studies showed that CXL was effective in halting the progression of keratoconus over a period of up to four years. The published studies also revealed a reduction of max K readings by more than 2 D, while the postoperative SEQ was reduced by an average of more than 1 D, and refractive cylinder decreased by about 1 D. No eyes lost any line of BCDVA. Moreover, there was no significant decrease in endothelial cell density. It was also found that CXL treatment was effective with reducing corneal and total wavefront aberrations. Corneal cross-linking has also led to an arrest and/or even a partial reversal of keratectasia in the treatment of iatrogenic ectasia after excimer laser ablation. A primary intervention such as CXL should be considered to potentially increase the biomechanical stability of the corneal tissue and postpone the need of lamellar or penetrating keratoplasty. PMID:21448301

  17. Corneal collagen cross-linking: a review.

    PubMed

    O'Brart, David P S

    2014-01-01

    The aim was to review the published literature on corneal collagen cross-linking. The emphasis was on the seminal publications, systemic reviews, meta-analyses and randomized controlled trials. Where such an evidence did not exist, selective large series cohort studies, case controlled studies and case series with follow-up preferably greater than 12 months were included. Riboflavin/Ultraviolet A (UVA) corneal collagen cross-linking appears to be the first treatment modality to halt the progression of keratoconus and other corneal ectatic disorders with improvement in visual, keratometric and topographic parameters documented by most investigators. Its precise mechanism of action at a molecular level is as yet not fully determined. Follow-up is limited to 4-6 years at present but suggests continued stability and improvement in corneal shape with time. Most published data are with epithelium-off techniques. Epithelium-on studies suggest some efficacy but less than with the epithelium-off procedures and long-term data are not currently available. The use of Riboflavin/UVA CXL for the management of infectious and non-infectious keratitis appears very promising. Its use in the management of bullous keratopathy is equivocal. Investigation of other methodologies for CXL are under investigation. PMID:25000866

  18. Corneal collagen cross-linking: A review

    PubMed Central

    O’Brart, David P.S.

    2014-01-01

    The aim was to review the published literature on corneal collagen cross-linking. The emphasis was on the seminal publications, systemic reviews, meta-analyses and randomized controlled trials. Where such an evidence did not exist, selective large series cohort studies, case controlled studies and case series with follow-up preferably greater than 12 months were included. Riboflavin/Ultraviolet A (UVA) corneal collagen cross-linking appears to be the first treatment modality to halt the progression of keratoconus and other corneal ectatic disorders with improvement in visual, keratometric and topographic parameters documented by most investigators. Its precise mechanism of action at a molecular level is as yet not fully determined. Follow-up is limited to 4–6 years at present but suggests continued stability and improvement in corneal shape with time. Most published data are with epithelium-off techniques. Epithelium-on studies suggest some efficacy but less than with the epithelium-off procedures and long-term data are not currently available. The use of Riboflavin/UVA CXL for the management of infectious and non-infectious keratitis appears very promising. Its use in the management of bullous keratopathy is equivocal. Investigation of other methodologies for CXL are under investigation. PMID:25000866

  19. Mitigating crosslinking reactions through preconversion strategies

    SciTech Connect

    Not Available

    1992-03-01

    The ultimate goal of this research is to develop preconversion techniques that will mitigate crosslinking reactions and thereby substantially increase liquid yields during subsequent liquefaction. The immediate objective is to explore the effect of several pretreatments on the evolution of oxygen functions, crosslinking, and conversion in laboratory studies. The pretreatments to be explored include several that hold promise for effecting deoxygenation or other reduction, for example, treatment with CO/water/base and hydroquinones, either alone or in conjunction. The effects of these pretreatments on functional group distribution, macromoleculer structure, and liquefaction will be compared with those that have shown promise in the past for improved conversions, such as simple hydrothermal pretreatment, mild hydrogenation with dispersed catalysts, and demineralization. A second objective is to develop suitable test procedures for assessing the effect of the pretreatment on subsequent liquefaction and achieve also an understanding the chemical origin of the effect. These test procedures will include the use of proton magnetic resonance thermal analysis (PMRTA) for determining the effect of pretreatment on fluidity as liquefaction conditions (temperature, pressure) are approached. They will also involve the use of simpler and more pertinent laboratory measures of volatile product yields following the batch liquefactions that will be run to test the susceptibility of pretreated coals to subsequent liquefaction.

  20. Protein flexibility is key to cisplatin crosslinking in calmodulin

    PubMed Central

    Li, Huilin; Wells, Stephen A; Jimenez-Roldan, J Emilio; Römer, Rudolf A; Zhao, Yao; Sadler, Peter J; O'Connor, Peter B

    2012-01-01

    Chemical crosslinking in combination with Fourier transform ion cyclotron resonance mass spectrometry (FTICR MS) has significant potential for studying protein structures and protein–protein interactions. Previously, cisplatin has been shown to be a crosslinker and crosslinks multiple methionine (Met) residues in apo-calmodulin (apo-CaM). However, the inter-residue distances obtained from nuclear magnetic resonance structures are inconsistent with the measured distance constraints by crosslinking. Met residues lie too far apart to be crosslinked by cisplatin. Here, by combining FTICR MS with a novel computational flexibility analysis, the flexible nature of the CaM structure is found to be key to cisplatin crosslinking in CaM. It is found that the side chains of Met residues can be brought together by flexible motions in both apo-CaM and calcium-bound CaM (Ca4-CaM). The possibility of cisplatin crosslinking Ca4-CaM is then confirmed by MS data. Therefore, flexibility analysis as a fast and low-cost computational method can be a useful tool for predicting crosslinking pairs in protein crosslinking analysis and facilitating MS data analysis. Finally, flexibility analysis also indicates that the crosslinking of platinum to pairs of Met residues will effectively close the nonpolar groove and thus will likely interfere with the binding of CaM to its protein targets, as was proved by comparing assays for cisplatin-modified/unmodified CaM binding to melittin. Collectively, these results suggest that cisplatin crosslinking of apo-CaM or Ca4-CaM can inhibit the ability of CaM to recognize its target proteins, which may have important implications for understanding the mechanism of tumor resistance to platinum anticancer drugs. PMID:22733664

  1. Large Scale Chemical Cross-linking Mass Spectrometry Perspectives

    PubMed Central

    Zybailov, Boris L.; Glazko, Galina V.; Jaiswal, Mihir; Raney, Kevin D.

    2014-01-01

    The spectacular heterogeneity of a complex protein mixture from biological samples becomes even more difficult to tackle when one’s attention is shifted towards different protein complex topologies, transient interactions, or localization of PPIs. Meticulous protein-by-protein affinity pull-downs and yeast-two-hybrid screens are the two approaches currently used to decipher proteome-wide interaction networks. Another method is to employ chemical cross-linking, which gives not only identities of interactors, but could also provide information on the sites of interactions and interaction interfaces. Despite significant advances in mass spectrometry instrumentation over the last decade, mapping Protein-Protein Interactions (PPIs) using chemical cross-linking remains time consuming and requires substantial expertise, even in the simplest of systems. While robust methodologies and software exist for the analysis of binary PPIs and also for the single protein structure refinement using cross-linking-derived constraints, undertaking a proteome-wide cross-linking study is highly complex. Difficulties include i) identifying cross-linkers of the right length and selectivity that could capture interactions of interest; ii) enrichment of the cross-linked species; iii) identification and validation of the cross-linked peptides and cross-linked sites. In this review we examine existing literature aimed at the large-scale protein cross-linking and discuss possible paths for improvement. We also discuss short-length cross-linkers of broad specificity such as formaldehyde and diazirine-based photo-cross-linkers. These cross-linkers could potentially capture many types of interactions, without strict requirement for a particular amino-acid to be present at a given protein-protein interface. How these shortlength, broad specificity cross-linkers be applied to proteome-wide studies? We will suggest specific advances in methodology, instrumentation and software that are needed to

  2. Unusual non-bifunctional mechanism for Co-PNP complex catalyzed transfer hydrogenation governed by the electronic configuration of metal center.

    PubMed

    Hou, Cheng; Jiang, Jingxing; Li, Yinwu; Zhang, Zhihan; Zhao, Cunyuan; Ke, Zhuofeng

    2015-10-01

    The mimic of hydrogenases has unleashed a myriad of bifunctional catalysts, which are widely used in the catalytic hydrogenation of polar multiple bonds. With respect to ancillary ligands, the bifunctional mechanism is generally considered to proceed via the metal-ligand cooperation transition state. Inspired by the interesting study conducted by Hanson et al. (Chem Commun., 2013, 49, 10151), we present a computational study of a distinctive example, where a Co(II)-PNP catalyst with an ancillary ligand exhibits efficient transfer hydrogenation through a non-bifunctional mechanism. Both the bifunctional and non-bifunctional mechanisms are discussed. The calculated results, which are based on a full model of the catalyst, suggest that the inner-sphere non-bifunctional mechanism is more favorable (by ∼11 kcal mol(-1)) than the outer-sphere bifunctional mechanism, which is in agreement with the experimental observations. The origin of this mechanistic preference of the Co(II)-PNP catalyst can be attributed to its preference for the square planar geometry. A traditional bifunctional mechanism is less plausible for Co(II)-PNP due to the high distortion energy caused by the change in electronic configuration with the varied ligand field. Considering previous studies that focus on the development of ligands more often, this computational study indicates that the catalytic hydrogenation mechanism is controlled not only by the structure of the ligand but also by the electronic configuration of the metal center. PMID:26332273

  3. Chlorine resistant glutaraldehyde crosslinked polyelectrolyte multilayer membranes for desalination.

    PubMed

    Cho, Kwun Lun; Hill, Anita J; Caruso, Frank; Kentish, Sandra E

    2015-05-01

    Crosslinked polyelectrolyte multilayer membranes are synthesized with salt rejection values approaching those of commercial desalination membranes, but with increased chlorine resistance. The membranes are fabricated directly onto porous commercial substrates. Subsequent crosslinking of the polycation layers with glutaraldehyde leads to NaCl rejections of up to 97%, while the incorporation of a highly sulfonated polysulfone polyanion leads to high chlorine resistance. PMID:25776340

  4. Rheology and structure of surface crosslinked surfactant-activated microgels.

    PubMed

    Li, Dongcui; Hsu, Raymond; Figura, Brian; Jacobs, Robert; Li, Sinan; Horvath, Steve; Clifford, Ted; Chari, Krishnan

    2016-09-14

    Nonionic surfactant-activated microgels (SAMs), composed of hydrophobic alkyl acrylates and hydrophilic hydroxyalkyl esters that utilize the effects of surfactant mediated swelling and interaction to provide pH-independent rheological properties, were previously reported as a new pathway to the rheology modification of surfactant solutions. Crosslinking was shown to play an important role in the properties of these soft microgel systems. To understand the impact of crosslinking chemistry on SAM polymers, we have compared two types of SAM polymers: a conventionally crosslinked SAM polymer via allyl pentaerythritol and a novel SAM polymer, where the surface is self-crosslinked via a reactive surfactant. We have systematically characterized the polymer's swelling, rheology and microstructure in a model system containing the polymer, sodium dodecyl sulfate (SDS) and water. Surface self-crosslinking is demonstrated to be a more effective crosslinking approach to create surfactant-mediated interactions between the microgel particles, resulting in more effective rheology modification. Internal crosslinking hinders both the full swelling of the SAM polymer as well as inter-particle bridging interactions, and is therefore less effective. To our best knowledge, this is the first report on creating a novel surface self-crosslinked microgel via a dual-functional reactive surfactant that interacts with a non-reactive surfactant to create a yield stress fluid. PMID:27470971

  5. IMPROVED PHYSICAL PROPERTIES OF ZEIN USING GLYOXAL AS A CROSSLINKER

    Technology Transfer Automated Retrieval System (TEKTRAN)

    The effect of crosslinkers glyoxal, methylglyoxal and formaldehyde on physical properties of zein films was studied. Zein was solubilized in 90%(v/v) aqueous ethanol and the pH was adjusted with either hydrochloric acid or sodium hydroxide. Crosslinkers were added to 0.3, 1, 3 and 6%(w/w by zein w...

  6. Post-Polymerization Crosslinked Polyurethane Shape-Memory Polymers.

    PubMed

    Hearon, K; Gall, K; Ware, T; Maitland, D J; Bearinger, J P; Wilson, T S

    2011-07-01

    Novel urethane shape-memory polymers (SMPs) of significant industrial relevance have been synthesized and characterized. Chemically crosslinked SMPs have traditionally been made in a one-step polymerization of monomers and crosslinking agents. However, these new post-polymerization crosslinked SMPs can be processed into complex shapes by thermoplastic manufacturing methods and later crosslinked by heat exposure or by electron beam irradiation. Several series of linear, olefinic urethane polymers were made from 2-butene-1,4-diol, other saturated diols, and various aliphatic diisocyanates. These thermoplastics were melt-processed into desired geometries and thermally crosslinked at 200°C or radiation crosslinked at 50 kGy. The SMPs were characterized by solvent swelling and extraction, differential scanning calorimetry (DSC), dynamic mechanical analysis (DMA), tensile testing, and qualitative shape-recovery analysis. Swelling and DMA results provided concrete evidence of chemical crosslinking, and further characterization revealed that the urethanes had outstanding mechanical properties. Key properties include tailorable transitions between 25 and 80°C, tailorable rubbery moduli between 0.2 and 4.2 MPa, recoverable strains approaching 100%, failure strains of over 500% at T(g), and qualitative shape-recovery times of less than 12 seconds at body temperature (37°C). Because of its outstanding thermo-mechanical properties, one polyurethane was selected for implementation in the design of a complex medical device. These post-polymerization crosslinked urethane SMPs are an industrially relevant class of highly processable shape-memory materials. PMID:21572577

  7. A photolithographic approach to spatially resolved cross-linked nanolayers.

    PubMed

    Fuchise, Keita; Lindemann, Peter; Heißler, Stefan; Gliemann, Hartmut; Trouillet, Vanessa; Welle, Alexander; Berson, Jonathan; Walheim, Stefan; Schimmel, Thomas; Meier, Michael A R; Barner-Kowollik, Christopher

    2015-03-17

    The preparation of cross-linked nanosheets with 1-2 nm thickness and predefined shape was achieved by lithographic immobilization of trimethacryloyl thioalkanoates onto the surface of Si wafers, which were functionalized with 2-(phenacylthio)acetamido groups via a photoinduced reaction. Subsequent cross-linking via free radical polymerization as well as a phototriggered Diels-Alder reaction under mild conditions on the surface led to the desired nanosheets. Electrospray ionization mass spectrometry (ESI-MS), X-ray photoelectron spectroscopy (XPS), time-of-flight secondary ion mass spectrometry (ToF-SIMS), as well as infrared reflection-absorption spectroscopy (IRRAS) confirmed the success of individual surface-modification and cross-linking reactions. The thickness and lateral size of the cross-linked structures were determined by atomic force microscopy (AFM) for samples prepared on Si wafers functionalized with a self-assembled monolayer of 1H,1H,2H,2H-perfluorodecyl groups bearing circular pores obtained via a polymer blend lithographic approach, which led to the cross-linking reactions occurring in circular nanoareas (diameter of 50-640 nm) yielding an average thickness of 1.2 nm (radical cross-linking), 1.8 nm (radical cross-linking in the presence of 2,2,2-trifluoroethyl methacrylate as a comonomer), and 1.1 nm (photochemical cross-linking) of the nanosheets. PMID:25705846

  8. Post-Polymerization Crosslinked Polyurethane Shape-Memory Polymers

    PubMed Central

    Hearon, K.; Gall, K.; Ware, T.; Maitland, D. J.; Bearinger, J. P.; Wilson, T. S.

    2011-01-01

    Novel urethane shape-memory polymers (SMPs) of significant industrial relevance have been synthesized and characterized. Chemically crosslinked SMPs have traditionally been made in a one-step polymerization of monomers and crosslinking agents. However, these new post-polymerization crosslinked SMPs can be processed into complex shapes by thermoplastic manufacturing methods and later crosslinked by heat exposure or by electron beam irradiation. Several series of linear, olefinic urethane polymers were made from 2-butene-1,4-diol, other saturated diols, and various aliphatic diisocyanates. These thermoplastics were melt-processed into desired geometries and thermally crosslinked at 200°C or radiation crosslinked at 50 kGy. The SMPs were characterized by solvent swelling and extraction, differential scanning calorimetry (DSC), dynamic mechanical analysis (DMA), tensile testing, and qualitative shape-recovery analysis. Swelling and DMA results provided concrete evidence of chemical crosslinking, and further characterization revealed that the urethanes had outstanding mechanical properties. Key properties include tailorable transitions between 25 and 80°C, tailorable rubbery moduli between 0.2 and 4.2 MPa, recoverable strains approaching 100%, failure strains of over 500% at Tg, and qualitative shape-recovery times of less than 12 seconds at body temperature (37°C). Because of its outstanding thermo-mechanical properties, one polyurethane was selected for implementation in the design of a complex medical device. These post-polymerization crosslinked urethane SMPs are an industrially relevant class of highly processable shape-memory materials. PMID:21572577

  9. Multi-Scale Modeling of Cross-Linked Nanotube Materials

    NASA Technical Reports Server (NTRS)

    Frankland, S. J. V.; Odegard, G. M.; Herzog, M. N.; Gates, T. S.; Fay, C. C.

    2005-01-01

    The effect of cross-linking single-walled carbon nanotubes on the Young's modulus of a nanotube-reinforced composite is modeled with a multi-scale method. The Young's modulus is predicted as a function of nanotube volume fraction and cross-link density. In this method, the constitutive properties of molecular representative volume elements are determined using molecular dynamics simulation and equivalent-continuum modeling. The Young's modulus is subsequently calculated for cross-linked nanotubes in a matrix which consists of the unreacted cross-linking agent. Two different cross-linking agents are used in this study, one that is short and rigid (Molecule A), and one that is long and flexible (Molecule B). Direct comparisons between the predicted elastic constants are made for the models in which the nanotubes are either covalently bonded or not chemically bonded to the cross-linking agent. At a nanotube volume fraction of 10%, the Young's modulus of Material A is not affected by nanotube crosslinking, while the Young's modulus of Material B is reduced by 64% when the nanotubes are cross-linked relative to the non-cross-linked material with the same matrix.

  10. Highly crosslinked silicon polymers for gas chromatography columns

    NASA Technical Reports Server (NTRS)

    Shen, Thomas C. (Inventor)

    1994-01-01

    A new highly crosslinked silicone polymer particle for gas chromatography application and a process for synthesizing such copolymer are described. The new copolymer comprises vinyltriethoxysilane and octadecyltrichlorosilane. The copolymer has a high degree of crosslinking and a cool balance of polar to nonpolar sites in the porous silicon polymer assuring fast separation of compounds of variable polarity.

  11. Unidirectional Adsorption of Bifunctional 1,4-Phenylene Diisocyanide on the Ge(100)-2 × 1 Surface.

    PubMed

    Shong, Bonggeun; Sandoval, Tania E; Crow, Allison M; Bent, Stacey F

    2015-03-19

    Adsorption of bifunctional organic molecules on semiconductor surfaces is important for surface modification; however, most bifunctional molecules previously studied have yielded mixtures of singly and dually tethered adsorbates. Here we report the adsorption of bifunctional 1,4-phenylene diisocyanide (PDI) on the Ge(100)-2 × 1 surface, in which singly bound adsorbates are selectively produced. As shown by polarized multiple internal reflection infrared spectroscopy experiments and density functional theory calculations, PDI adsorbates form a single C-dative bonding configuration through one of the isocyanide functionalities, retaining one unreacted isocyanide moiety per adsorbate. The angle of the molecular axis is ∼30° from the surface normal. The delocalized π* molecular orbital of the free molecule is also preserved upon adsorption. These results demonstrate the potential usefulness of isocyanide adsorbates as a means toward selective organic functionalization of semiconductor surfaces. PMID:26262866

  12. Integrating NiCo Alloys with Their Oxides as Efficient Bifunctional Cathode Catalysts for Rechargeable Zinc-Air Batteries.

    PubMed

    Liu, Xien; Park, Minjoon; Kim, Min Gyu; Gupta, Shiva; Wu, Gang; Cho, Jaephil

    2015-08-10

    The lack of high-efficient, low-cost, and durable bifunctional electrocatalysts that act simultaneously for the oxygen reduction reaction (ORR) and the oxygen evolution reaction (OER) is currently one of the major obstacles to commercializing the electrical rechargeability of zinc-air batteries. A nanocomposite CoO-NiO-NiCo bifunctional electrocatalyst supported by nitrogen-doped multiwall carbon nanotubes (NCNT/CoO-NiO-NiCo) exhibits excellent activity and stability for the ORR/OER in alkaline media. More importantly, real air cathodes made from the bifunctional NCNT/CoO-NiO-NiCo catalysts further demonstrated superior performance to state-of-the-art Pt/C or Pt/C+IrO2 catalysts in primary and rechargeable zinc-air batteries. PMID:26118973

  13. Nanostructured Perovskite LaCo1-xMnxO3 as Bifunctional Catalysts for Rechargeable Metal-Air Batteries

    NASA Astrophysics Data System (ADS)

    Ge, Xiaoming; Li, Bing; Wuu, Delvin; Sumboja, Afriyanti; An, Tao; Hor, T. S. Andy; Zong, Yun; Liu, Zhaolin

    2015-09-01

    Bifunctional catalyst that is active for both oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) is one of the most important components of rechargeable metal-air batteries. Nanostructured perovskite bifunctional catalysts comprising La, Co and Mn(LaCo1-xMnxO3, LCMO) are synthesized by hydrothermal methods. The morphology, structure and electrochemical activity of the perovskite bifunctional catalysts are characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD) and rotating disk electrode (RDE) techniques. Nanorod, nanodisc and nanoparticle are typical morphologies of LCMO. The electrocatalytic activity of LCMO is significantly improved by the addition of conductive materials such as carbon nanotube. To demonstrate the practical utilization, LCMO in the composition of LaCo0.8Mn0.2O3(LCMO82) is used as air cathode catalysts for rechargeable zinc-air batteries. The battery prototype can sustain 470 h or 40 discharge-charge cycles equivalent.

  14. Cross-linked polyvinyl alcohol and method of making same

    NASA Technical Reports Server (NTRS)

    Hsu, L. C.; Sheibley, D. W.; Philipp, W. H. (Inventor)

    1981-01-01

    A film-forming polyvinyl alcohol polymer is mixed with a polyaldehyde-polysaccharide cross-linking agent having at least two monosaccharide units and a plurality of aldehyde groups per molecule, perferably an average of at least one aldehyde group per monosaccharide units. The cross-linking agent, such as a polydialdehyde starch, is used in an amount of about 2.5 to 20% of the theoretical amount required to cross-link all of the available hydroxyl groups of the polyvinyl alcohol polymer. Reaction between the polymer and cross-linking agent is effected in aqueous acidic solution to produce the cross-linked polymer. The polymer product has low electrical resistivity and other properties rendering it suitable for making separators for alkaline batteries.

  15. Hydrophobic starch nanocrystals preparations through crosslinking modification using citric acid.

    PubMed

    Zhou, Jiang; Tong, Jin; Su, Xingguang; Ren, Lili

    2016-10-01

    Biodegradable starch nanocrystals prepared by an acid treatment process were modified through crosslinking modification using citric acid as reactant by a dry reaction method. The occurrence of crosslinking modification was evaluated by Fourier transform infrared spectroscopy and swelling degree. X-ray diffraction, wettability tests and contact angle measurements were used to characterize the modified starch nanocrystals. It was found that the crosslinked starch nanocrystals displayed a higher affinity for low polar solvents such as dichloromethane. The surface of starch nanocrystals became more roughness after crosslinking modification with citric acid and the size decreased as revealed by scanning electron microscopy and dynamic light scattering results. XRD analysis showed that the crystalline structure of starch nanocrystals was basically not changed after the crosslinking modification with shorter heating time. The resulting hydrophobic starch nanocrystals are versatile precursors to the development of nanocomposites. PMID:27365120

  16. Cross-linked polyvinyl alcohol films as alkaline battery separators

    NASA Technical Reports Server (NTRS)

    Sheibley, D. W.; Manzo, M. A.; Gonzalez-Sanabria, O. D.

    1982-01-01

    Cross-linking methods were investigated to determine their effect on the performance of polyvinyl alcohol (PVA) films as alkaline battery separators. The following types of cross-linked PVA films are discussed: (1) PVA-dialdehyde blends post-treated with an acid or acid periodate solution (two-step method) and (2) PVA-dialdehyde blends cross-linked during film formation (drying) by using a reagent with both aldehyde and acid functionality (one-step method). Laboratory samples of each cross-linked type of film were prepared and evaluated in standard separator screening tests. The pilot-plant batches of films were prepared and compared to measure differences due to the cross-linking method. The pilot-plant materials were then tested in nickel oxide - zinc cells to compare the two methods with respect to performance characteristics and cycle life. Cell test results are compared with those from tests with Celgard.

  17. Cross-linked polyvinyl alcohol films as alkaline battery separators

    NASA Technical Reports Server (NTRS)

    Sheibley, D. W.; Manzo, M. A.; Gonzalez-Sanabria, O. D.

    1983-01-01

    Cross-linking methods have been investigated to determine their effect on the performance of polyvinyl alcohol (PVA) films as alkaline battery separators. The following types of cross-linked PVA films are discussed: (1) PVA-dialdehyde blends post-treated with an acid or acid periodate solution (two-step method) and (2) PVA-dialdehyde blends cross-linked during film formation (drying) by using a reagent with both aldehyde and acid functionality (one-step method). Laboratory samples of each cross-linked type of film were prepared and evaluated in standard separator screening tests. Then pilot-plant batches of films were prepared and compared to measure differences due to the cross-linking method. The pilot-plant materials were then tested in nickel oxide-zinc cells to compare the two methods with respect to performance characteristics and cycle life. Cell test results are compared with those from tests with Celgard.

  18. Riboflavin for corneal cross-linking.

    PubMed

    O'Brart, D P S

    2016-06-01

    Corneal collagen cross-linking (CXL) with riboflavin and ultraviolet A (UVA) radiation is the first therapeutic modality that appears to arrest the progression of keratoconus and other corneal ectasias. Riboflavin is central to the process, acting as a photosensitizer for the production of oxygen singlets and riboflavin triplets. These free radicals drive the CXL process within the proteins of the corneal stroma, altering its biomechanical properties. Riboflavin also absorbs the majority of the UVA radiation, which is potentially cytotoxic and mutagenic, within the anterior stroma, preventing damage to internal ocular structures, such as the corneal endothelium, lens and retina. Clinical studies report cessation of ectatic progression in over 90% of cases and the majority document significant improvements in visual, keratometric and topographic parameters. Clinical follow-up is limited to 5-10 years, but suggests sustained stability and enhancement in corneal shape. Sight-threatening complications are rare. The optimal stromal riboflavin dosage for CXL is as yet undetermined. PMID:27458610

  19. Autophagy promotes DNA-protein crosslink clearance.

    PubMed

    Mu, Haibo; Liu, Qianjin; Niu, Hong; Wang, Dongdong; Tang, Jiangjiang; Duan, Jinyou

    2016-02-01

    Toxic DNA-protein crosslinks (DPCs) can result from exposure to radiation or chemotherapeutic agents. DPCs can also accumulate during aging or stress. However, the cellular mechanisms underlying clearance of DPCs remain largely unknown. Here, we have identified an important role of autophagy in the processing of DPCs induced by three representative agents: formaldehyde, a chemical used widely in industry; UV light; and camptothecin, a cytotoxic anticancer drug. Autophagy inhibitors, 3-methyladenine (3-MA) or chloroquine (CQ), promoted the accumulation of DPCs in damaged cells and injured organs. siRNA-mediated silencing of Atg5 or Atg7, two essential components for the formation of the autophagosome, gave similar results. In contrast, the autophagy inducer rapamycin (RAP) attenuated DPCs in vitro and in vivo. Our findings reveal the importance of autophagy in controlling the level of DPCs, and may open up a new avenue for understanding the formation and clearance of this detrimental DNA adduct. PMID:26921017

  20. Characterization of modular bifunctional processive endoglucanase Cel5 from Hahella chejuensis KCTC 2396.

    PubMed

    Ghatge, Sunil Subhash; Telke, Amar Anandrao; Kang, Seo-Hee; Arulalapperumal, Venkatesh; Lee, Keun-Woo; Govindwar, Sanjay Prabhu; Um, Youngsoon; Oh, Doo-Byoung; Shin, Hyun-Dong; Kim, Seon-Won

    2014-05-01

    Cel5 from marine Hahella chejuensis is composed of glycoside hydrolase family-5 (GH5) catalytic domain (CD) and two carbohydrate binding modules (CBM6-2). The enzyme was expressed in Escherichia coli and purified to homogeneity. The optimum endoglucanase and xylanase activities of recombinant Cel5 were observed at 65 °C, pH 6.5 and 55 °C, pH 5.5, respectively. It exhibited K m of 1.8 and 7.1 mg/ml for carboxymethyl cellulose and birchwood xylan, respectively. The addition of Ca(2+) greatly improved thermostability and endoglucanase activity of Cel5. The Cel5 retained 90 % of its endoglucanase activity after 24 h incubation in presence of 5 M concentration of NaCl. Recombinant Cel5 showed production of cellobiose after hydrolysis of cellulosic substrates (soluble/insoluble) and methylglucuronic acid substituted xylooligosaccharides after hydrolysis of glucuronoxylans by endo-wise cleavage. These results indicated that Cel5 as bifunctional enzyme having both processive endoglucanase and xylanase activities. The multidomain structure of Cel5 is clearly distinguished from the GH5 bifunctional glycoside hydrolases characterized to date, which are single domain enzymes. Sequence analysis and homology modeling suggested presence of two conserved binding sites with different substrate specificities in CBM6-2 and a single catalytic site in CD. Residues Glu132 and Glu219 were identified as key catalytic amino acids by sequence alignment and further verified by using site directed mutagenesis. CBM6-2 plays vital role in catalytic activity and thermostability of Cel5. The bifunctional activities and multiple substrate specificities of Cel5 can be utilized for efficient hydrolysis of cellulose and hemicellulose into soluble sugars. PMID:24343767

  1. Quinone cross-linked polysaccharide hybrid fiber.

    PubMed

    Kuboe, Yoshiko; Tonegawa, Hitomi; Ohkawa, Kousaku; Yamamoto, Hiroyuki

    2004-01-01

    The present article describes the synthesis of the N-(Lys-Gly-Tyr-Gly)-chitosan using the water-soluble active ester method, the preparation of the N-(Lys-Gly-Tyr-Gly)-chitosan-gellan hybrid fibers, and the reinforcement of the hybrid fibers by enzymatic cross-linking between the N-grafted peptides chains of chitosan. The cationic polysaccharide chitosan was treated with Boc-Lys(Z)-Gly-Tyr(Bzl)-Gly (4-hydroxyphenyl)dimethylsulfonium methyl sulfate ester in DMF-0.15 M acetic acid to incorporate the peptides into the side chain amino groups of chitosan followed by the acidic removals of the Z and Bzl groups. The degrees of N substitution were estimated to be 2.0 and 10 molar % by changing the molar ratios of the amino groups of the parent chitosan and the active ester. The resulting cationic N-(Lys-Gly-Tyr-Gly)-chitosan was spun into the hybrid fibers with the anionic polysaccharide gellan in water. The tensile strengths of the N-(Lys-Gly-Tyr-Gly)-chitosan hybrid fibers were superior to those of the original chitosan-gellan fibers. The mechanical strengths of the hybrid fibers further increased upon enzymatic oxidation using tyrosinase. Based on these results, we concluded that the covalent cross-linking due to the enzyme oxidation between the grafted peptides significantly contributed to reinforcement of the polysaccharide hybrid fibers. The present results afford a new methodology for the reinforcement achieved by the polymer modification inspired by a biological process. PMID:15002994

  2. Glutamyl Phosphate Is an Activated Intermediate in Actin Crosslinking by Actin Crosslinking Domain (ACD) Toxin

    PubMed Central

    Kudryashova, Elena; Kalda, Caitlin; Kudryashov, Dmitri S.

    2012-01-01

    Actin Crosslinking Domain (ACD) is produced by several life-threatening Gram-negative pathogenic bacteria as part of larger toxins and delivered into the cytoplasm of eukaryotic host cells via Type I or Type VI secretion systems. Upon delivery, ACD disrupts the actin cytoskeleton by catalyzing intermolecular amide bond formation between E270 and K50 residues of actin, leading to the formation of polymerization-deficient actin oligomers. Ultimately, accumulation of the crosslinked oligomers results in structural and functional failure of the actin cytoskeleton in affected cells. In the present work, we advanced in our understanding of the ACD catalytic mechanism by discovering that the enzyme transfers the gamma-phosphoryl group of ATP to the E270 actin residue, resulting in the formation of an activated acyl phosphate intermediate. This intermediate is further hydrolyzed and the energy of hydrolysis is utilized for the formation of the amide bond between actin subunits. We also determined the pH optimum for the reaction and the kinetic parameters of ACD catalysis for its substrates, ATP and actin. ACD showed sigmoidal, non-Michaelis-Menten kinetics for actin (K0.5 = 30 µM) reflecting involvement of two actin molecules in a single crosslinking event. We established that ACD can also utilize Mg2+-GTP to support crosslinking, but the kinetic parameters (KM = 8 µM and 50 µM for ATP and GTP, respectively) suggest that ATP is the primary substrate of ACD in vivo. The optimal pH for ACD activity was in the range of 7.0–9.0. The elucidated kinetic mechanism of ACD toxicity adds to understanding of complex network of host-pathogen interactions. PMID:23029200

  3. Supported bifunctional thioureas as recoverable and reusable catalysts for enantioselective nitro-Michael reactions

    PubMed Central

    Ceballos, Miriam; Maestro, Alicia; Sanz, Isabel

    2016-01-01

    Summary The catalytic activity of different supported bifunctional thioureas on sulfonylpolystyrene resins has been studied in the nitro-Michael addition of different nucleophiles to trans-β-nitrostyrene derivatives. The activity of the catalysts depends on the length of the tether linking the chiral thiourea to the polymer. The best results were obtained with the thiourea derived from (L)-valine and 1,6-hexanediamine. The catalysts can be used in only 2 mol % loading, and reused for at least four cycles in neat conditions. The ball milling promoted additions also worked very well. PMID:27340453

  4. Direct transformation of esters into arenes with 1,5-bifunctional organomagnesium reagents.

    PubMed

    Link, Achim; Fischer, Christian; Sparr, Christof

    2015-10-01

    A direct transformation of carboxylic acid esters into arenes with 1,5-bifunctional organomagnesium reagents is described. This efficient and practical method enables the one-step defunctionalization of various carboxylic acid esters to prepare benzene, anthracene, tetracene, and pentacene derivatives. A double nucleophilic addition of the 1,5-organodimagnesium reagent to the ester is followed by an immediate 1,4-elimination reaction that leads to the direct [5+1] formation of a new aromatic ring. PMID:26291060

  5. A novel bifunctional mitochondria-targeted anticancer agent with high selectivity for cancer cells.

    PubMed

    He, Huan; Li, Dong-Wei; Yang, Li-Yun; Fu, Li; Zhu, Xun-Jin; Wong, Wai-Kwok; Jiang, Feng-Lei; Liu, Yi

    2015-01-01

    Mitochondria have recently emerged as novel targets for cancer therapy due to its important roles in fundamental cellular function. Discovery of new chemotherapeutic agents that allow for simultaneous treatment and visualization of cancer is urgent. Herein, we demonstrate a novel bifunctional mitochondria-targeted anticancer agent (FPB), exhibiting both imaging capability and anticancer activity. It can selectively accumulate in mitochondria and induce cell apoptosis. Notably, it results in much higher toxicity toward cancer cells owing to much higher uptake by cancer cells. These features make it highly attractive in cancer imaging and treatment. PMID:26337336

  6. An efficient bifunctional electrocatalyst for water splitting based on cobalt phosphide

    NASA Astrophysics Data System (ADS)

    Yang, Libin; Qi, Honglan; Zhang, Chengxiao; Sun, Xuping

    2016-06-01

    The development of highly efficient electrocatalysts for water splitting is critical for various renewable-energy technologies. In this letter, we demonstrate a cobalt phosphide nanowire array grown on a Ti mesh (CoP/TM) behaving as a bifunctional electrocatalyst for water splitting. The CoP/TM electrode delivers 10 mA cm‑2 at an overpotential of 72 mV for the hydrogen evolution reaction (HER) and 310 mV for the oxygen evolution reaction (OER) in 1.0 M KOH. Furthermore, its corresponding two-electrode alkaline electrolyzer displays 10 mA cm‑2 at 1.64 V.

  7. Bifunctional phase-transfer catalysis in the asymmetric synthesis of biologically active isoindolinones

    PubMed Central

    Di Mola, Antonia; Tiffner, Maximilian; Scorzelli, Francesco; Palombi, Laura; Filosa, Rosanna; De Caprariis, Paolo

    2015-01-01

    Summary New bifunctional chiral ammonium salts were investigated in an asymmetric cascade synthesis of a key building block for a variety of biologically relevant isoindolinones. With this chiral compound in hand, the development of further transformations allowed for the synthesis of diverse derivatives of high pharmaceutical value, such as the Belliotti (S)-PD172938 and arylated analogues with hypnotic sedative activity, obtained in good overall total yield (50%) and high enantiomeric purity (95% ee). The synthetic routes developed herein are particularly convenient in comparison with the current methods available in literature and are particularly promising for large scale applications. PMID:26734105

  8. Au@Cu(II)-MOF: Highly Efficient Bifunctional Heterogeneous Catalyst for Successive Oxidation-Condensation Reactions.

    PubMed

    Wang, Jing-Si; Jin, Fa-Zheng; Ma, Hui-Chao; Li, Xiao-Bo; Liu, Ming-Yang; Kan, Jing-Lan; Chen, Gong-Jun; Dong, Yu-Bin

    2016-07-01

    A new composite Au@Cu(II)-MOF catalyst has been synthesized via solution impregnation and full characterized by HRTEM, SEM-EDS, XRD, gas adsorption-desorption, XPS, and ICP analysis. It has been shown here that the Cu(II)-framework can be a useful platform to stabilize and support gold nanoparticles (Au NPs). The obtained Au@Cu(II)-MOF exhibits a bifunctional catalytic behavior and is able to promote selective aerobic benzyl alcohol oxidation-Knoevenagel condensation in a stepwise way. PMID:27322613

  9. Highly Enantioselective, Intermolecular Hydroamination of Allenyl Esters Catalyzed by Bifunctional Phosphinothioureas

    PubMed Central

    2015-01-01

    Bifunctional phosphinothiourea catalysts have been developed successfully for the highly regio- and enantioselective γ-hydroamination of allenyl and propargyl esters with N-methoxy carbamate nucleophiles to yield α,β-unsaturated γ-amino acid ester products. In the case of propargyl ester substrates, the reaction proceeds through reversible phosphinothiourea-catalyzed isomerization to the corresponding allenyl ester. The high enantioselectivity of the process is attributed to a cooperative conjugate addition of a thiourea-bound carbamate anion to a vinyl phosphonium ion resulting from covalent activation of the allenyl ester substrate. PMID:25496451

  10. Bifunctional Organic Polymeric Catalysts with a Tunable Acid-Base Distance and Framework Flexibility

    NASA Astrophysics Data System (ADS)

    Chen, Huanhui; Wang, Yanan; Wang, Qunlong; Li, Junhui; Yang, Shiqi; Zhu, Zhirong

    2014-09-01

    Acid-base bifunctional organic polymeric catalysts were synthesized with tunable structures. we demonstrated two synthesis approaches for structural fine-tune. In the first case, the framework flexibility was tuned by changing the ratio of rigid blocks to flexible blocks within the polymer framework. In the second case, we precisely adjusted the acid-base distance by distributing basic monomers to be adjacent to acidic monomers, and by changing the chain length of acidic monomers. In a standard test reaction for the aldol condensation of 4-nitrobenzaldehyde with acetone, the catalysts showed good reusability upon recycling and maintained relatively high conversion percentage.

  11. Bifunctional Brønsted Base Catalyzes Direct Asymmetric Aldol Reaction of α-Keto Amides.

    PubMed

    Echave, Haizea; López, Rosa; Palomo, Claudio

    2016-03-01

    The first enantioselective direct cross-aldol reaction of α-keto amides with aldehydes, mediated by a bifunctional ureidopeptide-based Brønsted base catalyst, is described. The appropriate combination of a tertiary amine base and an aminal, and urea hydrogen-bond donor groups in the catalyst structure promoted the exclusive generation of the α-keto amide enolate which reacted with either non-enolizable or enolizable aldehydes to produce highly enantioenriched polyoxygenated aldol adducts without side-products resulting from dehydration, α-keto amide self-condensation, aldehyde enolization, and isotetronic acid formation. PMID:26835655

  12. An efficient bifunctional electrocatalyst for water splitting based on cobalt phosphide.

    PubMed

    Yang, Libin; Qi, Honglan; Zhang, Chengxiao; Sun, Xuping

    2016-06-10

    The development of highly efficient electrocatalysts for water splitting is critical for various renewable-energy technologies. In this letter, we demonstrate a cobalt phosphide nanowire array grown on a Ti mesh (CoP/TM) behaving as a bifunctional electrocatalyst for water splitting. The CoP/TM electrode delivers 10 mA cm(-2) at an overpotential of 72 mV for the hydrogen evolution reaction (HER) and 310 mV for the oxygen evolution reaction (OER) in 1.0 M KOH. Furthermore, its corresponding two-electrode alkaline electrolyzer displays 10 mA cm(-2) at 1.64 V. PMID:27146428

  13. A novel bifunctional mitochondria-targeted anticancer agent with high selectivity for cancer cells

    PubMed Central

    He, Huan; Li, Dong-Wei; Yang, Li-Yun; Fu, Li; Zhu, Xun-Jin; Wong, Wai-Kwok; Jiang, Feng-Lei; Liu, Yi

    2015-01-01

    Mitochondria have recently emerged as novel targets for cancer therapy due to its important roles in fundamental cellular function. Discovery of new chemotherapeutic agents that allow for simultaneous treatment and visualization of cancer is urgent. Herein, we demonstrate a novel bifunctional mitochondria-targeted anticancer agent (FPB), exhibiting both imaging capability and anticancer activity. It can selectively accumulate in mitochondria and induce cell apoptosis. Notably, it results in much higher toxicity toward cancer cells owing to much higher uptake by cancer cells. These features make it highly attractive in cancer imaging and treatment. PMID:26337336

  14. Bifunctional phase-transfer catalysis in the asymmetric synthesis of biologically active isoindolinones.

    PubMed

    Di Mola, Antonia; Tiffner, Maximilian; Scorzelli, Francesco; Palombi, Laura; Filosa, Rosanna; De Caprariis, Paolo; Waser, Mario; Massa, Antonio

    2015-01-01

    New bifunctional chiral ammonium salts were investigated in an asymmetric cascade synthesis of a key building block for a variety of biologically relevant isoindolinones. With this chiral compound in hand, the development of further transformations allowed for the synthesis of diverse derivatives of high pharmaceutical value, such as the Belliotti (S)-PD172938 and arylated analogues with hypnotic sedative activity, obtained in good overall total yield (50%) and high enantiomeric purity (95% ee). The synthetic routes developed herein are particularly convenient in comparison with the current methods available in literature and are particularly promising for large scale applications. PMID:26734105

  15. Tunable catalytic properties of bi-functional mixed oxides in ethanol conversion to high value compounds

    DOE PAGESBeta

    Ramasamy, Karthikeyan K.; Gray, Michel; Job, Heather; Smith, Colin; Wang, Yong

    2016-02-03

    Here, a highly versatile ethanol conversion process to selectively generate high value compounds is presented here. By changing the reaction temperature, ethanol can be selectively converted to >C2 alcohols/oxygenates or phenolic compounds over hydrotalcite derived bi-functional MgO–Al2O3 catalyst via complex cascade mechanism. Reaction temperature plays a role in whether aldol condensation or the acetone formation is the path taken in changing the product composition. This article contains the catalytic activity comparison between the mono-functional and physical mixture counterpart to the hydrotalcite derived mixed oxides and the detailed discussion on the reaction mechanisms.

  16. Recovery of uranium from acid media by macroporous bifunctional phosphinic acid resin

    SciTech Connect

    Sabharwal, K.N.; Srinivasan, T.G.; Rao, P.R.V.; Nandy, K.K.

    1996-11-01

    The extraction of uranium from various acid media such as nitric acid, sulphuric acid, hydrochloric acid, phosphoric acid and perchloric acid by a macroporous bifunctional phosphinic acid resin (MPBPA) has been studied. The distribution coefficients for the extraction of uranium by the MPBPA resin are compared with the corresponding values reported in literature for the conventional sulphonic acid resin. The results clearly indicate the suitability of the MPBPA resin to recover uranium from different types of acid solutions of widely ranging acidities. 17 refs., 6 figs., 5 tabs.

  17. Cobalt nanoparticles embedded in N-doped carbon as an efficient bifunctional electrocatalyst for oxygen reduction and evolution reactions

    NASA Astrophysics Data System (ADS)

    Su, Yunhe; Zhu, Yihua; Jiang, Hongliang; Shen, Jianhua; Yang, Xiaoling; Zou, Wenjian; Chen, Jianding; Li, Chunzhong

    2014-11-01

    Cobalt based catalysts are promising bifunctional electrocatalysts for both oxygen reduction and oxygen evolution reactions (ORR and OER) in unitized regenerative fuel cells (URFCs) operating with alkaline electrolytes. Here we report a hybrid composite of cobalt nanoparticles embedded in nitrogen-doped carbon (Co/N-C) via a solvothermal carbonization strategy. With the synergistic effect arising from the N-doped carbon and cobalt nanoparticles in the composite, the Co/N-C hybrid catalyst exhibits highly efficient bifunctional catalytic activity and excellent stability toward both ORR and OER. The ΔE (oxygen electrode activity parameter for judging the overall electrocatalytic activity of a bifunctional electrocatalyst) value for Co/N-C is 0.859 V, which is smaller than those of Pt/C and most of the non-precious metal catalysts in previous studies. Furthermore, the Co/N-C composite also shows better bifunctional catalytic activity than its oxidative counterparts, which could be attributed to the high specific surface area and the efficient charge transfer ability of the composite, as well as the good synergistic effect between N-doped carbon and the Co nanoparticles in the Co/N-C composite.Cobalt based catalysts are promising bifunctional electrocatalysts for both oxygen reduction and oxygen evolution reactions (ORR and OER) in unitized regenerative fuel cells (URFCs) operating with alkaline electrolytes. Here we report a hybrid composite of cobalt nanoparticles embedded in nitrogen-doped carbon (Co/N-C) via a solvothermal carbonization strategy. With the synergistic effect arising from the N-doped carbon and cobalt nanoparticles in the composite, the Co/N-C hybrid catalyst exhibits highly efficient bifunctional catalytic activity and excellent stability toward both ORR and OER. The ΔE (oxygen electrode activity parameter for judging the overall electrocatalytic activity of a bifunctional electrocatalyst) value for Co/N-C is 0.859 V, which is smaller than those

  18. NiCoMnO4: A Bifunctional Affinity Probe for His-Tagged Protein Purification and Phosphorylation Sites Recognition.

    PubMed

    Qi, Xiaoyue; Chen, Long; Zhang, Chaoqun; Xu, Xinyuan; Zhang, Yiding; Bai, Yu; Liu, Huwei

    2016-07-27

    A bifunctional affinity probe NiCoMnO4 was designed and prepared with controllable morphology and size using facile methods. It was observed that the probe could be applied in His-tagged proteins purification and phosphopeptides enrichment simply through the buffer modulation. NiCoMnO4 particles showed satisfactory cycling performance for His-tagged proteins purification and broad pH-tolerance of loading buffer for phosphopeptides affinity. Therefore, a high-throughput, cost-effective, and efficient protein/peptide purification method was developed within 10 min based on the novel bifunctional affinity probe. PMID:27381638

  19. Quaternary Diamines as Mass Spectrometry Cleavable Crosslinkers for Protein Interactions

    PubMed Central

    Clifford-Nunn, Billy; Showalter, H. D. Hollis; Andrews, Philip C.

    2013-01-01

    Mapping protein interactions and their dynamics is crucial to defining physiologic states, building effective models for understanding cell function, and to allow more effective targeting of new drugs. Crosslinking studies can estimate the proximity of proteins, determine sites of protein–protein interactions, and have the potential to provide a snapshot of dynamic interactions by covalently locking them in place for analysis. Several major challenges are associated with the use of crosslinkers in mass spectrometry, particularly in complex mixtures. We describe the synthesis and characterization of a MS-cleavable crosslinker containing cyclic amines, which address some of these challenges. The DC4 crosslinker contains two intrinsic positive charges, which allow crosslinked peptides to fragment into their component peptides by collision-induced dissociation (CID) or in-source decay. Initial fragmentation events result in cleavage on either side of the positive charges so crosslinked peptides are identified as pairs of ions separated by defined masses. The structures of the component peptides can then be robustly determined by MS3 because their fragmentation products rearrange to generate a mobile proton. The DC4 crosslinking reagent is stable to storage, highly reactive, highly soluble (1 M solutions), quite labile to CID, and MS3 results in productive backbone fragmentation. PMID:22131227

  20. Characterization of the crosslinking reaction in high performance phenolic resins

    NASA Astrophysics Data System (ADS)

    Patel, Jigneshkumar; Zou, Guo Xiang; Hsu, Shaw Ling; university of massachusetts/Polymer science; Engineering Team

    In this study, a combination of thermal analysis, infrared spectroscopy (near and mid) in conjunction with low field NMR, was used to characterize the crosslinking reaction involving phenol formaldehyde resin and a crosslinking agent, Hexamethylenetetramine (HMTA). The strong hydrogen bonds in the resin and the completely crystalline HMTA (Tm = 280 °C) severely hamper the crosslinking process. Yet the addition of a small amount of plasticizer can induce a highly efficient crosslinking reaction to achieve the desired mechanical properties needed in a number of high performance organic-inorganic composites. The infrared spectroscopy clarifies the dissolution process of the crystalline crosslinker and the specific interactions needed to achieve miscibility of the reactants. The thermal analysis enabled us to follow the changing mobility of the system as a function of temperature. The low field NMR with the T1 inverse recovery technique allowed us to monitor the crosslinking process directly. For the first time, it is now possible to identify the functionality of the plasticizer and correlate the crosslinked structure achieved to the macroscopic performance needed for high performance organic-inorganic composites.

  1. Fatigue crack propagation resistance of highly crosslinked polyethylene.

    PubMed

    Bradford, Letitia; Baker, David; Ries, Michael D; Pruitt, Lisa A

    2004-12-01

    A higher degree of cross-linking has been shown to improve wear properties of ultra-high molecular weight polyethylene in laboratory studies. However, cross-linking can also affect the mechanical properties of ultra-high molecular weight polyethylene. Fatigue crack propagation resistance was determined for electron beam cross-linked ultra-high molecular weight polyethylene and compared with gamma irradiation cross-linked and noncross-linked polyethylene fatigue specimens. Crosslinking was done with different dosages of irradiation followed by melting. For one irradiation dose (50 kGy) extrusion and molding processes were compared. A fracture mechanics approach was used to determine how the degree of cross-linking affects resistance to crack propagation in ultra-high molecular weight polyethylene. Fatigue crack propagation resistance was reduced in proportion to the irradiation dose. The type of irradiation (gamma or electron beam) or manufacturing method (extrusion or molding) did not affect fatigue crack propagation resistance. The reduced fatigue strength of highly cross-linked ultra-high molecular weight polyethylene could lead to mechanical failure in conditions that are associated with cyclic local tensile stresses. PMID:15577468

  2. Comparison of cross-linked polyethylene materials for orthopaedic applications.

    PubMed

    Collier, John P; Currier, Barbara H; Kennedy, Francis E; Currier, John H; Timmins, Graham S; Jackson, Simon K; Brewer, Robin L

    2003-09-01

    Cross-linked polyethylenes are being marketed by orthopaedic manufacturers to address the problem of osteolysis caused by polyethylene particulate wear debris. Wear testing of these cross-linked polyethylenes in hip simulators has shown dramatic reduction in wear rate compared with standard ultrahigh molecular weight polyethylene, either gamma irradiated in air or nitrogen - or ethylene oxide-sterilized. However, this reduction in wear rate is not without cost. The cross-linking processes can result in materials with lower mechanical properties than standard ultrahigh molecular weight polyethylene. To evaluate the effect of the various cross-linking processes on physical and mechanical properties of ultrahigh molecular weight polyethylene, commercially available cross-linked polyethylenes from six orthopaedic manufacturers were tested. This study was the culmination of collaboration with these manufacturers, who provided cross-linked polyethylene for this study, wear characteristics of the material they provided, and review of the physical and mechanical properties measure for their polyethylene. Cross-linked materials were evaluated as received and after an accelerated aging protocol. Free radical identity and concentration, oxidation, crystallinity, melt temperature, ultimate tensile strength, elongation at break, tensile stress at yield, and toughness are reported for each material. By comparing these physical and mechanical properties, surgeons can evaluate the trade-off that results from developing materials with substantially lower wear rates. PMID:12966304

  3. A constitutive model of nanocomposite hydrogels with nanoparticle crosslinkers

    NASA Astrophysics Data System (ADS)

    Wang, Qiming; Gao, Zheming

    2016-09-01

    Nanocomposite hydrogels with only nanoparticle crosslinkers exhibit extraordinarily higher stretchability and toughness than the conventional organically crosslinked hydrogels, thus showing great potential in the applications of artificial muscles and cartilages. Despite their potential, the microscopic mechanics details underlying their mechanical performance have remained largely elusive. Here, we develop a constitutive model of the nanoparticle hydrogels to elucidate the microscopic mechanics behaviors, including the microarchitecture and evolution of the nanoparticle crosslinked polymer chains during the mechanical deformation. The constitutive model enables us to understand the Mullins effect of the nanocomposite hydrogels, and the effects of nanoparticle concentrations and sizes on their cyclic stress-strain behaviors. The theory is quantitatively validated by the tensile tests on a nanocomposite hydrogel with nanosilica crosslinkers. The theory can also be extended to explain the mechanical behaviors of existing hydrogels with nanoclay crosslinkers, and the necking instability of the composite hydrogels with both nanoparticle crosslinkers and organic crosslinkers. We expect that this constitutive model can be further exploited to reveal mechanics behaviors of novel particle-polymer chain interactions, and to design unprecedented hydrogels with both high stretchability and toughness.

  4. Characteristics of bifunctional acidic endoglucanase (Cel5B) from Gloeophyllum trabeum.

    PubMed

    Kim, Ho Myeong; Lee, Yoon Gyo; Patel, Darshan H; Lee, Kwang Ho; Lee, Dae-Seok; Bae, Hyeun-Jong

    2012-07-01

    The endoglucanase (Cel5B) from the filamentous fungus Gloeophyllum trabeum was cloned and expressed without a signal peptide, and alanine residue 22 converted to glutamine in Pichia pastoris GS115. The DNA sequence of Cel5B had an open reading frame of 1,077 bp, encoding a protein of 359 amino acid residues with a molecular weight of 47 kDa. On the basis of sequence similarity, Cel5B displayed active site residues at Glu-175 and Glu-287. Both residues lost full hydrolytic activity when replaced with alanine through point mutation. The purified recombinant Cel5B showed very high specific activity, about 80- to 1,000-fold and 13- to 70-fold in comparison with other endoglucanases and cellobiohydrolase, on carboxymethylcellulose and filter paper, respectively, at pH 3.5 and 55°C. Cel5B displayed bifunctional characteristics under acidic conditions. The kinetic properties of the enzyme determined using a Lineweaver-Burk plot indicated that Cel5B is a catalytically efficient cellulolytic enzyme. These results suggest that Cel5B has high bifunctional endo- and exoglucanase activity under acidic conditions and is a good candidate for bioconversion of lignocellulose. PMID:22395898

  5. A bifunctional spin label reports the structural topology of phospholamban in magnetically-aligned bicelles.

    PubMed

    McCaffrey, Jesse E; James, Zachary M; Svensson, Bengt; Binder, Benjamin P; Thomas, David D

    2016-01-01

    We have applied a bifunctional spin label and EPR spectroscopy to determine membrane protein structural topology in magnetically-aligned bicelles, using monomeric phospholamban (PLB) as a model system. Bicelles are a powerful tool for studying membrane proteins by NMR and EPR spectroscopies, where magnetic alignment yields topological constraints by resolving the anisotropic spectral properties of nuclear and electron spins. However, EPR bicelle studies are often hindered by the rotational mobility of monofunctional Cys-linked spin labels, which obscures their orientation relative to the protein backbone. The rigid and stereospecific TOAC label provides high orientational sensitivity but must be introduced via solid-phase peptide synthesis, precluding its use in large proteins. Here we show that a bifunctional methanethiosulfonate spin label attaches rigidly and stereospecifically to Cys residues at i and i+4 positions along PLB's transmembrane helix, thus providing orientational resolution similar to that of TOAC, while being applicable to larger membrane proteins for which synthesis is impractical. Computational modeling and comparison with NMR data shows that these EPR experiments provide accurate information about helix tilt relative to the membrane normal, thus establishing a robust method for determining structural topology in large membrane proteins with a substantial advantage in sensitivity over NMR. PMID:26720587

  6. Bifunctional Spin Labeling of Muscle Proteins: Accurate Rotational Dynamics, Orientation, and Distance by EPR.

    PubMed

    Thompson, Andrew R; Binder, Benjamin P; McCaffrey, Jesse E; Svensson, Bengt; Thomas, David D

    2015-01-01

    While EPR allows for the characterization of protein structure and function due to its exquisite sensitivity to spin label dynamics, orientation, and distance, these measurements are often limited in sensitivity due to the use of labels that are attached via flexible monofunctional bonds, incurring additional disorder and nanosecond dynamics. In this chapter, we present methods for using a bifunctional spin label (BSL) to measure muscle protein structure and dynamics. We demonstrate that bifunctional attachment eliminates nanosecond internal rotation of the spin label, thereby allowing the accurate measurement of protein backbone rotational dynamics, including microsecond-to-millisecond motions by saturation transfer EPR. BSL also allows for accurate determination of helix orientation and disorder in mechanically and magnetically aligned systems, due to the label's stereospecific attachment. Similarly, labeling with a pair of BSL greatly enhances the resolution and accuracy of distance measurements measured by double electron-electron resonance (DEER). Finally, when BSL is applied to a protein with high helical content in an assembly with high orientational order (e.g., muscle fiber or membrane), two-probe DEER experiments can be combined with single-probe EPR experiments on an oriented sample in a process we call BEER, which has the potential for ab initio high-resolution structure determination. PMID:26477249

  7. Bifunctional catalysis of the dedeuteration of methoxyacetone-1,1,3,3,3-d

    SciTech Connect

    Hine, J.; Sinha, A.

    1984-06-15

    The dedeuteration of methoxyacetone-1,1,3,3,3-d/sub 5/ is subject to bifunctional catalysis by 3-(dimethylamino)-propylamine (3DP) and (1R,2S,3R,4R)-3-((dimethylamino)methyl)-1,7,7-trimethyl-2-norbornamine (DTN). These catalysts act by using their primary amino groups to transform the ketone to an iminium ion and their tertiary amino groups to transfer a deuteron internally, changing the iminium ion to an enamine. Although analogous monofunctional bases favor exchange at the methyl position relative to exchange at the methylene position by factors of up to 4-fold, bifunctional catalysis by the diamines used favors the methyl group by 11- to 15-fold. Exchange at the methylene group in the presence of DTN was strongly stereoselective. The pro-S deuteron was removed 12-20 times as rapidly as the pro-R deuteron. This is the result of the steric effect of the methoxy substituent. 19 references, 2 figures, 2 tables.

  8. Bifunctional Ag/C3N4.5 composite nanobelts for photocatalysis and antibacterium.

    PubMed

    Lei, Renbo; Jian, Jikang; Zhang, Zhihua; Song, Bo; Wu, Rong

    2016-09-30

    Multiple functions can be achieved in carbon nitride-based composite nanomaterials by tuning their components and structures. Here, we report on a large-scale synthesis of novel bifunctional Ag/C3N4.5 composite nanobelts (CNBs) with efficient photocatalytic and antibacterial activity. The Ag/C3N4.5 CNBs were synthesized in high yield by a two-step route including a homogeneous precipitation process and a subsequent calcination treatment. The structural, morphological, compositional, and spectroscopic characterizations revealed that the Ag/C3N4.5 CNBs are composed of N-deficient melem ultrathin nanobelts and crystalline Ag nanoparticles attached to the surface of the nanobelts with good contact. The band gap of the Ag/C3N4.5 CNBs is determined to be about 3.04 eV. The efficient photocatalytic and antibacterial activities of the composite nanomaterials are verified by testing the degradation of Rhodamine B (RhB) and the inhibition zone to bacterium E. coli. The work provides a facile route to bifunctional carbon nitride-based composites with potential applications in the fields of the environment and biology. PMID:27560165

  9. Bifunctional graphene/γ-Fe₂O₃ hybrid aerogels with double nanocrystalline networks for enzyme immobilization.

    PubMed

    Chen, Liang; Wei, Bin; Zhang, Xuetong; Li, Chun

    2013-07-01

    Highly porous hosting materials with conducting (favorable to electron transfer) and magnetic (favorable to product separation) bicontinuous networks should possess great potentials for immobilization of various enzymes in the field of biocatalytic engineering, but the synthesis of such materials is still a great challenge. Herein, bifunctional graphene/γ-Fe2 O3 hybrid aerogels with quite low density (30-65 mg cm(-3) ), large specific surface area (270-414 m(2) g(-1) ), high electrical conductivity (0.5-5 × 10(-2) S m(-1) ), and superior saturation magnetization (23-54 emu g(-1) ) are fabricated. Single networks of either graphene aerogels or γ-Fe2 O3 aerogels are obtained by etching of the hybrid aerogels with acid solution or calcining of the hybrid aerogels in air, indicative of the double networks of the as-synthesized graphene/γ-Fe2 O3 hybrid aerogels for the first time. The resulting bifunctional aerogels are used to immobilize β-glucuronidase for biocatalytic transformation of glycyrrhizin into glycyrrhetinic acid monoglucuronide or glycyrrhetinic acid, with high biocatalytic activity and definite repeatability. PMID:23423944

  10. Binuclear platinum (II)-terpyridine complexes. A new class of bifunctional DNA-intercalating agent.

    PubMed Central

    McFadyen, W D; Wakelin, L P; Roos, I A; Hillcoat, B L

    1986-01-01

    A series of binuclear DNA-binding ligands was prepared by linking two (2,2':6',2"-terpyridine)platinum(II) moieties via alpha omega-dithiols of the type HS-[CH2]n-SH where n = 4-10. A monomeric analogue was also synthesized. Compounds were characterized by elemental analysis and electronic and n.m.r. spectroscopy. Viscometric measurements with sonicated rod-like DNA fragments and covalently closed circular DNA were performed to investigate the mode of binding of these agents. The ligands with n = 5 and 6 function as bis intercalators and form a single 'base-pair sandwich' in violation of neighbour-exclusion binding. Bifunctional reaction occurs for the ligand with n = 7, whereas the ligands with n = 8 and 10 show a preference for mixed monofunctional/bifunctional binding. The data do not permit definitive assignment of the binding mode of the ligands with n = 4 and 9. All compounds are growth-inhibitory against mouse leukaemia L1210 cells in culture with IC50 values in the range 2-14 microM. PMID:3800959

  11. Magnetically labelled gold and epoxy bi-functional microcarriers for suspension based bioassay technologies.

    PubMed

    Vyas, Kunal N; Palfreyman, Justin J; Love, David M; Mitrelias, Thanos; Barnes, Crispin H W

    2012-12-21

    Microarrays and suspension-based assay technologies have attracted significant interest over the past decade with applications ranging from medical diagnostics to high throughput molecular biology. The throughput and sensitivity of a microarray will always be limited by the array density and slow reaction kinetics. Suspension (or bead) based technologies offer a conceptually different approach, improving detection by substituting a fixed plane of operation with many individually distinguishable microcarriers. In addition to all the features of a suspension based assay technology, our technology offers a rewritable label. This has the potential to be truly revolutionary by opening up the possibility of generating, on chip, extensive labelled molecular libraries. We unveil our latest SU-8 microcarrier design with embedded magnetic films that can be utilized for both magnetic and optical labelling. The novel design significantly simplifies fabrication and additionally incorporates a gold cap to provide a dual surface, bi-functional architecture. The microcarriers are fabricated using deep-ultraviolet lithography techniques and metallic thin film growth by evaporation. The bi-functional properties of the microcarriers will allow us to use each microcarrier as its own positive control thereby increasing the reliability of our technology. Here we present details of the design, fabrication, magnetic detection and functionalization of these microcarriers. PMID:23128508

  12. A bifunctional spin label reports the structural topology of phospholamban in magnetically-aligned bicelles

    NASA Astrophysics Data System (ADS)

    McCaffrey, Jesse E.; James, Zachary M.; Svensson, Bengt; Binder, Benjamin P.; Thomas, David D.

    2016-01-01

    We have applied a bifunctional spin label and EPR spectroscopy to determine membrane protein structural topology in magnetically-aligned bicelles, using monomeric phospholamban (PLB) as a model system. Bicelles are a powerful tool for studying membrane proteins by NMR and EPR spectroscopies, where magnetic alignment yields topological constraints by resolving the anisotropic spectral properties of nuclear and electron spins. However, EPR bicelle studies are often hindered by the rotational mobility of monofunctional Cys-linked spin labels, which obscures their orientation relative to the protein backbone. The rigid and stereospecific TOAC label provides high orientational sensitivity but must be introduced via solid-phase peptide synthesis, precluding its use in large proteins. Here we show that a bifunctional methanethiosulfonate spin label attaches rigidly and stereospecifically to Cys residues at i and i + 4 positions along PLB's transmembrane helix, thus providing orientational resolution similar to that of TOAC, while being applicable to larger membrane proteins for which synthesis is impractical. Computational modeling and comparison with NMR data shows that these EPR experiments provide accurate information about helix tilt relative to the membrane normal, thus establishing a robust method for determining structural topology in large membrane proteins with a substantial advantage in sensitivity over NMR.

  13. Pushing the Theoretical Limit of Li-CFx Batteries: A Tale of Bi-functional Electrolyte

    SciTech Connect

    Rangasamy, Ezhiylmurugan; Li, Juchuan; Sahu, Gayatri; Dudney, Nancy J; Liang, Chengdu

    2014-01-01

    In a typical battery, electrodes deliver capacities less or equal the theoretical maxima of the electrode materials.1 The inert electrolyte functions solely as the ionic conductor without contribution to the cell capacity because of its distinct mono-function in the concept of conventional batteries. Here we demonstrate that the most energy-dense Li-CFx battery2 delivers a capacity exceeding the theoretical maximum of CFx with a solid electrolyte of Li3PS4 (LPS) that has dual functions: as the inert electrolyte at the anode and the active component at the cathode. Such a bi-functional electrolyte reconciles both inert and active characteristics through a synergistic discharge mechanism of CFx and LPS. Li3PS4 is known as an inactive solid electrolyte with a broad electrochemical window over 5 V.3 The synergy at the cathode is through LiF, the discharge product of CFx, which activates the electrochemical discharge of LPS at a close electrochemical potential of CFx. Therefore, the solid-state Li-CFx batteries output 126.6% energy beyond their theoretic limits without compromising the stability of the cell voltage. The extra energy comes from the electrochemical discharge of LPS, the inert electrolyte. This bi-functional electrolyte revolutionizes the concept of conventional batteries and opens a new avenue for the design of batteries with an unprecedentedly high energy density.

  14. Determining the Origin of Half-bandgap-voltage Electroluminescence in Bifunctional Rubrene/C60 Devices

    PubMed Central

    Chen, Qiusong; Jia, Weiyao; Chen, Lixiang; Yuan, De; Zou, Yue; Xiong, Zuhong

    2016-01-01

    Lowering the driving voltage of organic light-emitting diodes (OLEDs) is an important approach to reduce their energy consumption. We have fabricated a series of bifunctional devices (OLEDs and photovoltaics) using rubrene and fullerene (C60) as the active layer, in which the electroluminescence threshold voltage(~1.1 V) was half the value of the bandgap of rubrene. Magneto-electroluminescence (MEL) response of planner heterojunction diodes exhibited a small increase in response to a low magnetic field strength (<20 mT); however, a very large decay was observed at a high magnetic field strength (>20 mT). When a hole-transport layer with a low mobility was included in these devices, the MEL response reversed in shape, and simultaneously, the EL threshold voltage became larger than the bandgap voltage. When bulk heterojunction device was examined, the amplitude of MEL curves presented an anomalous voltage-dependence. Following an analysis of the MEL responses of these devices, we proposed that the EL of half-bandgap-voltage device originated from bimolecular triplet-triplet annihilation in the rubrene film, rather than from singlet excitons that formed via an interface auger recombination. This work provides critical insight into the mechanisms of OLED emission and will help advance the applications of bifunctional devices. PMID:27142285

  15. Construction of a bifunctional enzyme fusion for the combined determination of biogenic amines in foods.

    PubMed

    Lee, Jae-Ick; Jang, Jun-Hyuck; Yu, Mi-Ji; Kim, Young-Wan

    2013-09-25

    Biogenic amines (BAs) are a group of low-molecular-mass organic bases derived from free amino acids. Due to the undesirable effects of BAs on human health, amine oxidase-based detection methods for BAs in foods have been developed. Here, we developed a bifunctional enzyme fusion (MAPO) using a Cu(2+)-containing monoamine oxidase (AMAO2) and a flavin adenine dinucleotide-containing putrescine oxidase (APUO) from Arthrobacter aurescens. It was necessary to activate MAPO with supplementary Cu(2+) ions, leading to a 6- to 12-fold improvement in catalytic efficiency (kcat/KM) for monoamines. The optimal temperatures of Cu(2+)-activated MAPO (cMAPO) for both tyramine and putrescine were 50 °C, and the optimal pH values for tyramine and putrescine were pH 7.0 and pH 8.0, respectively, consistent with those of AMAO2 and APUO, respectively. The cMAPO showed relative specific activities of 100, 99, 32, and 32 for 2-phenylethylamine, tyramine, histamine, and putrescine, respectively. The tyramine-equivalent BA contents of fermented soybean pastes by cMAPO were more than 90% of the total BA determined by HPLC. In conclusion, cMAPO is fully bifunctional toward biogenic monoamines and putrescine, allowing the combined determination of multiple BAs in foods. This colorimetric determination method could be useful for point-of-care testing to screen safety-guaranteed products prior to instrumental analyses. PMID:24001036

  16. Conversion of cellulose into isosorbide over bifunctional ruthenium nanoparticles supported on niobium phosphate.

    PubMed

    Sun, Peng; Long, Xiangdong; He, Hao; Xia, Chungu; Li, Fuwei

    2013-11-01

    Considerable effort has been applied to the development of new processes and catalysts for cellulose conversion to valuable platform chemicals. Isosorbide is among the most interesting products as it can be applied as a monomer and building block for the future replacement of fossil resource-based products. A sustainable method of isosorbide production from cellulose is presented in this work. The strategy relies on a bifunctional Ru catalyst supported on mesoporous niobium phosphate in a H2 atmosphere under pressure without further addition of any soluble acid. Over 50 % yield of isosorbide with almost 100 % cellulose conversion can be obtained in 1 h. The large surface area, pore size, and strong acidity of mesoporous niobium phosphate promote the hydrolysis of cellulose and dehydration of sorbitol; additionally, the appropriate size of the supported Ru nanoparticles avoids unnecessary hydrogenolysis of sorbitol. Under a cellulose/catalyst mass ratio of 43.3, the present bifunctional catalyst could be stably used up to six times, with its mesoporous structure well preserved and without detectable Ru leaching into the reaction solution. PMID:24115374

  17. Bifunctional Ligands for Inhibition of Tight-Binding Protein-Protein Interactions.

    PubMed

    Ivan, Taavi; Enkvist, Erki; Viira, Birgit; Manoharan, Ganesh Babu; Raidaru, Gerda; Pflug, Alexander; Alam, Kazi Asraful; Zaccolo, Manuela; Engh, Richard Alan; Uri, Asko

    2016-08-17

    The acknowledged potential of small-molecule therapeutics targeting disease-related protein-protein interactions (PPIs) has promoted active research in this field. The strategy of using small molecule inhibitors (SMIs) to fight strong (tight-binding) PPIs tends to fall short due to the flat and wide interfaces of PPIs. Here we propose a biligand approach for disruption of strong PPIs. The potential of this approach was realized for disruption of the tight-binding (KD = 100 pM) tetrameric holoenzyme of cAMP-dependent protein kinase (PKA). Supported by X-ray analysis of cocrystals, bifunctional inhibitors (ARC-inhibitors) were constructed that simultaneously associated with both the ATP-pocket and the PPI interface area of the catalytic subunit of PKA (PKAc). Bifunctional inhibitor ARC-1411, possessing a KD value of 3 pM toward PKAc, induced the dissociation of the PKA holoenzyme with a low-nanomolar IC50, whereas the ATP-competitive inhibitor H89 bound to the PKA holoenzyme without disruption of the protein tetramer. PMID:27389935

  18. Highly Efficient and Robust Nickel Phosphides as Bifunctional Electrocatalysts for Overall Water-Splitting.

    PubMed

    Li, Jiayuan; Li, Jing; Zhou, Xuemei; Xia, Zhaoming; Gao, Wei; Ma, Yuanyuan; Qu, Yongquan

    2016-05-01

    To search for the efficient non-noble metal based and/or earth-abundant electrocatalysts for overall water-splitting is critical to promote the clean-energy technologies for hydrogen economy. Herein, we report nickel phosphide (NixPy) catalysts with the controllable phases as the efficient bifunctional catalysts for water electrolysis. The phases of NixPy were determined by the temperatures of the solid-phase reaction between the ultrathin Ni(OH)2 plates and NaH2PO2·H2O. The NixPy with the richest Ni5P4 phase synthesized at 325 °C (NixPy-325) delivered efficient and robust catalytic performance for hydrogen evolution reaction (HER) in the electrolytes with a wide pH range. The NixPy-325 catalysts also exhibited a remarkable performance for oxygen evolution reaction (OER) in a strong alkaline electrolyte (1.0 M KOH) due to the formation of surface NiOOH species. Furthermore, the bifunctional NixPy-325 catalysts enabled a highly performed overall water-splitting with ∼100% Faradaic efficiency in 1.0 M KOH electrolyte, in which a low applied external potential of 1.57 V led to a stabilized catalytic current density of 10 mA/cm(2) over 60 h. PMID:27064172

  19. Active-site remodelling in the bifunctional fructose-1,6-bisphosphate aldolase/phosphatase.

    PubMed

    Du, Juan; Say, Rafael F; Lü, Wei; Fuchs, Georg; Einsle, Oliver

    2011-10-27

    Fructose-1,6-bisphosphate (FBP) aldolase/phosphatase is a bifunctional, thermostable enzyme that catalyses two subsequent steps in gluconeogenesis in most archaea and in deeply branching bacterial lineages. It mediates the aldol condensation of heat-labile dihydroxyacetone phosphate (DHAP) and glyceraldehyde-3-phosphate (GAP) to FBP, as well as the subsequent, irreversible hydrolysis of the product to yield the stable fructose-6-phosphate (F6P) and inorganic phosphate; no reaction intermediates are released. Here we present a series of structural snapshots of the reaction that reveal a substantial remodelling of the active site through the movement of loop regions that create different catalytic functionalities at the same location. We have solved the three-dimensional structures of FBP aldolase/phosphatase from thermophilic Thermoproteus neutrophilus in a ligand-free state as well as in complex with the substrates DHAP and FBP and the product F6P to resolutions up to 1.3 Å. In conjunction with mutagenesis data, this pinpoints the residues required for the two reaction steps and shows that the sequential binding of additional Mg(2+) cations reversibly facilitates the reaction. FBP aldolase/phosphatase is an ancestral gluconeogenic enzyme optimized for high ambient temperatures, and our work resolves how consecutive structural rearrangements reorganize the catalytic centre of the protein to carry out two canonical reactions in a very non-canonical type of bifunctionality. PMID:21983965

  20. Structural basis for the bifunctionality of fructose-1,6-bisphosphate aldolase/phosphatase.

    PubMed

    Fushinobu, Shinya; Nishimasu, Hiroshi; Hattori, Daiki; Song, Hyun-Jin; Wakagi, Takayoshi

    2011-10-27

    Enzymes catalyse specific reactions and are essential for maintaining life. Although some are referred to as being bifunctional, they consist of either two distinct catalytic domains or a single domain that displays promiscuous substrate specificity. Thus, one enzyme active site is generally responsible for one biochemical reaction. In contrast to this conventional concept, archaeal fructose-1,6-bisphosphate (FBP) aldolase/phosphatase (FBPA/P) consists of a single catalytic domain, but catalyses two chemically distinct reactions of gluconeogenesis: (1) the reversible aldol condensation of dihydroxyacetone phosphate (DHAP) and glyceraldehyde-3-phosphate (GA3P) to FBP; (2) the dephosphorylation of FBP to fructose-6-phosphate (F6P). Thus, FBPA/P is fundamentally different from ordinary enzymes whose active sites are responsible for a specific reaction. However, the molecular mechanism by which FBPA/P achieves its unusual bifunctionality remains unknown. Here we report the crystal structure of FBPA/P at 1.5-Å resolution in the aldolase form, where a critical lysine residue forms a Schiff base with DHAP. A structural comparison of the aldolase form with a previously determined phosphatase form revealed a dramatic conformational change in the active site, demonstrating that FBPA/P metamorphoses its active-site architecture to exhibit dual activities. Thus, our findings expand the conventional concept that one enzyme catalyses one biochemical reaction. PMID:21983966

  1. Determining the Origin of Half-bandgap-voltage Electroluminescence in Bifunctional Rubrene/C60 Devices

    NASA Astrophysics Data System (ADS)

    Chen, Qiusong; Jia, Weiyao; Chen, Lixiang; Yuan, De; Zou, Yue; Xiong, Zuhong

    2016-05-01

    Lowering the driving voltage of organic light-emitting diodes (OLEDs) is an important approach to reduce their energy consumption. We have fabricated a series of bifunctional devices (OLEDs and photovoltaics) using rubrene and fullerene (C60) as the active layer, in which the electroluminescence threshold voltage(~1.1 V) was half the value of the bandgap of rubrene. Magneto-electroluminescence (MEL) response of planner heterojunction diodes exhibited a small increase in response to a low magnetic field strength (<20 mT) however, a very large decay was observed at a high magnetic field strength (>20 mT). When a hole-transport layer with a low mobility was included in these devices, the MEL response reversed in shape, and simultaneously, the EL threshold voltage became larger than the bandgap voltage. When bulk heterojunction device was examined, the amplitude of MEL curves presented an anomalous voltage-dependence. Following an analysis of the MEL responses of these devices, we proposed that the EL of half-bandgap-voltage device originated from bimolecular triplet-triplet annihilation in the rubrene film, rather than from singlet excitons that formed via an interface auger recombination. This work provides critical insight into the mechanisms of OLED emission and will help advance the applications of bifunctional devices.

  2. Large-scale Generation of Patterned Bubble Arrays on Printed Bi-functional Boiling Surfaces

    NASA Astrophysics Data System (ADS)

    Choi, Chang-Ho; David, Michele; Gao, Zhongwei; Chang, Alvin; Allen, Marshall; Wang, Hailei; Chang, Chih-Hung

    2016-04-01

    Bubble nucleation control, growth and departure dynamics is important in understanding boiling phenomena and enhancing nucleate boiling heat transfer performance. We report a novel bi-functional heterogeneous surface structure that is capable of tuning bubble nucleation, growth and departure dynamics. For the fabrication of the surface, hydrophobic polymer dot arrays are first printed on a substrate, followed by hydrophilic ZnO nanostructure deposition via microreactor-assisted nanomaterial deposition (MAND) processing. Wettability contrast between the hydrophobic polymer dot arrays and aqueous ZnO solution allows for the fabrication of heterogeneous surfaces with distinct wettability regions. Heterogeneous surfaces with various configurations were fabricated and their bubble dynamics were examined at elevated heat flux, revealing various nucleate boiling phenomena. In particular, aligned and patterned bubbles with a tunable departure frequency and diameter were demonstrated in a boiling experiment for the first time. Taking advantage of our fabrication method, a 6 inch wafer size heterogeneous surface was prepared. Pool boiling experiments were also performed to demonstrate a heat flux enhancement up to 3X at the same surface superheat using bi-functional surfaces, compared to a bare stainless steel surface.

  3. Large-scale Generation of Patterned Bubble Arrays on Printed Bi-functional Boiling Surfaces.

    PubMed

    Choi, Chang-Ho; David, Michele; Gao, Zhongwei; Chang, Alvin; Allen, Marshall; Wang, Hailei; Chang, Chih-hung

    2016-01-01

    Bubble nucleation control, growth and departure dynamics is important in understanding boiling phenomena and enhancing nucleate boiling heat transfer performance. We report a novel bi-functional heterogeneous surface structure that is capable of tuning bubble nucleation, growth and departure dynamics. For the fabrication of the surface, hydrophobic polymer dot arrays are first printed on a substrate, followed by hydrophilic ZnO nanostructure deposition via microreactor-assisted nanomaterial deposition (MAND) processing. Wettability contrast between the hydrophobic polymer dot arrays and aqueous ZnO solution allows for the fabrication of heterogeneous surfaces with distinct wettability regions. Heterogeneous surfaces with various configurations were fabricated and their bubble dynamics were examined at elevated heat flux, revealing various nucleate boiling phenomena. In particular, aligned and patterned bubbles with a tunable departure frequency and diameter were demonstrated in a boiling experiment for the first time. Taking advantage of our fabrication method, a 6 inch wafer size heterogeneous surface was prepared. Pool boiling experiments were also performed to demonstrate a heat flux enhancement up to 3X at the same surface superheat using bi-functional surfaces, compared to a bare stainless steel surface. PMID:27034255

  4. MULT1E/mIL-12: a novel bifunctional protein for natural killer cell activation.

    PubMed

    Tietje, A; Li, J; Yu, X; Wei, Y

    2014-05-01

    Natural killer (NK) cells have the potential to be effective killers of tumor cells. They are governed by inhibitory and activating receptors like NKG2D, whose ligands are normally upregulated in cells that are stressed, like cancer cells. Advanced cancer cells, however, have ways to reduce these ligands' expression, leaving them less detectable by NK cells. Along with these receptors, NK cells also require activating cytokines, like interleukin 12 (IL-12). The goal of this study is to develop a novel bi-functional fusion protein for enhanced NK cell activation. The proposed protein combines the extracellular domain of the NKG2D ligand Mouse UL-16-binding protein-like transcript 1 (MULT1E) and mouse IL-12 (mIL-12). It is hypothesized that when expressed by tumor cells, the protein will activate NK and other killer cells using the NKG2D receptor, and deliver mIL-12 to the NK cells where it can interact with the IL-12R and enhance cytotoxicity. The fusion protein, when expressed by engineered tumor cells, indeed activated NK cells in vitro as assayed by increased production of interferon-γ and cytotoxicity and significantly reduced tumor growth in vivo. Although the study is preliminary, the data suggest that the MULT1E/mIL-12 bi-functional fusion protein is an effective activator of NK cells for cancer treatment. PMID:24572784

  5. Subnanometer Cobalt-Hydroxide-Anchored N-Doped Carbon Nanotube Forest for Bifunctional Oxygen Catalyst.

    PubMed

    Kim, Ji Eun; Lim, Joonwon; Lee, Gil Yong; Choi, Sun Hee; Maiti, Uday Narayan; Lee, Won Jun; Lee, Ho Jin; Kim, Sang Ouk

    2016-01-27

    Electrochemical oxygen redox reactions are the crucial elements for energy conversion and storage including fuel cells and metal air batteries. Despite tremendous research efforts, developing high-efficient, low-cost, and durable bifunctional oxygen catalysts remains a major challenge. We report a new class of hybrid material consisting of subnanometer thick amorphous cobalt hydroxide anchored on NCNT as a durable ORR/OER bifunctional catalyst. Although amorphous cobalt species-based catalysts are known as good OER catalysts, hybridizing with NCNT successfully enhanced ORR activity by promoting a 4e reduction pathway. Abundant charge carriers in amorphous cobalt hydroxide are found to trigger the superior OER activity with high current density and low Tafel slope as low as 36 mV/decade. A remarkably high OER turnover frequency (TOF) of 2.3 s(-1) at an overpotential of 300 mV was obtained, one of the highest values reported so far. Moreover, the catalytic activity was maintained over 120 h of cycling. The unique subnanometer scale morphology of amorphous hydroxide cobalt species along with intimate cobalt species-NCNT interaction minimizes the deactivation of catalyst during prolonged repeated cycles. PMID:26766495

  6. Determining the Origin of Half-bandgap-voltage Electroluminescence in Bifunctional Rubrene/C60 Devices.

    PubMed

    Chen, Qiusong; Jia, Weiyao; Chen, Lixiang; Yuan, De; Zou, Yue; Xiong, Zuhong

    2016-01-01

    Lowering the driving voltage of organic light-emitting diodes (OLEDs) is an important approach to reduce their energy consumption. We have fabricated a series of bifunctional devices (OLEDs and photovoltaics) using rubrene and fullerene (C60) as the active layer, in which the electroluminescence threshold voltage(~1.1 V) was half the value of the bandgap of rubrene. Magneto-electroluminescence (MEL) response of planner heterojunction diodes exhibited a small increase in response to a low magnetic field strength (<20 mT); however, a very large decay was observed at a high magnetic field strength (>20 mT). When a hole-transport layer with a low mobility was included in these devices, the MEL response reversed in shape, and simultaneously, the EL threshold voltage became larger than the bandgap voltage. When bulk heterojunction device was examined, the amplitude of MEL curves presented an anomalous voltage-dependence. Following an analysis of the MEL responses of these devices, we proposed that the EL of half-bandgap-voltage device originated from bimolecular triplet-triplet annihilation in the rubrene film, rather than from singlet excitons that formed via an interface auger recombination. This work provides critical insight into the mechanisms of OLED emission and will help advance the applications of bifunctional devices. PMID:27142285

  7. Large-scale Generation of Patterned Bubble Arrays on Printed Bi-functional Boiling Surfaces

    PubMed Central

    Choi, Chang-Ho; David, Michele; Gao, Zhongwei; Chang, Alvin; Allen, Marshall; Wang, Hailei; Chang, Chih-hung

    2016-01-01

    Bubble nucleation control, growth and departure dynamics is important in understanding boiling phenomena and enhancing nucleate boiling heat transfer performance. We report a novel bi-functional heterogeneous surface structure that is capable of tuning bubble nucleation, growth and departure dynamics. For the fabrication of the surface, hydrophobic polymer dot arrays are first printed on a substrate, followed by hydrophilic ZnO nanostructure deposition via microreactor-assisted nanomaterial deposition (MAND) processing. Wettability contrast between the hydrophobic polymer dot arrays and aqueous ZnO solution allows for the fabrication of heterogeneous surfaces with distinct wettability regions. Heterogeneous surfaces with various configurations were fabricated and their bubble dynamics were examined at elevated heat flux, revealing various nucleate boiling phenomena. In particular, aligned and patterned bubbles with a tunable departure frequency and diameter were demonstrated in a boiling experiment for the first time. Taking advantage of our fabrication method, a 6 inch wafer size heterogeneous surface was prepared. Pool boiling experiments were also performed to demonstrate a heat flux enhancement up to 3X at the same surface superheat using bi-functional surfaces, compared to a bare stainless steel surface. PMID:27034255

  8. A Bifunctional Enzyme That Has Both Monoacylglycerol Acyltransferase and Acyl Hydrolase Activities1[W][OA

    PubMed Central

    Vijayaraj, Panneerselvam; Jashal, Charnitkaur B.; Vijayakumar, Anitha; Rani, Sapa Hima; Venkata Rao, D.K.; Rajasekharan, Ram

    2012-01-01

    Monoacylglycerol acyltransferase (MGAT) catalyzes the synthesis of diacylglycerol, the precursor of triacylglycerol biosynthesis and an important signaling molecule. Here, we describe the isolation and characterization of the peanut (Arachis hypogaea) MGAT gene. The soluble enzyme utilizes invariant histidine-62 and aspartate-67 residues of the acyltransferase motif for its MGAT activity. A sequence analysis revealed the presence of a hydrolase (GXSXG) motif, and enzyme assays revealed the presence of monoacylglycerol (MAG) and lysophosphatidylcholine (LPC) hydrolytic activities, indicating the bifunctional nature of the enzyme. The overexpression of the MGAT gene in yeast (Saccharomyces cerevisiae) caused an increase in triacylglycerol accumulation. Similar to the peanut MGAT, the Arabidopsis (Arabidopsis thaliana) homolog (At1g52760) also exhibited both acyltransferase and hydrolase activities. Interestingly, the yeast homolog lacks the conserved HX4D motif, and it is deficient in the acyltransferase function but exhibits MAG and LPC hydrolase activities. This study demonstrates the presence of a soluble MGAT/hydrolase in plants. The predicted three-dimensional homology modeling and substrate docking suggested the presence of two separate substrate (MAG and LPC)-binding sites in a single polypeptide. Our study describes a soluble bifunctional enzyme that has both MGAT and hydrolase functions. PMID:22915575

  9. Carbon Nitrogen Nanotubes as Efficient Bifunctional Electrocatalysts for Oxygen Reduction and Evolution Reactions.

    PubMed

    Yadav, Ram Manohar; Wu, Jingjie; Kochandra, Raji; Ma, Lulu; Tiwary, Chandra Sekhar; Ge, Liehui; Ye, Gonglan; Vajtai, Robert; Lou, Jun; Ajayan, Pulickel M

    2015-06-10

    Oxygen reduction and evolution reactions are essential for broad range of renewable energy technologies such as fuel cells, metal-air batteries and hydrogen production through water splitting, therefore, tremendous effort has been taken to develop excellent catalysts for these reactions. However, the development of cost-effective and efficient bifunctional catalysts for both reactions still remained a grand challenge. Herein, we report the electrocatalytic investigations of bamboo-shaped carbon nitrogen nanotubes (CNNTs) having different diameter distribution synthesized by liquid chemical vapor deposition technique using different nitrogen containing precursors. These CNNTs are found to be efficient bifunctional electrocatalyst for oxygen reduction and evolution reactions. The electrocatalytic activity strongly depends on the nanotube diameter as well as nitrogen functionality type. The higher diameter CNNTs are more favorable for these reactions. The increase in nanotube diameter itself enhances the catalytic activity by lowering the oxygen adsorption energy, better conductivity, and further facilitates the reaction by increasing the percentage of catalytically active nitrogen moieties in CNNTs. PMID:25970133

  10. A mesoscopic network model for permanent set in crosslinked elastomers

    SciTech Connect

    Weisgraber, T H; Gee, R H; Maiti, A; Clague, D S; Chinn, S; Maxwell, R S

    2009-01-29

    A mesoscopic computational model for polymer networks and composites is developed as a coarse-grained representation of the composite microstructure. Unlike more complex molecular dynamics simulations, the model only considers the effects of crosslinks on mechanical behavior. The elastic modulus, which depends only on the crosslink density and parameters in the bond potential, is consistent with rubber elasticity theory, and the network response satisfies the independent network hypothesis of Tobolsky. The model, when applied to a commercial filled silicone elastomer, quantitatively reproduces the experimental permanent set and stress-strain response due to changes in the crosslinked network from irradiation.

  11. Cross-Linked Nanotube Materials with Variable Stiffness Tethers

    NASA Technical Reports Server (NTRS)

    Frankland, Sarah-Jane V.; Odegard, Gregory M.; Herzog, Matthew N.; Gates, Thomas S.; Fay, Catherine C.

    2004-01-01

    The constitutive properties of a cross-linked single-walled carbon nanotube material are predicted with a multi-scale model. The material is modeled as a transversely isotropic solid using concepts from equivalent-continuum modeling. The elastic constants are determined using molecular dynamics simulation. Some parameters of the molecular force field are determined specifically for the cross-linker from ab initio calculations. A demonstration of how the cross-linked nanotubes may affect the properties of a nanotube/polyimide composite is included using a micromechanical analysis.

  12. Redox-Responsive, Core Cross-Linked Polyester Micelles

    PubMed Central

    Zhang, Zhonghai; Yin, Lichen; Tu, Chunlai; Song, Ziyuan; Zhang, Yanfeng; Xu, Yunxiang; Tong, Rong; Zhou, Qin; Ren, Jie; Cheng, Jianjun

    2013-01-01

    Monomethoxy poly(ethylene glycol)-b-poly(Tyr(alkynyl)-OCA), a biodegradable amphiphilic block copolymer, was synthesized by means of ring-opening polymerization of 5-(4-(prop-2-yn-1-yloxy)benzyl)-1,3-dioxolane-2,4-dione (Tyr(alkynyl)-OCA) and used to prepare core cross-linked polyester micelles via click chemistry. Core cross-linking not only improved the structural stability of the micelles but also allowed controlled release of cargo molecules in response to the reducing reagent. This new class of core cross-linked micelles can potentially be used in controlled release and drug delivery applications. PMID:23536920

  13. Crosslinked crystalline polymer and methods for cooling and heating

    DOEpatents

    Salyer, Ival O.; Botham, Ruth A.; Ball, III, George L.

    1980-01-01

    The invention relates to crystalline polyethylene pieces having optimum crosslinking for use in storage and recovery of heat, and it further relates to methods for storage and recovery of heat using crystalline polymer pieces having optimum crosslinking for these uses. Crystalline polymer pieces are described which retain at least 70% of the heat of fusion of the uncrosslinked crystalline polymer and yet are sufficiently crosslinked for the pieces not to stick together upon being cycled above and below the melting point of said polymer, preferably at least 80% of the heat of fusion with no substantial sticking together.

  14. Long-Term Persistence of Bi-functionality Contributes to the Robustness of Microbial Life through Exaptation

    PubMed Central

    Sterner, Reinhard; Merkl, Rainer

    2016-01-01

    Modern enzymes are highly optimized biocatalysts that process their substrates with extreme efficiency. Many enzymes catalyze more than one reaction; however, the persistence of such ambiguities, their consequences and evolutionary causes are largely unknown. As a paradigmatic case, we study the history of bi-functionality for a time span of approximately two billion years for the sugar isomerase HisA from histidine biosynthesis. To look back in time, we computationally reconstructed and experimentally characterized three HisA predecessors. We show that these ancient enzymes catalyze not only the HisA reaction but also the isomerization of a similar substrate, which is commonly processed by the isomerase TrpF in tryptophan biosynthesis. Moreover, we found that three modern-day HisA enzymes from Proteobacteria and Thermotogae also possess low TrpF activity. We conclude that this bi-functionality was conserved for at least two billion years, most likely without any evolutionary pressure. Although not actively selected for, this trait can become advantageous in the case of a gene loss. Such exaptation is exemplified by the Actinobacteria that have lost the trpF gene but possess the bi-functional HisA homolog PriA, which adopts the roles of both HisA and TrpF. Our findings demonstrate that bi-functionality can perpetuate in the absence of selection for very long time-spans. PMID:26824644

  15. Facile synthesis of 4-vinyl- and 4-fluorovinyl-1,2,3-triazoles via bifunctional “click-olefination” reagents

    PubMed Central

    Kumar, Rakesh; Pradhan, Padmanava; Zajc, Barbara

    2011-01-01

    Modular synthesis of vinyl and fluorovinyl triazoles can be achieved from bifunctional propargyl and fluoropropargyl sulfones by Cu-catalyzed azide-alkyne ligation and Julia-Kocienski olefination. Competitive click reactions of the protio and fluoropropargyl sulfones show higher reactivity of the latter, and a preliminary DFT analysis was performed. PMID:21336351

  16. Scalable Fabrication of Nanoporous Carbon Fiber Films as Bifunctional Catalytic Electrodes for Flexible Zn-Air Batteries.

    PubMed

    Liu, Qin; Wang, Yaobing; Dai, Liming; Yao, Jiannian

    2016-04-01

    A flexible nanoporous carbon-fiber film for wearable electronics is prepared by a facile and scalable method through pyrolysis of electrospun polyimide. It exhibits excellent bifunctional electrocatalytic activities for oxygen reduction and oxygen evolution. Flexible rechargeable zinc-air batteries based on the carbon-fiber film show high round-trip efficiency and mechanical stability. PMID:26914270

  17. Bifunctional-Phosphine-Catalyzed Sequential Annulations of Allenoates and Ketimines: Construction of Functionalized Poly-heterocycle Rings.

    PubMed

    Li, Erqing; Jin, Hongxing; Jia, Penghao; Dong, Xuelin; Huang, You

    2016-09-12

    A highly stereoselective sequential annulation reaction between γ-substituted allenoates and ketimines was reported. By using bifunctional N-acyl aminophosphine catalysts, poly-heterocycle rings were obtained with high stereocontrol in good to excellent yields. The desired products have four contiguous stereogenic centers (one quaternary and three tertiary carbon centers), and only one isomer was obtained in all reactions. PMID:27529614

  18. Covalently crosslinked diels-alder polymer networks.

    SciTech Connect

    Bowman, Christopher; Adzima, Brian J.; Anderson, Benjamin John

    2011-09-01

    This project examines the utility of cycloaddition reactions for the synthesis of polymer networks. Cycloaddition reactions are desirable because they produce no unwanted side reactions or small molecules, allowing for the formation of high molecular weight species and glassy crosslinked networks. Both the Diels-Alder reaction and the copper-catalyzed azide-alkyne cycloaddition (CuAAC) were studied. Accomplishments include externally triggered healing of a thermoreversible covalent network via self-limited hysteresis heating, the creation of Diels-Alder based photoresists, and the successful photochemical catalysis of CuAAC as an alternative to the use of ascorbic acid for the generation of Cu(I) in click reactions. An analysis of the results reveals that these new methods offer the promise of efficiently creating robust, high molecular weight species and delicate three dimensional structures that incorporate chemical functionality in the patterned material. This work was performed under a Strategic Partnerships LDRD during FY10 and FY11 as part of a Sandia National Laboratories/University of Colorado-Boulder Excellence in Science and Engineering Fellowship awarded to Brian J. Adzima, a graduate student at UC-Boulder. Benjamin J. Anderson (Org. 1833) was the Sandia National Laboratories point-of-contact for this fellowship.

  19. Corneal Cross-Linking and Safety Issues

    PubMed Central

    Spoerl, Eberhard; Hoyer, Anne; Pillunat, Lutz E; Raiskup, Frederik

    2011-01-01

    Purpose: To compile the safety aspects of the corneal collagen cross-linking (CXL) by means of the riboflavin/UVA (370 nm) approach. Materials and Methodology: Analysis of the current treatment protocol with respect to safety during CXL. Results: The currently used UVA dose density of 5.4 J/cm2 and the corresponding irradiance of 3 mW/cm2 are below the known damage thresholds of UVA for the corneal endothelium, lens, and retina. Regarding the photochemical damages due to the free radicals the damage threshold for endothelial cells is 0.35 mW/cm2. In a 400μm thick corneal stroma saturated with riboflavin, the irradiance at the endothelial level is about 0.18 mW/cm2, which is a factor of 2 smaller than the damage threshold. Conclusion: As long as the corneal stroma treated has a minimal thickness of 400 microns (as recommended), neither corneal endothelium nor deeper structures such as lens and retina will suffer any damages. The light source should provide a homogenous irradiance avoiding hot spots. PMID:21399770

  20. Nonlinear elasticity of cross-linked networks

    NASA Astrophysics Data System (ADS)

    John, Karin; Caillerie, Denis; Peyla, Philippe; Raoult, Annie; Misbah, Chaouqi

    2013-04-01

    Cross-linked semiflexible polymer networks are omnipresent in living cells. Typical examples are actin networks in the cytoplasm of eukaryotic cells, which play an essential role in cell motility, and the spectrin network, a key element in maintaining the integrity of erythrocytes in the blood circulatory system. We introduce a simple mechanical network model at the length scale of the typical mesh size and derive a continuous constitutive law relating the stress to deformation. The continuous constitutive law is found to be generically nonlinear even if the microscopic law at the scale of the mesh size is linear. The nonlinear bulk mechanical properties are in good agreement with the experimental data for semiflexible polymer networks, i.e., the network stiffens and exhibits a negative normal stress in response to a volume-conserving shear deformation, whereby the normal stress is of the same order as the shear stress. Furthermore, it shows a strain localization behavior in response to an uniaxial compression. Within the same model we find a hierarchy of constitutive laws depending on the degree of nonlinearities retained in the final equation. The presented theory provides a basis for the continuum description of polymer networks such as actin or spectrin in complex geometries and it can be easily coupled to growth problems, as they occur, for example, in modeling actin-driven motility.

  1. Driven Polymer Translocation into a Crosslinked Gel

    NASA Astrophysics Data System (ADS)

    Sean, David; Slater, Gary

    2015-03-01

    In a typical polymer translocation setup, a thin membrane is used to separate two chambers and a polyelectrolyte is driven by an electric field to translocate from one side of the membrane to the other via a small nanopore. However, the high translocation rate that results from the forces required to drive this process makes optical and/or electrical analysis of the translocating polymer challenging. Using coarse-grained Langevin Dynamics simulations we investigate how the translocation process can be slowed down by placing a crosslinked gel on the trans-side of the membrane. Since the driving electric field is localized in the neighborhood of the nanopore, electrophoretic migration is only achieved by a ``pushing'' action from the polymer segment residing in the nanopore. For the case of a flexible polymer we find that the polymer fills the gel pores via multiple ``herniation'' processes, whereas for a semi-flexible chain in a tight gel there are no hernias and the polymer follows a smooth curvilinear path. Moreover, for the case of a semi-flexible polymer the gel makes the translocation process more uniform by reducing the acceleration at the end of the process.

  2. Crosslink-induced shrinkage of grafted Gaussian chains

    NASA Astrophysics Data System (ADS)

    Benetatos, Panayotis

    2014-04-01

    The statistical mechanics of polymers grafted on surfaces has been the subject of intense research activity because of many potential applications. In this paper, we analytically investigate the conformational changes caused by a single crosslink on two ideal (Gaussian) chains grafted onto a rigid planar surface. Both the crosslink and the surface reduce the number of allowed configurations. In the absence of the hard substrate, the sole effect of the crosslink is a reduction in the effective Kuhn length of a tethered chain. The crosslink-induced shrinkage (collapse) of the grafted chains (mushrooms) turns out to be a reduction in the variance of the distribution of the height of the chain rather than a reduction of the height itself.

  3. Evaluating Dimethyldiethoxysilane for use in Polyurethane Crosslinked Silica Aerogels

    NASA Technical Reports Server (NTRS)

    Randall, Jason P.; Meador, Mary Ann B.; Jana, Sadhan C.

    2008-01-01

    Silica aerogels are highly porous materials which exhibit exceptionally low density and thermal conductivity. Their "pearl necklace" nanostructure, however, is inherently weak; most silica aerogels are brittle and fragile. The strength of aerogels can be improved by employing an additional crosslinking step using isocyanates. In this work, dimethyldiethoxysilane (DMDES) is evaluated for use in the silane backbone of polyurethane crosslinked aerogels. Approximately half of the resulting aerogels exhibited a core/shell morphology of hard crosslinked aerogel surrounding a softer, uncrosslinked center. Solid state NMR and scanning electron microscopy results indicate the DMDES incorporated itself as a conformal coating around the outside of the secondary silica particles, in much the same manner as isocyanate crosslinking. Response surface curves were generated from compression data, indicating levels of reinforcement comparable to that in previous literature, despite the core/shell morphology.

  4. Biothermoplastics from hydrolyzed and citric acid crosslinked chicken feathers.

    PubMed

    Reddy, Narendra; Chen, Lihong; Yang, Yiqi

    2013-04-01

    We demonstrate a novel approach of developing thermoplastic films from feathers by alkaline hydrolysis and crosslinking with citric acid. Unlike previous approaches that used toxic chemicals, complicated and/or expensive methods to develop films, in this research, feathers were hydrolyzed using various concentrations of alkali and the hydrolyzed feathers were compression molded into films using glycerol as plasticizer and crosslinked with citric acid to improve water stability. Alkali hydrolyzed feathers could be compression molded into films with tensile strength of 5.9 MPa and elongation of 31.7% but had poor wet strength. Feather films crosslinked with citric acid had tensile strength of 1.9 MPa and elongation of 24.6% after being in 90% humidity at 21 °C for 24 hours. Alkaline hydrolysis and citric acid crosslinking provides an opportunity to develop inexpensive and biodegradable thermoplastics from the inexpensive, renewable and sustainable poultry feathers. PMID:23827561

  5. Simulation of interfacial fracture in highly crosslinked adhesives

    SciTech Connect

    STEVENS,MARK J.

    2000-05-22

    The fracture of highly-crosslinked networks is investigated by molecular dynamics simulations. The network is modeled as a bead-spring polymer network between two solid surfaces. The network is dynamically formed by crosslinking an equilibrated liquid mixture. Tensile pull fracture is simulated as a function of the number of interracial bonds. The sequence of molecular structural deformations that lead to failure are determined, and the connectivity is found to strongly control the stress-strain response and failure modes. The failure strain is related to the minimal paths in the network that connect the two solid surfaces. The failure stress is a fraction of the ideal stress required to fracture all the interracial bonds, and is linearly proportional to the number of interracial bonds. By allowing only a single bond between a crosslinker and the surface, interracial failure always occurs. Allowing up to half of the crosslinker's bonds to occur with the surface, cohesive failure can occur.

  6. Hydroxyl radicals do not crosslink a DNA-lysozyme complex

    SciTech Connect

    Werbin, H.; Cheng, C.J.

    1985-12-01

    The ionic complex between lysozyme and either Escherichia coli DNA or pBR322 DNA was not crosslinked by two systems capable of producing nanomolar amounts of hydroxyl radicals, the oxidation of xanthine by xanthine oxidase and the iron catalyzed oxidation of ascorbic acid. Nor did effective crosslinking occur with micromolar quantities of hydroxyl radicals raised by the addition of adenosine nucleotides to ferrous iron and hydrogen peroxide. In this case, radical content was estimated by colorimetric analysis of formaldehyde following hydroxyl radical oxidation of dimethyl sulfoxide. Similar amounts of radicals generated by pulse radiolysis in a nitrous oxide atmosphere failed also to induce crosslinking. These findings do not support a role for hydroxy radicals in the N-acetoxy-2-acetylaminofluorene induced crosslinking of DNA to lysozyme proposed earlier.

  7. Bifunctional μ/δ Opioid Peptides: Variation of the Type and Length of the Linker Connecting the Two Components

    PubMed Central

    Ding, Jinguo; Lemieux, Carole; Chung, Nga N.; Schiller, Peter W.

    2011-01-01

    On the basis of evidence that opioid compounds with a mixed μ agonist/δ antagonist profile may produce an antinociceptive effect with low propensity to induce side effects, bifunctional opioid peptides containing the μ agonist [Dmt1]DALDA (H-Dmt-D-Arg-Phe-Lys-NH2; Dmt = 2',6’-dimethyltyrosine) connected tail-to-tail via various α,ω-diaminoalkyl- or diaminocyclohexane linkers to the δ antagonists TICP[Ψ] (H-Tyr-TicΨ[CH2-NH]Cha-Phe-OH; Cha = cyclohexylalanine, Tic = 1,2,3,4-tetrahydroisoquinoline-3-carboxylic acid), H-Dmt-Tic-OH or H-Bcp-Tic-OH (Bcp = 4'-[N-((4'-phenyl)phenethyl)carboxamido]phenylalanine) were synthesized and pharmacologically characterized in vitro. Bifunctional [Dmt1]DALDA→NH-(CH2)n-NH←TICP[Ψ] compounds (n = 0–12) showed decreasing μ and δ receptor binding affinities with increasing linker length. As expected, several of the bifunctional peptides were μ agonist/δ antagonists with low nanomolar μ and δ receptor binding affinities. However, compounds with unexpected opioid activity profiles, including a μ partial agonist/δ partial agonist, μ antagonist/δ antagonists and μ agonist/δ agonists, were also identified. These results indicate that the binding affinities and intrinsic efficacies of these bifunctional compounds at both receptors depend on the length and type of the linker connecting the μ and δ components. An important recommendation emerging from this study is that the in vitro activity profiles of bifunctional compounds containing an agonist and an antagonist component connected via a linker need to be determined prior to their pharmacological evaluation in vivo. PMID:22070627

  8. Photocontrolled Cargo Release from Dual Cross-Linked Polymer Particles.

    PubMed

    Tan, Shereen; Cui, Jiwei; Fu, Qiang; Nam, Eunhyung; Ladewig, Katharina; Ren, Jing M; Wong, Edgar H H; Caruso, Frank; Blencowe, Anton; Qiao, Greg G

    2016-03-01

    Burst release of a payload from polymeric particles upon photoirradiation was engineered by altering the cross-linking density. This was achieved via a dual cross-linking concept whereby noncovalent cross-linking was provided by cyclodextrin host-guest interactions, and irreversible covalent cross-linking was mediated by continuous assembly of polymers (CAP). The dual cross-linked particles (DCPs) were efficiently infiltrated (∼80-93%) by the biomacromolecule dextran (molecular weight up to 500 kDa) to provide high loadings (70-75%). Upon short exposure (5 s) to UV light, the noncovalent cross-links were disrupted resulting in increased permeability and burst release of the cargo (50 mol % within 1 s) as visualized by time-lapse fluorescence microscopy. As sunlight contains UV light at low intensities, the particles can potentially be incorporated into systems used in agriculture, environmental control, and food packaging, whereby sunlight could control the release of nutrients and antimicrobial agents. PMID:26862769

  9. Cross-linking and the molecular packing of corneal collagen

    NASA Technical Reports Server (NTRS)

    Yamauchi, M.; Chandler, G. S.; Tanzawa, H.; Katz, E. P.

    1996-01-01

    We have quantitatively characterized, for the first time, the cross-linking in bovine cornea collagen as a function of age. The major iminium reducible cross-links were dehydro-hydroxylysinonorleucine (deH-HLNL) and dehydro-histidinohydroxymerodesmosine (deH-HHMD). The former rapidly diminished after birth; however, the latter persisted in mature animals at a level of 0.3 - 0.4 moles/mole of collagen. A nonreducible cross-link, histidinohydroxylysinonorleucine (HHL), previously found only in skin, was also found to be a major mature cross-link in cornea. The presence of HHL indicates that cornea fibrils have a molecular packing similar to skin collagen. However, like deH-HHMD, the HHL content in corneal fibrils only reaches a maximum value with time about half that of skin. These data suggest that the corneal fibrils are comprised of discrete filaments that are internally stabilized by HHL and deH-HHMD cross-links. This pattern of intermolecular cross-linking would facilitate the special collagen swelling property required for corneal transparency.

  10. Synthesis of a novel photoactivatable glucosylceramide cross-linker.

    PubMed

    Budani, Monique; Mylvaganam, Murugesapillai; Binnington, Beth; Lingwood, Clifford

    2016-09-01

    The biosynthesis of glucosylceramide (GlcCer) is a key rate-limiting step in complex glycosphingolipid (GSL) biosynthesis. To further define interacting partners of GlcCer, we have made a cleavable, biotinylated, photoreactive GlcCer analog in which the reactive nitrene is closely apposed to the GlcCer head group, by substituting the native fatty acid with d, l-2-aminohexadecanoic acid. Two amino-GlcCer diastereomer cross-linkers (XLA and XLB) were generated. XLB proved an effective lactosylceramide (LacCer) synthase substrate while XLA was inhibitory. Both probes specifically bound and cross-linked the GlcCer binding protein, glycolipid transfer protein (GLTP), but not other GSL binding proteins (Shiga toxin and cholera toxin). GlcCer inhibited GLTP cross-linking. Both GlcCer cross-linkers competed with microsomal nitrobenzoxadiazole (NBD)-GlcCer anabolism to NBD-LacCer. GLTP showed marked, ATP-dependent enhancement of cell-free intact microsomal LacCer synthesis from endogenous or exogenous liposomal GlcCer, supporting a role in the transport/membrane translocation of cytosolic and extra-Golgi GlcCer. GLTP was specifically labeled by either XLA or XLB GlcCer cross-linker during this process, together with a (the same) small subset of microsomal proteins. These cross-linkers will serve to probe physiologically relevant GlcCer-interacting cellular proteins. PMID:27412675

  11. Structural analysis of photosystem I polypeptides using chemical crosslinking

    NASA Technical Reports Server (NTRS)

    Armbrust, T. S.; Odom, W. R.; Guikema, J. A.; Spooner, B. S. (Principal Investigator)

    1994-01-01

    Thylakoid membranes, obtained from leaves of 14 d soybean (Glycine max L. cv. Williams) plants, were treated with the chemical crosslinkers glutaraldehyde or 1-ethyl-3-(3-dimethylaminopropyl)-carbodiimide (EDC) to investigate the structural organization of photosystem I. Polypeptides were resolved using lithium dodecyl sulfate polyacrylamide gel electrophoresis, and were identified by western blot analysis using a library of polyclonal antibodies specific for photosystem I subunits. An electrophoretic examination of crosslinked thylakoids revealed numerous crosslinked products, using either glutaraldehyde or EDC. However, only a few of these could be identified by western blot analysis using subunit-specific polyclonal antibodies. Several glutaraldehyde dependent crosslinked species were identified. A single band was identified minimally composed of PsaC and PsaD, documenting the close interaction between these two subunits. The most interesting aspect of these studies was a crosslinked species composed of the PsaB subunit observed following EDC treatment of thylakoids. This is either an internally crosslinked species, which will provide structural information concerning the topology of the complex PsaB protein, a linkage with a polypeptide for which we do not yet have an immunological probe, or a masking of epitopes by the EDC linkage at critical locations in the peptide which is linked to PsaB.

  12. Intra-spike crosslinking overcomes antibody evasion by HIV-1.

    PubMed

    Galimidi, Rachel P; Klein, Joshua S; Politzer, Maria S; Bai, Shiyu; Seaman, Michael S; Nussenzweig, Michel C; West, Anthony P; Bjorkman, Pamela J

    2015-01-29

    Antibodies developed during HIV-1 infection lose efficacy as the viral spike mutates. We postulated that anti-HIV-1 antibodies primarily bind monovalently because HIV's low spike density impedes bivalent binding through inter-spike crosslinking, and the spike structure prohibits bivalent binding through intra-spike crosslinking. Monovalent binding reduces avidity and potency, thus expanding the range of mutations permitting antibody evasion. To test this idea, we engineered antibody-based molecules capable of bivalent binding through intra-spike crosslinking. We used DNA as a "molecular ruler" to measure intra-epitope distances on virion-bound spikes and construct intra-spike crosslinking molecules. Optimal bivalent reagents exhibited up to 2.5 orders of magnitude increased potency (>100-fold average increases across virus panels) and identified conformational states of virion-bound spikes. The demonstration that intra-spike crosslinking lowers the concentration of antibodies required for neutralization supports the hypothesis that low spike densities facilitate antibody evasion and the use of molecules capable of intra-spike crosslinking for therapy or passive protection. PMID:25635457

  13. Covalent protein crosslinks: general detection, quantitation, and characterization via modification with diphenylborinic acid.

    PubMed

    Graham, L; Gallop, P M

    1994-03-01

    Progressive crosslinking of proteins appears to be a general phenomenon in aging cells and tissues. Crosslinked proteins can form insoluble aggregates which become increasingly resistant to proteolysis as more crosslinks form. However, most evidence for progressive crosslinking with age is indirect, and little is known about the chemical mechanisms involved. We have therefore developed a method for detection and isolation of any type of stable covalent crosslink from protein hydrolysates which requires no prior knowledge of the molecular structure of whatever crosslink(s) may be present. It utilizes the specificity of the diphenylborinic acid reagent for alpha-amino acid groups and the chromatographic properties and uv absorbance of the crosslink derivatives. The method is demonstrated using eight different crosslinks from collagen and fibrin, and a general procedure is given for detection of any type of crosslink in a protein hydrolysate. PMID:8203759

  14. Oxygen electrode bifunctional electrocatalyst NiCo2O4 spinel

    NASA Technical Reports Server (NTRS)

    Fielder, William L.; Singer, Joseph

    1988-01-01

    A significant increase in energy density may be possible if a two-unit alkaline regenerative H2-O2 fuel cell is replaced with a single-unit system that uses passive means for H2O transfer and thermal control. For this single-unit system, new electrocatalysts for the O2 electrode will be required which are not only bifunctionally active but also chemically and electrochemically stable between the voltage range of about 0.7 and 1.5 V. NiCo2O4 spinel is reported to have certain characteristics that make it useful for a study of electrode fabrication techniques. High surface area NiCo2O4 powder was fabricated into unsupported, bifunctional, PTFE-bonded, porous gas fuel cell electrodes by commercial sources using varying PTFE contents and sintering temperatures. The object of this study is to measure the bifunctional activities of these electrodes and to observe what performance differences might result from different commercial electrode fabricators. O2 evolution and O2 reduction data were obtained at 80 C (31 percent KOH). An irreversible reaction (i.e., aging) occurred during O2 evolution at potentials greater than about 1.5 V. Anodic Tafel slopes of 0.06 and 0.12 V/decade were obtained for the aged electrodes. Within the range of 15 to 25 percent, the PTFE content was not a critical parameter for optimizing the electrode for O2 evolution activity. Sintering temperatures between 300 and 340 C may be adequate but heating at 275 C may not be sufficient to properly sinter the PTFE-NiCo2O4 mixture. Electrode disintegration was observed during O2 reduction. Transport of O2 to the NiCo2O4 surface became prohibitive at greater than about -0.02 A/sq cm. Cathodic Tafel slopes of -0.6 and -0.12 V/decade were assumed for the O2 reduction process. A PTFE content of 25 percent (or greater) appears to be preferable for sintering the PTFE-NiCo2O4 mixture.

  15. Adsorptive removal of Congo red from aqueous solutions using crosslinked chitosan and crosslinked chitosan immobilized bentonite.

    PubMed

    Huang, Ruihua; Zhang, Lujie; Hu, Pan; Wang, Jing

    2016-05-01

    Batch experiments were executed to investigate the removal of Congo red (CR) from aqueous solutions using the crosslinked chitosan (CCS) and crosslinked chitosan immobilized bentonite (CCS/BT composite). The CCS and CCS/BT composite were characterized by X-ray diffraction (XRD) and Fourier transform infrared spectroscopy (FTIR) techniques. The removal of CR was examined as a function of pH value of CR solution, contact time, and inorganic sodium salt and ionic strength. The equilibrium data of CCS and CCS/BT composite agreed well with the Langmuir model. The adsorption capacities of CCS and CCS/BT composite at 298K and natural pH value were 405 and 500mg/g, respectively. The kinetic data correlated well with the pseudo-second-order model. The adsorption of CR onto the CCS was mainly controlled by chemisorption while the adsorption of CR onto the CCS/BT composite was controlled by chemisorption and the electrostatic attraction. PMID:26820350

  16. Wear of highly crosslinked polyethylene acetabular components

    PubMed Central

    Callary, Stuart A; Solomon, Lucian B; Holubowycz, Oksana T; Campbell, David G; Munn, Zachary; Howie, Donald W

    2015-01-01

    Background and purpose Wear rates of highly crosslinked polyethylene (XLPE) acetabular components have varied considerably between different published studies. This variation is in part due to the different techniques used to measure wear and to the errors inherent in measuring the relatively low amounts of wear in XLPE bearings. We undertook a scoping review of studies that have examined the in vivo wear of XLPE acetabular components using the most sensitive method available, radiostereometric analysis (RSA). Methods A systematic search of the PubMed, Scopus, and Cochrane databases was performed to identify published studies in which RSA was used to measure wear of XLPE components in primary total hip arthroplasty (THA). Results 18 publications examined 12 primary THA cohorts, comprising only 260 THAs at 2–10 years of follow-up. The mean or median proximal wear rate reported ranged from 0.00 to 0.06 mm/year. However, differences in the manner in which wear was determined made it difficult to compare some studies. Furthermore, differences in RSA methodology between studies, such as the use of supine or standing radiographs and the use of beaded or unbeaded reference segments, may limit future meta-analyses examining the effect of patient and implant variables on wear rates. Interpretation This scoping review confirmed the low wear rates of XLPE in THA, as measured by RSA. We make recommendations to enhance the standardization of reporting of RSA wear results, which will facilitate early identification of poorly performing implants and enable a better understanding of the effects of surgical and patient factors on wear. PMID:25301435

  17. Vascular Gene Transfer from Metallic Stent Surfaces Using Adenoviral Vectors Tethered through Hydrolysable Cross-linkers

    PubMed Central

    Fishbein, Ilia; Forbes, Scott P.; Adamo, Richard F.; Chorny, Michael; Levy, Robert J.; Alferiev, Ivan S.

    2014-01-01

    In-stent restenosis presents a major complication of stent-based revascularization procedures widely used to re-establish blood flow through critically narrowed segments of coronary and peripheral arteries. Endovascular stents capable of tunable release of genes with anti-restenotic activity may present an alternative strategy to presently used drug-eluting stents. In order to attain clinical translation, gene-eluting stents must exhibit predictable kinetics of stent-immobilized gene vector release and site-specific transduction of vasculature, while avoiding an excessive inflammatory response typically associated with the polymer coatings used for physical entrapment of the vector. This paper describes a detailed methodology for coatless tethering of adenoviral gene vectors to stents based on a reversible binding of the adenoviral particles to polyallylamine bisphosphonate (PABT)-modified stainless steel surface via hydrolysable cross-linkers (HC). A family of bifunctional (amine- and thiol-reactive) HC with an average t1/2 of the in-chain ester hydrolysis ranging between 5 and 50 days were used to link the vector with the stent. The vector immobilization procedure is typically carried out within 9 hr and consists of several steps: 1) incubation of the metal samples in an aqueous solution of PABT (4 hr); 2) deprotection of thiol groups installed in PABT with tris(2-carboxyethyl) phosphine (20 min); 3) expansion of thiol reactive capacity of the metal surface by reacting the samples with polyethyleneimine derivatized with pyridyldithio (PDT) groups (2 hr); 4) conversion of PDT groups to thiols with dithiothreitol (10 min); 5) modification of adenoviruses with HC (1 hr); 6) purification of modified adenoviral particles by size-exclusion column chromatography (15 min) and 7) immobilization of thiol-reactive adenoviral particles on the thiolated steel surface (1 hr). This technique has wide potential applicability beyond stents, by facilitating surface engineering of

  18. Mono- and bi-functional arenethiols as surfactants for gold nanoparticles: synthesis and characterization

    NASA Astrophysics Data System (ADS)

    Vitale, Floriana; Fratoddi, Ilaria; Battocchio, Chiara; Piscopiello, Emanuela; Tapfer, Leander; Russo, Maria Vittoria; Polzonetti, Giovanni; Giannini, Cinzia

    2011-12-01

    Stable gold nanoparticles stabilized by different mono and bi-functional arenethiols, namely, benzylthiol and 1,4-benzenedimethanethiol, have been prepared by using a modified Brust's two-phase synthesis. The size, shape, and crystalline structure of the gold nanoparticles have been determined by high-resolution electron microscopy and full-pattern X-ray powder diffraction analyses. Nanocrystals diameters have been tuned in the range 2 ÷ 9 nm by a proper variation of Au/S molar ratio. The chemical composition of gold nanoparticles and their interaction with thiols have been investigated by X-ray photoelectron spectroscopy. In particular, the formation of networks has been observed with interconnected gold nanoparticles containing 1,4-benzenedimethanethiol as ligand.

  19. Bi-functional Mo-doped WO3 nanowire array electrochromism-plus electrochemical energy storage.

    PubMed

    Zhou, D; Shi, F; Xie, D; Wang, D H; Xia, X H; Wang, X L; Gu, C D; Tu, J P

    2016-03-01

    Metal-doping is considered to be an effective way for construction of advanced semiconducting metal oxides with tailored physicochemical properties. Herein, Mo-doped WO3 nanowire arrays are rationally fabricated by a sulfate-assisted hydrothermal method. Compared to the pure WO3, the optimized Mo-doped WO3 nanowire arrays exhibit improved electrochromic properties with fast switching speed (3.2s and 2.6s for coloration and bleaching, respectively), significant optical modulation (56.7% at 750nm, 83.0% at 1600nm and 48.5% at 10μm), high coloration efficiency (123.5cm(2)C(-1)) and excellent cycling stability. In addition, as a proof of concept, the Mo-doped WO3 nanowire arrays are demonstrated with electrochemical energy storage monitored by the electrochromism. This electrode design protocol can provide an alternative way for developing high-performance active materials for bi-functional electrochromic batteries. PMID:26669497

  20. Novel 3-nitrotriazole-based amides and carbinols as bifunctional anti-Chagasic agents

    PubMed Central

    Papadopoulou, Maria V.; Bloomer, William D.; Lepesheva, Galina I.; Rosenzweig, Howard S.; Kaiser, Marcel; Aguilera-Venegas, Benjamín; Wilkinson, Shane R.; Chatelain, Eric; Ioset, Jean-Robert

    2015-01-01

    3-Nitro-1H-1,2,4-triazole-based amides with a linear, rigid core and 3-nitrotriazole-based fluconazole analogs were synthesized as dual functioning antitrypanosomal agents. Such compounds are excellent substrates for type I nitroreductase (NTR) located in the mitochondrion of trypanosomatids and, at the same time, act as inhibitors of the sterol 14α-demethylase (T. cruzi CYP51) enzyme. Because combination treatments against parasites are often superior to monotherapy, we believe that this emerging class of bifunctional compounds may introduce a new generation of antitrypanosomal drugs. In the present work, the synthesis and in vitro and in vivo evaluation of such compounds is discussed. PMID:25580906

  1. Chimeric bifunctional oligonucleotides as a novel tool to invade telomerase assembly

    PubMed Central

    Azhibek, Dulat; Zvereva, Maria; Zatsepin, Timofei; Rubtsova, Maria; Dontsova, Olga

    2014-01-01

    Telomerase is a key participant in the telomere length maintaining system in eukaryotic cells. Telomerase RNA and protein reverse transcriptase subunits are essential for the appearance of active telomerase in vitro. Telomerase is active in many cancer types and is a potential target for anticancer drug development. Here we report a new approach for impairing telomerase function at the stage of human telomerase assembly. The approach is based on the application of chimeric bifunctional oligonucleotides that contain two oligonucleotide parts complementary to the functional domains of telomerase RNA connected with non-nucleotide linkers in different orientations (5′-3′, 5′-5′ or 3′-3′). Such chimeras inhibited telomerase in vitro in the nM range, but were effective in vivo in sub-nM concentrations, predominantly due to their effect on telomerase assembly and dimerization. PMID:25081209

  2. Cage-like bifunctional chelators, copper-64 radiopharmaceuticals and PET imaging using the same

    DOEpatents

    Conti, Peter S.; Cai, Hancheng; Li, Zibo; Liu, Shuanglong

    2016-08-02

    Disclosed is a class of versatile Sarcophagine based bifunctional chelators (BFCs) containing a hexa-aza cage for labeling with metals having either imaging, therapeutic or contrast applications radiolabeling and one or more linkers (A) and (B). The compounds have the general formula ##STR00001## where A is a functional group selected from group consisting of an amine, a carboxylic acid, an ester, a carbonyl, a thiol, an azide and an alkene, and B is a functional group selected from the group consisting of hydrogen, an amine, a carboxylic acid, and ester, a carbonyl, a thiol, an azide and an alkene. Also disclosed are conjugate of the BFC and a targeting moiety, which may be a peptide or antibody. Also disclosed are metal complexes of the BFC/targeting moiety conjugates that are useful as radiopharmaceuticals, imaging agents or contrast agents.

  3. Polarization holograms in a bifunctional amorphous polymer exhibiting equal values of photoinduced linear and circular birefringences.

    PubMed

    Provenzano, Clementina; Pagliusi, Pasquale; Cipparrone, Gabriella; Royes, Jorge; Piñol, Milagros; Oriol, Luis

    2014-10-01

    Light-controlled molecular alignment is a flexible and useful strategy introducing novelty in the fields of mechanics, self-organized structuring, mass transport, optics, and photonics and addressing the development of smart optical devices. Azobenzene-containing polymers are well-known photocontrollable materials with large and reversible photoinduced optical anisotropies. The vectorial holography applied to these materials enables peculiar optical devices whose properties strongly depend on the relative values of the photoinduced birefringences. Here is reported a polarization holographic recording based on the interference of two waves with orthogonal linear polarization on a bifunctional amorphous polymer that, exceptionally, exhibits equal values of linear and circular birefringence. The peculiar photoresponse of the material coupled with the holographic technique demonstrates an optical device capable of decomposing the light into a set of orthogonally polarized linear components. The holographic structures are theoretically described by the Jones matrices method and experimentally investigated. PMID:25187982

  4. Oxychlorination-Dehydrochlorination Chemistry on Bifunctional Ceria Catalysts for Intensified Vinyl Chloride Production.

    PubMed

    Scharfe, Matthias; Lira-Parada, Pedro A; Paunović, Vladimir; Moser, Maximilian; Amrute, Amol P; Pérez-Ramírez, Javier

    2016-02-24

    Ceria catalyzes the one-step production of the vinyl chloride monomer (VCM) from ethylene with a high yield because of its bifunctional character: redox centers oxychlorinate ethylene to ethylene dichloride (EDC), which is subsequently dehydrochlorinated to VCM over strong acid sites generated in situ. Nanocrystalline CeO2 and CeO2-ZrO2 lead to a VCM yield of 25 % in a single pass, outperforming the best reported systems and reaching industrially attractive levels. The use of CeO2 intensifies the current two-step process within PVC production encompassing CuCl2 -catalyzed oxychlorination and thermal cracking. In addition, ceria-based materials offer stability advantages with respect to the archetypical CuCl2 -based catalysts. PMID:26823027

  5. Bifunctional nanoparticles for SERS monitoring and magnetic intervention of assembly and enzyme cutting of DNAs

    SciTech Connect

    Lin, Liqin; Crew, Elizabeth; Yan, Hong; Shan, Shiyao; Skeete, Zakiya; Mott, Derrick; Krentsel, Tatiana; Yin, Jun; Chernova, Natasha A.; Luo, Jin; Engelhard, Mark H.; Wang, Chong M.; Li, Qingbiao; Zhong, Chuan-Jian

    2013-07-27

    The ability to detect and intervene in DNA assembly, disassembly, and enzyme cutting processes in a solution phase requires effective signal transduction and stimulus response. This report demonstrates a novel bifunctional strategy for the creation of this ability using gold- and silver-coated MnZn ferrite nanoparticles (MZF@Au or MZF@Ag) that impart magnetic and surfaceenhanced Raman scattering (SERS) functionalities to these processes. The double-stranded DNA linkage of labeled gold nanoparticles with MZF@Au (or MZF@Ag) produces interparticle "hot-spots" for real-time SERS monitoring of the DNA assembly, disassembly, or enzyme cutting processes, during which the magnetic component provides an effective means for intervention in the solution. The unique combination of the nanoprobes functionalities serves a new paradigm for the design of functional nanoprobes in biomolecular recognition and intervention.

  6. The fabrication of a bifunctional oxygen electrode without carbon components for alkaline secondary batteries

    NASA Astrophysics Data System (ADS)

    Price, Stephen W. T.; Thompson, Stephen J.; Li, Xiaohong; Gorman, Scott F.; Pletcher, Derek; Russell, Andrea E.; Walsh, Frank C.; Wills, Richard G. A.

    2014-08-01

    The fabrication of a gas diffusion electrode (GDE) without carbon components is described. It is therefore suitable for use as a bifunctional oxygen electrode in alkaline secondary batteries. The electrode is fabricated in two stages (a) the formation of a PTFE-bonded nickel powder layer on a nickel foam substrate and (b) the deposition of a NiCo2O4 spinel electrocatalyst layer by dip coating in a nitrate solution and thermal decomposition. The influence of modifications to the procedure on the performance of the GDEs in 8 M NaOH at 333 K is described. The GDEs can support current densities up to 100 mA cm-2 with state-of-the-art overpotentials for both oxygen evolution and oxygen reduction. Stable performance during >50 successive, 1 h oxygen reduction/evolution cycles at a current density of 50 mA cm-2 has been achieved.

  7. A Bifunctional Electrocatalyst for Oxygen Evolution and Oxygen Reduction Reactions in Water

    PubMed Central

    Faschinger, Felix; Chattopadhyay, Samir; Bhakta, Snehadri; Mondal, Biswajit; Elemans, Johannes A. A. W.; Müllegger, Stefan; Tebi, Stefano; Koch, Reinhold; Klappenberger, Florian; Paszkiewicz, Mateusz; Barth, Johannes V.; Rauls, Eva; Aldahhak, Hazem; Schmidt, Wolf Gero

    2016-01-01

    Abstract Oxygen reduction and water oxidation are two key processes in fuel cell applications. The oxidation of water to dioxygen is a 4 H+/4 e− process, while oxygen can be fully reduced to water by a 4 e−/4 H+ process or partially reduced by fewer electrons to reactive oxygen species such as H2O2 and O2 −. We demonstrate that a novel manganese corrole complex behaves as a bifunctional catalyst for both the electrocatalytic generation of dioxygen as well as the reduction of dioxygen in aqueous media. Furthermore, our combined kinetic, spectroscopic, and electrochemical study of manganese corroles adsorbed on different electrode materials (down to a submolecular level) reveals mechanistic details of the oxygen evolution and reduction processes. PMID:27478281

  8. A Bifunctional Electrocatalyst for Oxygen Evolution and Oxygen Reduction Reactions in Water

    PubMed Central

    Faschinger, Felix; Chattopadhyay, Samir; Bhakta, Snehadri; Mondal, Biswajit; Elemans, Johannes A. A. W.; Müllegger, Stefan; Tebi, Stefano; Koch, Reinhold; Klappenberger, Florian; Paszkiewicz, Mateusz; Barth, Johannes V.; Rauls, Eva; Aldahhak, Hazem; Schmidt, Wolf Gero

    2016-01-01

    Abstract Oxygen reduction and water oxidation are two key processes in fuel cell applications. The oxidation of water to dioxygen is a 4 H+/4 e− process, while oxygen can be fully reduced to water by a 4 e−/4 H+ process or partially reduced by fewer electrons to reactive oxygen species such as H2O2 and O2 −. We demonstrate that a novel manganese corrole complex behaves as a bifunctional catalyst for both the electrocatalytic generation of dioxygen as well as the reduction of dioxygen in aqueous media. Furthermore, our combined kinetic, spectroscopic, and electrochemical study of manganese corroles adsorbed on different electrode materials (down to a submolecular level) reveals mechanistic details of the oxygen evolution and reduction processes. PMID:26773287

  9. Bifunctional hairy silica nanoparticles as high-performance additives for lubricant

    PubMed Central

    Sui, Tianyi; Song, Baoyu; Wen, Yu-ho; Zhang, Feng

    2016-01-01

    Bifunctional hairy silica nanoparticles (BHSNs), which are silica nanoparticles covered with alkyl and amino organic chains, were prepared as high-performance additives for lubricants. Compared with hairy silica nanoparticles covered by a single type of organic chain, binary hairy silica nanoparticles exhibit the advantages of both types of organic chains, which exhibit excellent compatibility with lubricants and adsorbability to metal surfaces. Nanoparticles with different ratios of amino and alkyl ligands were investigated. In comparison to an untreated lubricant, BHSNs reduce the friction coefficient and wear scar diameter by 40% and 60%, respectively. The wear mechanism of BHSNs was investigated, and the protective and filling effect of the nanoparticles improved because of collaboration of amino and alkyl ligands. PMID:26936117

  10. A crystal structure of the bifunctional antibiotic simocyclinone D8, bound to DNA gyrase.

    PubMed

    Edwards, Marcus J; Flatman, Ruth H; Mitchenall, Lesley A; Stevenson, Clare E M; Le, Tung B K; Clarke, Thomas A; McKay, Adam R; Fiedler, Hans-Peter; Buttner, Mark J; Lawson, David M; Maxwell, Anthony

    2009-12-01

    Simocyclinones are bifunctional antibiotics that inhibit bacterial DNA gyrase by preventing DNA binding to the enzyme. We report the crystal structure of the complex formed between the N-terminal domain of the Escherichia coli gyrase A subunit and simocyclinone D8, revealing two binding pockets that separately accommodate the aminocoumarin and polyketide moieties of the antibiotic. These are close to, but distinct from, the quinolone-binding site, consistent with our observations that several mutations in this region confer resistance to both agents. Biochemical studies show that the individual moieties of simocyclinone D8 are comparatively weak inhibitors of gyrase relative to the parent compound, but their combination generates a more potent inhibitor. Our results should facilitate the design of drug molecules that target these unexploited binding pockets. PMID:19965760

  11. A Bifunctional Electrocatalyst for Oxygen Evolution and Oxygen Reduction Reactions in Water.

    PubMed

    Schöfberger, Wolfgang; Faschinger, Felix; Chattopadhyay, Samir; Bhakta, Snehadri; Mondal, Biswajit; Elemans, Johannes A A W; Müllegger, Stefan; Tebi, Stefano; Koch, Reinhold; Klappenberger, Florian; Paszkiewicz, Mateusz; Barth, Johannes V; Rauls, Eva; Aldahhak, Hazem; Schmidt, Wolf Gero; Dey, Abhishek

    2016-02-12

    Oxygen reduction and water oxidation are two key processes in fuel cell applications. The oxidation of water to dioxygen is a 4 H(+)/4 e(-) process, while oxygen can be fully reduced to water by a 4 e(-)/4 H(+) process or partially reduced by fewer electrons to reactive oxygen species such as H2O2 and O2(-). We demonstrate that a novel manganese corrole complex behaves as a bifunctional catalyst for both the electrocatalytic generation of dioxygen as well as the reduction of dioxygen in aqueous media. Furthermore, our combined kinetic, spectroscopic, and electrochemical study of manganese corroles adsorbed on different electrode materials (down to a submolecular level) reveals mechanistic details of the oxygen evolution and reduction processes. PMID:26773287

  12. An Efficient Bifunctional Decadentate Ligand 3p-C-DEPA for Targeted Alpha Radioimmunotherapy Applications

    PubMed Central

    Song, Hyun A; Kang, Chi Soo; Baidoo, Kwamena E.; Milenic, Diane E.; Chen, Yunwei; Dai, Anzhi; Brechbiel, M. W.; Chong, Hyun-Soon

    2011-01-01

    A new bifunctional ligand 3p-C-DEPA was synthesized and evaluated for use in targeted alpha radioimmunotherapy. 3p-C-DEPA was efficiently prepared via regiospecific ring opening of an aziridinium ion and conjugated with trastuzumab. The 3p-C-DEPA-trastuzumab conjugate was extremely rapid in binding 205/6Bi, and the corresponding 205/6Bi-3p-C-DEPA-trastuzumab complex was stable in human serum. Biodistribution studies were performed to evaluate in vivo stability and tumor targeting of 205/6Bi-3p-C-DEPA-trastuzumab conjugate in tumor bearing athymic mice. 205/6Bi-3p-C-DEPA-trastuzumab conjugate displayed excellent in vivo stability and targeting as evidenced by low organ uptake and high tumor uptake. The results of the in vitro and in vivo studies indicate that 3p-C-DEPA is a promising chelator for radioimmunotherapy of 212Bi and 213Bi. PMID:21604692

  13. Bifunctional hairy silica nanoparticles as high-performance additives for lubricant.

    PubMed

    Sui, Tianyi; Song, Baoyu; Wen, Yu-Ho; Zhang, Feng

    2016-01-01

    Bifunctional hairy silica nanoparticles (BHSNs), which are silica nanoparticles covered with alkyl and amino organic chains, were prepared as high-performance additives for lubricants. Compared with hairy silica nanoparticles covered by a single type of organic chain, binary hairy silica nanoparticles exhibit the advantages of both types of organic chains, which exhibit excellent compatibility with lubricants and adsorbability to metal surfaces. Nanoparticles with different ratios of amino and alkyl ligands were investigated. In comparison to an untreated lubricant, BHSNs reduce the friction coefficient and wear scar diameter by 40% and 60%, respectively. The wear mechanism of BHSNs was investigated, and the protective and filling effect of the nanoparticles improved because of collaboration of amino and alkyl ligands. PMID:26936117

  14. Development and computational modeling of novel bifunctional organophosphorus extractants for lanthanoid separation

    SciTech Connect

    Goto, Masahiro; Matsumoto, Satoshi; Uezu, Kazuya; Nakashio, Fumiyuki; Yoshizuka, Kazuharu; Inoue, Katsutoshi

    1999-08-01

    Novel organophosphorus extractants, which have two functional groups in the molecular structure, have been developed for the separation of lanthanoids using the liquid-liquid extraction technique. The separation efficiency and extractability of the novel extractants were investigated for nine lanthanoids. These bifunctional extractants have an extremely high extractability to all the lanthanoids compared to those of commercially available organophosphorus extractants. Two isomers having an identical chemical formulation show significantly different behaviors in lanthanoid extraction. This means that the extraction and separation abilities are quite sensitive to the structure of the spacer connecting the two functional groups. The authors also discuss the experimental results with a computational modeling by means of molecular mechanics and semiempirical molecular orbital methods. The novel molecular mechanics (MM) calculation program MOMEC enables them to analyze the stable conformation of a series of lanthanoid complexes. The calculation suggests that the structural effect of the spacer is one of the decisive factors for enhancing selectivity and extractability in lanthanoid extraction.

  15. Bifunctional Nanoparticle-SILP Catalysts (NPs@SILP) for the Selective Deoxygenation of Biomass Substrates

    SciTech Connect

    Luska, Kylie L.; Julis, Jennifer; Stavitski, Eli; Zakharov, Dmitri N.; Adams, Alina; Leitner, Walter

    2014-08-27

    We immobilized ruthenium nanoparticles onto an acidic supported ionic liquid phase (RuNPs@SILP) in the development of bifunctional catalysts for the selective deoxygenation of biomass substrates. RuNPs@SILPs possessed high catalytic activities, selectivities and recyclabilities in the hydrogenolytic deoxygenation and ring opening of C8- and C9-substrates derived from furfural or 5-hydroxymethylfurfural and acetone. When we tailor the acidity of the SILP through the ionic liquid loading provided a molecular parameter by which the catalytic activity and selectivity of the RuNPs@SILPs were controlled to provide a flexible catalyst system toward the formation of different classes of value-added products: cyclic ethers, primary alcohols or aliphatic ethers.

  16. Bi-functional biobased packing of the cassava starch, glycerol, licuri nanocellulose and red propolis.

    PubMed

    Costa, Samantha Serra; Druzian, Janice Izabel; Machado, Bruna Aparecida Souza; de Souza, Carolina Oliveira; Guimarães, Alaíse Gil

    2014-01-01

    The aim of this study was to characterize and determine the bi-functional efficacy of active packaging films produced with starch (4%) and glycerol (1.0%), reinforced with cellulose nanocrystals (0-1%) and activated with alcoholic extracts of red propolis (0.4 to 1.0%). The cellulose nanocrystals used in this study were extracted from licuri leaves. The films were characterized using moisture, water-activity analyses and water vapor-permeability tests and were tested regarding their total phenolic compounds and mechanical properties. The antimicrobial and antioxidant efficacy of the films were evaluated by monitoring the use of the active films for packaging cheese curds and butter, respectively. The cellulose nanocrystals increased the mechanical strength of the films and reduced the water permeability and water activity. The active film had an antimicrobial effect on coagulase-positive staphylococci in cheese curds and reduced the oxidation of butter during storage. PMID:25383783

  17. Improving battery safety by early detection of internal shorting with a bifunctional separator.

    PubMed

    Wu, Hui; Zhuo, Denys; Kong, Desheng; Cui, Yi

    2014-01-01

    Lithium-based rechargeable batteries have been widely used in portable electronics and show great promise for emerging applications in transportation and wind-solar-grid energy storage, although their safety remains a practical concern. Failures in the form of fire and explosion can be initiated by internal short circuits associated with lithium dendrite formation during cycling. Here we report a new strategy for improving safety by designing a smart battery that allows internal battery health to be monitored in situ. Specifically, we achieve early detection of lithium dendrites inside batteries through a bifunctional separator, which offers a third sensing terminal in addition to the cathode and anode. The sensing terminal provides unique signals in the form of a pronounced voltage change, indicating imminent penetration of dendrites through the separator. This detection mechanism is highly sensitive, accurate and activated well in advance of shorting and can be applied to many types of batteries for improved safety. PMID:25308055

  18. Synthesis and evaluation of novel bifunctional oligomer-based composites for dental applications.

    PubMed

    Xie, Dong; Chung, Il-Doo; Wang, Guigui; Mays, Jimmy

    2006-01-01

    Five novel bifunctional oligomers containing both carboxylic acid and methacrylate groups are synthesized, characterized, and used to formulate compomers by mixing with strontium fluoroaluminosilicate glass powder at a filler level of 75% (by weight). Compressive strength (CS) of the cements and viscosity of the resin liquids are used as screening tools to find the optimal formulation. Diametral tensile (DTS) and flexural strengths (FS) are also determined. Results show that the oligomers derivatized with glycerol dimethacrylate exhibit higher CS than those with 2-hydroxyethyl methacrylate. The CS increases with increasing diluent content, filler level, and light-exposure time. During aging, the cement shows an increase of strength over 24 h and then remains unaltered for up to 3 months. The experimental compomer is 45 and 69% higher in CS, 35 and 174% higher in DTS, and 39 and 170% higher in FS, respectively, as compared to Dyract and Fuji II LC. PMID:16364963

  19. A novel copper(II) coordination polymer with carboxylate and isoindol backbones of a bifunctional ligand

    NASA Astrophysics Data System (ADS)

    Patra, Ayan; Sen, Tamal K.; Musie, Ghezai T.; Mandal, Swadhin K.; Bera, Manindranath

    2013-09-01

    The reaction of a bifunctional ligand, 3-(1-oxo-1,3-dihydro-isoindol-2-yl)-propionic acid (Hpda) with Cu(NO3)2ṡ3H2O in methanol-water in the presence of NaOH at room temperature produces a novel dinuclear copper(II) coordination polymer [Cu2(pda)4]n. The complex is fully characterized in the solid state as well as in solution using various analytical techniques including single crystal X-ray diffraction study. The single crystal X-ray structure analysis reveals that the monomeric unit of complex consists of Cu2(O2CR)4 paddlewheel building unit, where the two copper centers acquire a distorted square pyramidal geometry with amide oxygen of the isoindol ring of an adjacent Hpda ligand sitting on the axial positions.

  20. "Click" chemistry mildly stabilizes bifunctional gold nanoparticles for sensing and catalysis.

    PubMed

    Li, Na; Zhao, Pengxiang; Liu, Na; Echeverria, María; Moya, Sergio; Salmon, Lionel; Ruiz, Jaime; Astruc, Didier

    2014-07-01

    A large family of bifunctional 1,2,3-triazole derivatives that contain both a polyethylene glycol (PEG) chain and another functional fragment (e.g., a polymer, dendron, alcohol, carboxylic acid, allyl, fluorescence dye, redox-robust metal complex, or a β-cyclodextrin unit) has been synthesized by facile "click" chemistry and mildly coordinated to nanogold particles, thus providing stable water-soluble gold nanoparticles (AuNPs) in the size range 3.0-11.2 nm with various properties and applications. In particular, the sensing properties of these AuNPs are illustrated through the detection of an analogue of a warfare agent (i.e., sulfur mustard) by means of a fluorescence "turn-on" assay, and the catalytic activity of the smallest triazole-AuNPs (core of 3.0 nm) is excellent for the reduction of 4-nitrophenol in water. PMID:24891131

  1. Dyes as bifunctional markers of DNA hybridization on surfaces and mutation detection.

    PubMed

    García-Mendiola, Tania; Cerro, María Ramos; López-Moreno, José María; Pariente, Félix; Lorenzo, Encarnación

    2016-10-01

    The interaction of small molecules with DNA has found diagnostic and therapeutic applications. In this work, we propose the use of two different dyes, in particular Azure A and Safranine, as bifunctional markers of on-surface DNA hybridization and potent tools for screening of specific gene mutations directly in real DNA PCR amplicons extracted from blood cells. By combining spectroscopic and electrochemical methods we demonstrate that both dyes can interact with single and double stranded DNA to a different extent, allowing reliable hybridization detection. From these data, we have also elucidated the nature of the interaction. We conclude that the binding mode is fundamentally intercalative with an electrostatic component. The dye fluorescence allows their use as nucleic acid stains for the detection of on-surfaces DNA hybridization. Its redox activity is exploited in the development of selective electrochemical DNA biosensors. PMID:27317997

  2. Bifunctional hairy silica nanoparticles as high-performance additives for lubricant

    NASA Astrophysics Data System (ADS)

    Sui, Tianyi; Song, Baoyu; Wen, Yu-Ho; Zhang, Feng

    2016-03-01

    Bifunctional hairy silica nanoparticles (BHSNs), which are silica nanoparticles covered with alkyl and amino organic chains, were prepared as high-performance additives for lubricants. Compared with hairy silica nanoparticles covered by a single type of organic chain, binary hairy silica nanoparticles exhibit the advantages of both types of organic chains, which exhibit excellent compatibility with lubricants and adsorbability to metal surfaces. Nanoparticles with different ratios of amino and alkyl ligands were investigated. In comparison to an untreated lubricant, BHSNs reduce the friction coefficient and wear scar diameter by 40% and 60%, respectively. The wear mechanism of BHSNs was investigated, and the protective and filling effect of the nanoparticles improved because of collaboration of amino and alkyl ligands.

  3. Novel 3-nitrotriazole-based amides and carbinols as bifunctional antichagasic agents.

    PubMed

    Papadopoulou, Maria V; Bloomer, William D; Lepesheva, Galina I; Rosenzweig, Howard S; Kaiser, Marcel; Aguilera-Venegas, Benjamín; Wilkinson, Shane R; Chatelain, Eric; Ioset, Jean-Robert

    2015-02-12

    3-Nitro-1H-1,2,4-triazole-based amides with a linear, rigid core and 3-nitrotriazole-based fluconazole analogues were synthesized as dual functioning antitrypanosomal agents. Such compounds are excellent substrates for type I nitroreductase (NTR) located in the mitochondrion of trypanosomatids and, at the same time, act as inhibitors of the sterol 14α-demethylase (T. cruzi CYP51) enzyme. Because combination treatments against parasites are often superior to monotherapy, we believe that this emerging class of bifunctional compounds may introduce a new generation of antitrypanosomal drugs. In the present work, the synthesis and in vitro and in vivo evaluation of such compounds is discussed. PMID:25580906

  4. Mono- and bi-functional arenethiols as surfactants for gold nanoparticles: synthesis and characterization

    PubMed Central

    2011-01-01

    Stable gold nanoparticles stabilized by different mono and bi-functional arenethiols, namely, benzylthiol and 1,4-benzenedimethanethiol, have been prepared by using a modified Brust's two-phase synthesis. The size, shape, and crystalline structure of the gold nanoparticles have been determined by high-resolution electron microscopy and full-pattern X-ray powder diffraction analyses. Nanocrystals diameters have been tuned in the range 2 ÷ 9 nm by a proper variation of Au/S molar ratio. The chemical composition of gold nanoparticles and their interaction with thiols have been investigated by X-ray photoelectron spectroscopy. In particular, the formation of networks has been observed with interconnected gold nanoparticles containing 1,4-benzenedimethanethiol as ligand. PMID:21711615

  5. Mechanistic Insights into the Mode of Action of Bifunctional Pyrrolidine-Squaramide-Derived Organocatalysts.

    PubMed

    Roca-López, David; Uria, Uxue; Reyes, Efraim; Carrillo, Luisa; Jørgensen, Karl Anker; Vicario, Jose L; Merino, Pedro

    2016-01-18

    The catalytic modes of action of three squaramide-derived bifunctional organocatalysts have been investigated using DFT methods. The [5+2] cycloaddition between oxidopyrylium ylides and enals was used as the model reaction. Two primary modes were possible for the different catalysts studied. The preference for one mode over the other was due to the possibility of additional favorable π-π interactions between the hydrogen-bond activated pyrylium ylide and an electron-deficient aromatic ring bonded to the squaramide NH group. The model can be extended to other reactions catalyzed by the same catalysts, such as formal [2+2] cycloadditions between nitroalkenes and α,β-unsaturated aldehydes. The computational results were in excellent concurrence with the available experimental reports on the observed total enantioselectivity and differences in diastereoselectivity depending on the substrate and the reaction. PMID:26612630

  6. Bi-Functional Biobased Packing of the Cassava Starch, Glycerol, Licuri Nanocellulose and Red Propolis

    PubMed Central

    Costa, Samantha Serra; Druzian, Janice Izabel; Machado, Bruna Aparecida Souza; de Souza, Carolina Oliveira; Guimarães, Alaíse Gil

    2014-01-01

    The aim of this study was to characterize and determine the bi-functional efficacy of active packaging films produced with starch (4%) and glycerol (1.0%), reinforced with cellulose nanocrystals (0–1%) and activated with alcoholic extracts of red propolis (0.4 to 1.0%). The cellulose nanocrystals used in this study were extracted from licuri leaves. The films were characterized using moisture, water-activity analyses and water vapor-permeability tests and were tested regarding their total phenolic compounds and mechanical properties. The antimicrobial and antioxidant efficacy of the films were evaluated by monitoring the use of the active films for packaging cheese curds and butter, respectively. The cellulose nanocrystals increased the mechanical strength of the films and reduced the water permeability and water activity. The active film had an antimicrobial effect on coagulase-positive staphylococci in cheese curds and reduced the oxidation of butter during storage. PMID:25383783

  7. A Cascade-Reaction Nanoreactor Composed of a Bifunctional Molecularly Imprinted Polymer that Contains Pt Nanoparticles.

    PubMed

    Wang, Jiao; Zhu, Maiyong; Shen, Xiaojuan; Li, Songjun

    2015-05-11

    This study was aimed at addressing the present challenge of cascade reactions, namely, how to furnish the catalysts with desired and hierarchical catalytic ability. This issue was addressed by constructing a cascade-reaction nanoreactor made of a bifunctional molecularly imprinted polymer containing acidic catalytic sites and Pt nanoparticles. The acidic catalytic sites within the imprinted polymer allowed one specified reaction, whereas the encapsulated Pt nanoparticles were responsible for another coupled reaction. To that end, the unique imprinted polymer was fabricated by using two well-coupled templates, that is, 4-nitrophenyl acetate and 4-nitrophenol. The catalytic hydrolysis of the former compound at the acidic catalytic sites led to the formation of the latter compound, which was further reduced by the encapsulated Pt nanoparticles to 4-aminophenol. Therefore, this nanoreactor demonstrated a catalytic-cascade ability. This protocol opens up the opportunity to develop functional catalysts for complicated chemical processes. PMID:25846700

  8. Bifunctional mechanism of catalysis in reactions leading to formation of /alpha/-amino ketones

    SciTech Connect

    Popov, A.F.; Anikeev, A.V.

    1988-10-20

    The kinetics of the reaction of /alpha/-bromoacetophenone and benzyl bromide with aniline and pyridine in the presence of additions of acetic acid and phenol in benzene at 30/degree/C were investigated. The catalytic effects due to the activity of the uncombined forms of the catalyst, their dimers, and their 1:1 complexes with the amines were separated quantitatively. The change in the catalytic activity of the respective particles in the solutions with variation in the structure of the reagents is examined, and possible mechanisms for the catalytic reactions are discussed on this basis. It is concluded that there is a bifunctional mechanism of catalysis by acetic acid in the reaction of /alpha/-bromoacetophenone with aniline.

  9. RNA Secondary Structure Modulates FMRP's Bi-Functional Role in the MicroRNA Pathway.

    PubMed

    Kenny, Phillip; Ceman, Stephanie

    2016-01-01

    MicroRNAs act by post-transcriptionally regulating the gene expression of 30%-60% of mammalian genomes. MicroRNAs are key regulators in all cellular processes, though the mechanism by which the cell activates or represses microRNA-mediated translational regulation is poorly understood. In this review, we discuss the RNA binding protein Fragile X Mental Retardation Protein (FMRP) and its role in microRNA-mediated translational regulation. Historically, FMRP is known to function as a translational suppressor. However, emerging data suggests that FMRP has both an agonistic and antagonistic role in regulating microRNA-mediated translational suppression. This bi-functional role is dependent on FMRP's interaction with the RNA helicase Moloney leukemia virus 10 (MOV10), which modifies the structural landscape of bound mRNA, therefore facilitating or inhibiting its association with the RNA-Induced Silencing Complex. PMID:27338369

  10. Overexpression of GSTA2 protects against cell cycle arrest and apoptosis induced by the DNA inter-strand crosslinking nitrogen mustard, mechlorethamine.

    PubMed

    Xie, Jingping; Shults, Keith; Flye, Leanne; Jiang, Fen; Head, David R; Briggs, Robert C

    2005-05-15

    The effectiveness of bifunctional alkylating nitrogen mustard compounds in chemotherapy is related to their ability to form DNA inter-strand crosslinks. Patients exposed to DNA inter-strand crosslinking (ICL) agents subsequently experience an elevated incidence of myelodysplastic syndromes (MDS) and MDS related acute myeloid leukemia. Fanconi's anemia (FA) patients are deficient in the repair of crosslink DNA damage and they experience a high incidence of MDS. These observations indicate that hematopoietic cells are specific target for the transforming effects of DNA crosslinking damage. Changes in transcript levels were characterized in human hematopoietic cells occurring in response to the nitrogen mustard, mechlorethamine (HN2), but not in response to monofunctional analogs. Only modest changes in a few gene transcripts were detected in HL60 cells exposed to levels of HN2 tittered to maximal dose that caused growth suppression with minimal cell death and allowed eventual resumption of normal cell growth. Under conditions of transient growth suppression, a subset of glutathione-S-transferase (GST) isoenzyme genes was consistently upregulated three to fourfold by HN2, but not by monofunctional analogs. Subsequent efforts to confirm the changes detected by microarray analyses revealed an unexpected dependence on treatment conditions. The GST alpha class A2 subfamily member transcripts were upregulated 24 h after a 1 h exposure to HN2 that caused an extensive, but transient block in late S/G2 cell cycle phase, but were minimally altered with continuous exposure. The 1-h exposure to HN2 caused a transient late S/G2 cell cycle arrest in both the HL-60 cell line and the Colo 320HSR human colon cancer cell line. Overexpression of GSTA2 by transient transfection protected Colo 320HSR cells against both cycle arrest and apoptosis following exposure to HN2. Overexpression of GSTA2 in Colo 320HSR cells induced after exposure to HN2 did not alter cycle arrest or apoptosis

  11. Eggplant-derived microporous carbon sheets: towards mass production of efficient bifunctional oxygen electrocatalysts at low cost for rechargeable Zn-air batteries.

    PubMed

    Li, Bing; Geng, Dongsheng; Lee, Xinjing Shannon; Ge, Xiaoming; Chai, Jianwei; Wang, Zhijuan; Zhang, Jie; Liu, Zhaolin; Hor, T S Andy; Zong, Yun

    2015-05-25

    We report 2D microporous carbon sheets with high surface area, derived from eggplant via simple carbonization and KOH activation, as low cost yet efficient bifunctional catalysts for high performance rechargeable zinc-air batteries. PMID:25920952

  12. Proteasome inhibitors act as bifunctional antagonists of human immunodeficiency virus type 1 latency and replication

    PubMed Central

    2013-01-01

    Background Existing highly active antiretroviral therapy (HAART) effectively controls viral replication in human immunodeficiency virus type 1 (HIV-1) infected individuals but cannot completely eradicate the infection, at least in part due to the persistence of latently infected cells. One strategy that is being actively pursued to eliminate the latent aspect of HIV-1 infection involves therapies combining latency antagonists with HAART. However, discordant pharmacokinetics between these types of drugs can potentially create sites of active viral replication within certain tissues that might be impervious to HAART. Results A preliminary reverse genetic screen indicated that the proteasome might be involved in the maintenance of the latent state. This prompted testing to determine the effects of proteasome inhibitors (PIs) on latently infected cells. Experiments demonstrated that PIs effectively activated latent HIV-1 in several model systems, including primary T cell models, thereby defining PIs as a new class of HIV-1 latency antagonists. Expanding upon experiments from previous reports, it was also confirmed that PIs inhibit viral replication. Moreover, it was possible to show that PIs act as bifunctional antagonists of HIV-1. The data indicate that PIs activate latent provirus and subsequently decrease viral titers and promote the production of defective virions from activated cells. Conclusions These results represent a proof-of-concept that bifunctional antagonists of HIV-1 can be developed and have the capacity to ensure precise tissue overlap of anti-latency and anti-replication functions, which is of significant importance in the consideration of future drug therapies aimed at viral clearance. PMID:24156270

  13. Cobalt Selenide Nanostructures: An Efficient Bifunctional Catalyst with High Current Density at Low Coverage.

    PubMed

    Masud, Jahangir; Swesi, Abdurazag T; Liyanage, Wipula P R; Nath, Manashi

    2016-07-13

    Electrodeposited Co7Se8 nanostructures exhibiting flake-like morphology show bifunctional catalytic activity for oxygen evolution and hydrogen evolution reaction (OER and HER, respectively) in alkaline medium with long-term durability (>12 h) and high Faradaic efficiency (99.62%). In addition to low Tafel slope (32.6 mV per decade), the Co7Se8 OER electrocatalyst also exhibited very low overpotential to achieve 10 mA cm(-2) (0.26 V) which is lower than other transition metal chalcogenide based OER electrocatalysts reported in the literature and significantly lower than the state-of-the-art precious metal oxides. A low Tafel slope (59.1 mV per decade) was also obtained for the HER catalytic activity in alkaline electrolyte. The OER catalytic activity could be further improved by creating arrays of 3-dimensional rod-like and tubular structures of Co7Se8 through confined electrodeposition on lithographically patterned nanoelectrodes. Such arrays of patterned nanostructures produced exceptionally high mass activity and gravimetric current density (∼68 000 A g(-1)) compared to the planar thin films (∼220 A g(-1)). Such high mass activity of the catalysts underlines reduction in usage of the active material without compromising efficiency and their practical applicability. The catalyst layer could be electrodeposited on different substrates, and an effect of the substrate surface on the catalytic activity was also investigated. The Co7Se8 bifunctional catalyst enabled water electrolysis in alkaline solution at a cell voltage of 1.6 V. The electrodeposition works with exceptional reproducibility on any conducting substrate and shows unprecedented catalytic performance especially with the patterned growth of catalyst rods and tubes. PMID:27309595

  14. Luminomagnetic bifunctionality of Mn2+-bonded graphene oxide/reduced graphene oxide two dimensional nanosheets

    NASA Astrophysics Data System (ADS)

    Amandeep; Kedawat, Garima; Kumar, Pawan; Anshul, Avaneesh; Deshmukh, Abhay D.; Singh, Om Pal; Gupta, R. K.; Amritphale, S. S.; Gupta, Govind; Singh, V. N.; Gupta, Bipin Kumar

    2015-07-01

    Herein, we report the luminomagnetic bifunctional properties of two-dimensional (2D) Mn2+ bonded graphene oxide (GO)/reduced graphene oxide (RGO) nanosheets synthesized using a facile route of oxidation followed by a solvothermal reduction method. Photoluminescence (PL) studies (excited by different wavelengths) revealed that the resonant energy transfer between Mn2+ and sp3/sp2 clusters of GO/RGO is responsible for the enhancement of emissions. Moreover, pH-sensitive PL behaviors have also been investigated in detail. The ferromagnetic behavior is believed to arise due to defects in Mn2+ bonded GO composites. Thus, present reduction method provides a direct route to tune and enhance the optical properties of GO and RGO nanosheets bonded with Mn2+ ions, which creates an opportunity for various technological applications.Herein, we report the luminomagnetic bifunctional properties of two-dimensional (2D) Mn2+ bonded graphene oxide (GO)/reduced graphene oxide (RGO) nanosheets synthesized using a facile route of oxidation followed by a solvothermal reduction method. Photoluminescence (PL) studies (excited by different wavelengths) revealed that the resonant energy transfer between Mn2+ and sp3/sp2 clusters of GO/RGO is responsible for the enhancement of emissions. Moreover, pH-sensitive PL behaviors have also been investigated in detail. The ferromagnetic behavior is believed to arise due to defects in Mn2+ bonded GO composites. Thus, present reduction method provides a direct route to tune and enhance the optical properties of GO and RGO nanosheets bonded with Mn2+ ions, which creates an opportunity for various technological applications. Electronic supplementary information (ESI) available. See DOI: 10.1039/c5nr01095k

  15. Preparation of Ga-67 labeled monoclonal antibodies using deferoxamine as a bifunctional chelating agent

    SciTech Connect

    Endo, K.; Furukawa, T.; Ohmomo, Y.; Sakahara, H.; Ohta, H.; Nakashima, T.; Okada, K.; Yoshida, O.; Yokoyama, A.; Torizuka, K.

    1984-01-01

    Ga-67 labeled monoclonal IgG or F(ab')/sub 2/ fragments against ..cap alpha..-fetoprotein and ..beta..-subunit of human choriogonadotropin (HCG), were prepared using Deferoxamine (DFO) as a bifunctional chelating agent. DFO, a well-known iron chelating agent, was conjugated with monoclonal antibodies (Ab) by a glutaraldehyde two step method and the effect of conjugation on the Ab activities was examined by RIA and Scatchard plot analysis. In both monoclonal Ab preparations, the conjugation reaction was favored as the pH increased. However, Ab-binding activities decreased as the molecular ratios of DFO to Ab increased. Preserved Ab activities were observed when Ab contained DFO per Ab molecule less than 2.1. At a ratio of over 3.3 DFO molecules per Ab, the maximal binding capacity rather than the affinity constant decreased. The inter-molecular cross linkage seemed to be responsible for the deactivation of binding activities. The obtained DFO-Ab conjugates, were then easily labeled with high efficiency and reproducibility and Ga-67 DFO-Ab complexes were highly stable both in vitro and in vivo. Thus, biodistribution of Ga-67 labeled F(ab')/sub 2/ fragments of monoclonal Ab to HCG ..beta..-subunit was attempted in nude mice transplanted with HCG-producing human teratocarcinoma. Tumor could be visualized, in spite of relatively high background imaging of liver, kidney and spleen. The use of DFO as a bifunctional chelating agent provided good evidence for its applicability to labeling monoclonal Ab with almost full retention of Ab activities. Further, availability of Ga-68 will make Ga-68 DFO-monoclonal Ab a very useful tool for positron tomography imaging of various tumors.

  16. Synthesis and Evaluation of New Generation Cross-Bridged Bifunctional Chelator for (64)Cu Radiotracers.

    PubMed

    Dale, Ajit V; An, Gwang Il; Pandya, Darpan N; Ha, Yeong Su; Bhatt, Nikunj; Soni, Nisarg; Lee, Hochun; Ahn, Heesu; Sarkar, Swarbhanu; Lee, Woonghee; Huynh, Phuong Tu; Kim, Jung Young; Gwon, Mi-Ri; Kim, Sung Hong; Park, Jae Gyu; Yoon, Young-Ran; Yoo, Jeongsoo

    2015-09-01

    Bifunctional chelators have been successfully used to construct (64)Cu-labeled radiopharmaceuticals. Previously reported chelators with cross-bridged cyclam backbones have various essential features such as high stability of the copper(II) complex, high efficiency of radiolabeling at room temperature, and good biological inertness of the radiolabeled complex, along with rapid body clearance. Here, we report a new generation propylene-cross-bridged chelator with hybrid acetate/phosphonate pendant groups (PCB-TE1A1P) developed with the aim of combining these key properties in a single chelator. The PCB-TE1A1P was synthesized from cyclam with good overall yield. The Cu(II) complex of our chelator showed good robustness in kinetic stability evaluation experiments, such as acidic decomplexation and cyclic voltammetry studies. The Cu(II) complex of PCB-TE1A1P remained intact under highly acidic conditions (12 M HCl, 90 °C) for 8 d and showed quasi-reversible reduction/oxidation peaks at -0.77 V in electrochemical studies. PCB-TE1A1P was successfully radiolabeled with (64)Cu ions in an acetate buffer at 60 °C within 60 min. The electrophoresis study revealed that the (64)Cu-PCB-TE1A1P complex has net negative charge in aqueous solution. The biodistribution and in vivo stability study profiles of (64)Cu-PCB-TE1A1P indicated that the radioactive complex was stable under physiological conditions and cleared rapidly from the body. A whole body positron emission tomography (PET) imaging study further confirmed high in vivo stability and fast clearance of the complex in mouse models. In conclusion, PCB-TE1A1P has good potential as a bifunctional chelator for (64)Cu-based radiopharmaceuticals, especially those involving peptides. PMID:26286436

  17. Increased Catalytic Efficiency Following Gene Fusion of Bifunctional Methionine Sulfoxide Reductase Enzymes from Shewanella oneidensis

    SciTech Connect

    Chen, Baowei; Markillie, Lye Meng; Xiong, Yijia; Mayer, M. Uljana; Squier, Thomas C.

    2007-11-11

    Methionine sulfoxide reductase enzymes MsrA and MsrB have complementary stereospecificies that respectively reduce the S- and R-stereoisomers of methionine sulfoxide (MetSO), and together function as critical antioxidant enzymes. In some pathogenic and metal reducing bacteria these genes are fused to form a bifunctional methionine sulfoxide reductase (i.e., MsrBA) enzyme. To investigate the impact of gene fusion on the substrate specificity and catalytic activities of Msr, we have cloned and expressed the MsrBA enzyme from Shewanella oneidensis, a metal reducing bacterium and fish pathogen. For comparison, we also cloned and expressed the wild-type MsrA enzyme and a genetically engineered MsrB protein. We report that MsrBA is able to completely reduce (i.e., repair) MetSO in the calcium regulatory protein calmodulin; in comparison only partial repair is observed using both MsrA and MsrB enzymes together at 25 °C. MsrBA has a twenty-fold enhanced rate of repair for MetSO in proteins in comparison with the individual MsrA or MsrB enzymes alone and respective 14- and 50-fold increases in catalytic efficiency (i.e., kcat/KM). In comparison, MsrBA and MsrA have similar catalytic efficiencies when free MetSO is used as a substrate. These results indicate that the individual domains within bifunctional MsrBA work cooperatively to selectively recognize and reduce MetSO in highly oxidized proteins. The enhanced catalytic activity of MsrBA against oxidized proteins and its common expression in bacterial pathogens is consistent with an important role for this enzyme activity in promoting bacterial survival under highly oxidizing conditions associated with pathogenesis or bioremediation.

  18. Mitigation of nitrogen mustard mediated skin injury by a novel indomethacin bifunctional prodrug.

    PubMed

    Composto, Gabriella M; Laskin, Jeffrey D; Laskin, Debra L; Gerecke, Donald R; Casillas, Robert P; Heindel, Ned D; Joseph, Laurie B; Heck, Diane E

    2016-06-01

    Nitrogen mustard (NM) is a bifunctional alkylating agent that is highly reactive in the skin causing extensive tissue damage and blistering. In the present studies, a modified cutaneous murine patch model was developed to characterize NM-induced injury and to evaluate the efficacy of an indomethacin pro-drug in mitigating toxicity. NM (20μmol) or vehicle control was applied onto 6mm glass microfiber filters affixed to the shaved dorsal skin of CD-1 mice for 6min. This resulted in absorption of approximately 4μmol of NM. NM caused localized skin damage within 1 d, progressing to an eschar within 2-3 d, followed by wound healing after 4-5 d. NM-induced injury was associated with increases in skin thickness, inflammatory cell infiltration, reduced numbers of sebocytes, basal keratinocyte double stranded DNA breaks, as measured by phospho-histone 2A.X expression, mast cell degranulation and increases in inducible nitric oxide synthase (iNOS) and cyclooxygenase-2 (COX-2). Wound healing was characterized by epidermal hyperplasia and marked increases in basal cells expressing proliferating cell nuclear antigen. A novel indomethacin-anticholinergic prodrug (4338) designed to target cyclooxygenases and acetylcholinesterase (AChE), was found to markedly suppress NM toxicity, decreasing wound thickness and eschar formation. The prodrug also inhibited mast cell degranulation, suppressed keratinocyte expression of iNOS and COX-2, as well as markers of epidermal proliferation. These findings indicate that a novel bifunctional pro-drug is effective in limiting NM mediated dermal injury. Moreover, our newly developed cutaneous patch model is a sensitive and reproducible method to assess the mechanism of action of countermeasures. PMID:27189522

  19. Dimerization and Bifunctionality Confer Robustness to the Isocitrate Dehydrogenase Regulatory System in Escherichia coli*

    PubMed Central

    Dexter, Joseph P.; Gunawardena, Jeremy

    2013-01-01

    An important goal of systems biology is to develop quantitative models that explain how specific molecular features give rise to systems-level properties. Metabolic and regulatory pathways that contain multifunctional proteins are especially interesting to study from this perspective because they have frequently been observed to exhibit robustness: the ability for a system to perform its proper function even as levels of its components change. In this study, we use extensive biochemical data and algebraic modeling to develop and analyze a model that shows how robust behavior arises in the isocitrate dehydrogenase (IDH) regulatory system of Escherichia coli, which was shown in 1985 to experimentally exhibit robustness. E. coli IDH is regulated by reversible phosphorylation catalyzed by the bifunctional isocitrate dehydrogenase kinase/phosphatase (IDHKP), and the level of IDH activity determines whether carbon flux is directed through the glyoxylate bypass (for growth on two-carbon substrates) or the full tricarboxylic acid cycle. Our model, which incorporates recent structural data on IDHKP, identifies several specific biochemical features of the system (including homodimerization of IDH and bifunctionality of IDHKP) that provide a potential explanation for robustness. Using algebraic techniques, we derive an invariant that summarizes the steady-state relationship between the phospho-forms of IDH. We use the invariant in combination with kinetic data on IDHKP to calculate IDH activity at a range of total IDH levels and find that our model predicts robustness. Our work unifies much of the known biochemistry of the IDH regulatory system into a single quantitative framework and highlights the importance of constructing biochemically realistic models in systems biology. PMID:23192354

  20. UV Crosslinking of Donor Corneas Confers Resistance to Keratolysis

    PubMed Central

    Arafat, Samer N.; Robert, Marie-Claude; Shukla, Anita N.; Dohlman, Claes H.; Chodosh, James; Ciolino, Joseph B.

    2014-01-01

    Purpose To develop a modified ex vivo corneal crosslinking method that increases stromal resistance to enzymatic degradation for use as a carrier for the Boston keratoprosthesis. Methods Ex vivo crosslinking of human corneas was performed using Barron® artificial anterior chambers. The corneas were de-epithelialized, pre-treated with riboflavin solution (0.1% riboflavin/20% dextran) and irradiated with ultraviolet A (UVA) light (λ=370nm, irradiance=3mW/cm2) for various durations. The combined effect of UVA and gamma (γ) irradiation was also assessed using the commercially available γ-irradiated corneal donors. The corneas were then trephined and incubated at 37 degrees Celsius with 0.3% collagenase A solution. The time to dissolution of each cornea was compared across treatments. Results De-epithelialized corneas (no UV light, no riboflavin) dissolved in 5.8 ± 0.6 hours. Crosslinked corneas demonstrated increased resistance to dissolution, with a time to dissolution of 17.8 +/− 2.6 hours (p < 0.0001). The corneal tissues’ resistance to collagenase increased with longer UVA exposure, reaching a plateau at 30 minutes. Crosslinking both the anterior and posterior corneas did not provide added resistance when compared to crosslinking the anterior corneas only (p>0.05). γ-irradiated corneas dissolved as readily as de-epithelialized controls regardless of whether they were further crosslinked (5.6 ± 1.2 hours) or not (6.1 ± 0.6 hours) (p=0.43) Conclusions Collagen crosslinking of the de-epithelialized anterior cornea surface for 30 minutes conferred optimal resistance to in vitro keratolysis by collagenase A. PMID:25014151

  1. Synthesis of borate cross-linked rhamnogalacturonan II

    PubMed Central

    Funakawa, Hiroya; Miwa, Kyoko

    2015-01-01

    In the present review, we describe current knowledge about synthesis of borate crosslinked rhamnogalacturonan II (RG-II) and it physiological roles. RG-II is a portion of pectic polysaccharide with high complexity, present in primary cell wall. It is composed of homogalacturonan backbone and four distinct side chains (A–D). Borate forms ester bonds with the apiosyl residues of side chain A of two RG-II monomers to generate borate dimerized RG-II, contributing for the formation of networks of pectic polysaccharides. In plant cell walls, more than 90% of RG-II are dimerized by borate under boron (B) sufficient conditions. Borate crosslinking of RG-II in primary cell walls, to our knowledge, is the only experimentally proven molecular function of B, an essential trace-element. Although abundance of RG-II and B is quite small in cell wall polysaccharides, increasing evidence supports that RG-II and its borate crosslinking are critical for plant growth and development. Significant advancement was made recently on the location and the mechanisms of RG-II synthesis and borate cross-linking. Molecular genetic studies have successfully identified key enzymes for RG-II synthesis and regulators including B transporters required for efficient formation of RG-II crosslinking and consequent normal plant growth. The present article focuses recent advances on (i) RG-II polysaccharide synthesis, (ii) occurrence of borate crosslinking and (iii) B transport for borate supply to RG-II. Molecular mechanisms underlying formation of borate RG-II crosslinking and the physiological impacts are discussed. PMID:25954281

  2. Mechano-responsive hydrogels crosslinked by reactive block copolymer micelles

    NASA Astrophysics Data System (ADS)

    Xiao, Longxi

    Hydrogels are crosslinked polymeric networks that can swell in water without dissolution. Owing to their structural similarity to the native extracelluar matrices, hydrogels have been widely used in biomedical applications. Synthetic hydrogels have been designed to respond to various stimuli, but mechanical signals have not incorporated into hydrogel matrices. Because most tissues in the body are subjected to various types of mechanical forces, and cells within these tissues have sophisticated mechano-transduction machinery, this thesis is focused on developing hydrogel materials with built-in mechano-sensing mechanisms for use as tissue engineering scaffolds or drug release devices. Self-assembled block copolymer micelles (BCMs) with reactive handles were employed as the nanoscopic crosslinkers for the construction of covalently crosslinked networks. BCMs were assembled from amphiphilic diblock copolymers of poly(n-butyl acrylate) and poly(acrylic acid) partially modified with acrylate. Radical polymerization of acrylamide in the presence of micellar crosslinkers gave rise to elastomeric hydrogels whose mechanical properties can be tuned by varying the BCM composition and concentration. TEM imaging revealed that the covalently integrated BCMs underwent strain-dependent reversible deformation. A model hydrophobic drug, pyrene, loaded into the core of BCMs prior to the hydrogel formation, was dynamically released in response to externally applied mechanical forces, through force-induced reversible micelle deformation and the penetration of water molecules into the micelle core. The mechano-responsive hydrogel has been studied for tissue repair and regeneration purposes. Glycidyl methacrylate (GMA)-modified hyaluronic acid (HA) was photochemically crosslinked in the presence of dexamethasone (DEX)-loaded crosslinkable BCMs. The resultant HA gels (HAxBCM) contain covalently integrated micellar compartments with DEX being sequestered in the hydrophobic core. Compared

  3. Redox-Responsive Micelles with Cores Crosslinked via Click Chemistry.

    PubMed

    Zhang, Xiaojin; Dong, Hui; Fu, Shuangli; Zhong, Zhenlin; Zhuo, Renxi

    2016-06-01

    Redox-responsive micelles with cores crosslinked via click chemistry are developed to improve the stability of polymer micelles. Amphiphilic block copolymer mPEG-b-P(DTC-ADTC) with pendant azido groups on the hydrophobic chains is synthesized by the ring-opening polymerization of 2,2-bis(azidomethyl)trimethylene carbonate (ADTC) and 2,2-dimethyltrimethylene carbonate (DTC) with monomethoxy poly(ethylene glycol) (mPEG) as an initiator. mPEG-b-P(DTC-ADTC) self-assemble to form the micelles in aqueous solution and the cores of the micelles are crosslinked via click chemistry to afford redox-responsive core-crosslinked micelles. Core-crosslinking enhances the stability of the micelles in aqueous solution and improve the drug-loading property. The redox-responsive core-crosslinked micelles can be reduced by the addition of reducing agents such as dithiothreitol (DTT), and thus release the loaded drug quickly in the presence of DTT. PMID:27150437

  4. Collagen/elastin hydrogels cross-linked by squaric acid.

    PubMed

    Skopinska-Wisniewska, J; Kuderko, J; Bajek, A; Maj, M; Sionkowska, A; Ziegler-Borowska, M

    2016-03-01

    Hydrogels based on collagen and elastin are very valuable materials for medicine and tissue engineering. They are biocompatible; however their mechanical properties and resistance for enzymatic degradation need to be improved by cross-linking. Up to this point many reagents have been tested but more secure reactants are still sought. Squaric acid (SqAc), 3,4-dihydroxy 3-cyclobutene 1,2-dione, is a strong, cyclic acid, which reacts easily with amine groups. The properties of hydrogels based on collagen/elastin mixtures (95/5, 90/10) containing 5%, 10% and 20% of SqAc and neutralized via dialysis against deionized water were tested. Cross-linked, 3-D, transparent hydrogels were created. The cross-linked materials are stiffer and more resistant to enzymatic degradation than those that are unmodified. The pore size, swelling ability and surface polarity are reduced due to 5% and 10% of SqAc addition. At the same time, the cellular response is not significantly affected by the cross-linking. Therefore, squaric acid would be regarded as a safe, effective cross-linking agent. PMID:26706512

  5. Tea derived galloylated polyphenols cross-link purified gastrointestinal mucins.

    PubMed

    Georgiades, Pantelis; Pudney, Paul D A; Rogers, Sarah; Thornton, David J; Waigh, Thomas A

    2014-01-01

    Polyphenols derived from tea are thought to be important for human health. We show using a combination of particle tracking microrheology and small-angle neutron scattering that polyphenols acts as cross-linkers for purified gastrointestinal mucin, derived from the stomach and the duodenum. Both naturally derived purified polyphenols, and green and black tea extracts are shown to act as cross-linkers. The main active cross-linking component is found to be the galloylated forms of catechins. The viscosity, elasticity and relaxation time of the mucin solutions experience an order of magnitude change in value upon addition of the polyphenol cross-linkers. Similarly small-angle neutron scattering experiments demonstrate a sol-gel transition with the addition of polyphenols, with a large increase in the scattering at low angles, which is attributed to the formation of large scale (>10 nm) heterogeneities during gelation. Cross-linking of mucins by polyphenols is thus expected to have an impact on the physicochemical environment of both the stomach and duodenum; polyphenols are expected to modulate the barrier properties of mucus, nutrient absorption through mucus and the viscoelastic microenvironments of intestinal bacteria. PMID:25162539

  6. Crosslinked Linear Polyethyleneimine Enhances Delivery of DNA to the Cytoplasm

    PubMed Central

    Bonner, Daniel K.; Zhao, Xiaoyong; Buss, Hilda; Langer, Robert

    2014-01-01

    Crosslinked polyethylenimines (PEIs) have been frequently examined over the past decade since they can maintain the transfection efficiency of commercially available, 25k branched PEI, but exhibit less cytotoxicity. The argument is often made that the degradability of such polymers, generally synthesized with either disulfide or hydrolytically degradable crosslinkers, is critical to the high efficiency and low toxicity of the system. In this work, we present a crosslinked linear PEI (xLPEI) system in which either disulfide-responsive or non-degradable linkages are incorporated. As with previous systems, strong transfection efficiency in comparison with commercial standards was achieved with low cytotoxicity. However, these properties were shown to be present when either the degradable or non-degradable crosslinker was used. Uncomplexed polymer was demonstrated to be the critical factor determining transfection efficiency for these polymers, mediating efficient endosomal escape without signs of cell membrane damage. While several crosslinked PEI systems in the literature have demonstrated the effect of the disulfide moiety, this work demonstrates that disulfide-mediated unpackaging may not be as important as conventionally thought for some PEI systems. PMID:22995755

  7. Spectroscopic characterization of collagen cross-links in bone

    NASA Technical Reports Server (NTRS)

    Paschalis, E. P.; Verdelis, K.; Doty, S. B.; Boskey, A. L.; Mendelsohn, R.; Yamauchi, M.

    2001-01-01

    Collagen is the most abundant protein of the organic matrix in mineralizing tissues. One of its most critical properties is its cross-linking pattern. The intermolecular cross-linking provides the fibrillar matrices with mechanical properties such as tensile strength and viscoelasticity. In this study, Fourier transform infrared (FTIR) spectroscopy and FTIR imaging (FTIRI) analyses were performed in a series of biochemically characterized samples including purified collagen cross-linked peptides, demineralized bovine bone collagen from animals of different ages, collagen from vitamin B6-deficient chick homogenized bone and their age- and sex-matched controls, and histologically stained thin sections from normal human iliac crest biopsy specimens. One region of the FTIR spectrum of particular interest (the amide I spectral region) was resolved into its underlying components. Of these components, the relative percent area ratio of two subbands at approximately 1660 cm(-1) and approximately 1690 cm(-1) was related to collagen cross-links that are abundant in mineralized tissues (i.e., pyridinoline [Pyr] and dehydrodihydroxylysinonorleucine [deH-DHLNL]). This study shows that it is feasible to monitor Pyr and DHLNL collagen cross-links spatial distribution in mineralized tissues. The spectroscopic parameter established in this study may be used in FTIRI analyses, thus enabling the calculation of relative Pyr/DHLNL amounts in thin (approximately 5 microm) calcified tissue sections with a spatial resolution of approximately 7 microm.

  8. Crosslinked macromolecular structures in bituminous coals: Theoretical and experimental considerations

    NASA Astrophysics Data System (ADS)

    Lucht, Lucy M.; Peppas, Nicolaos A.

    1981-02-01

    Ample evidence from physicochemical experiments suggests that bituminous coals can be described as highly crosslinked and entangled networks of macromolecular chains of irregular structure. Theoretically these structures can be analyzed by statistical mechanical models considering non-Gaussian distribution of the macro-molecular chains along with departure from the Flory theories of crosslinked macromolecules. The models of Kovac (1978) and Peppas and Lucht (1979) have been developed in order to describe non-extractable coal matrices and their behavior during swelling in appropriate swelling agents. The molecular weight between cross-links Mc and the crosslinking density ρx can be determined for various solvents and equilibrium swelling ratios. Few experimental data are available to which these models can be applied. Thus, in view of these new theoretical models, experimental research must be directed towards the reexamination of extraction and swelling behavior of bituminous coals. Some of the important parameters to be determined for characterization of the physical structure of coals include the thermodynamic interaction parameter χ, the crosslinking parameters Mc and ρx and the molecular weight distribution of the extractable coal portion.

  9. Simulations of Polymer Crazing: Effect of Crosslinks and Dilution

    NASA Astrophysics Data System (ADS)

    Robbins, Mark O.; Barsky, Sandra

    2000-03-01

    Molecular dynamics simulations were used to study the growth and structure of crazes in adhesive films of entangled linear polymers that have been either (a) crosslinked or (b) diluted by smaller molecules. The films were ruptured by separating the two bounding walls (adherends) at a small constant velocity. In all systems the force on the walls rose to the same value before the first yield event caused cavities to form in the film. These cavities grew as the walls were displaced further. In systems that formed a stable craze, cavity growth was eventually stopped by entanglements or crosslinks. Stress concentrations then caused new cavities to form in neighboring regions. This process continued at a constant plateau stress until the entire film had been stretched by an extension ratio λ. The plateau stress increased slightly with increasing crosslink density, and decreased with decreasing fraction of long chains in diluted systems. As in experiments, when the fraction decreased below about 30plateau stress vanished and there was no longer a stable craze. The extension ratio fell with increasing crosslink density and rose as the fraction of long chains dropped. These changes can be fit with a simple geometric model based on the ability to stretch a random coil whose length is the mean spacing between crosslinks or entanglements. No chain scission was found for reasonable bond strengths. Void formation and elastic constants were also studied.

  10. A first demonstration of Mars crosslink occultation measurements

    NASA Astrophysics Data System (ADS)

    Ao, C. O.; Edwards, C. D.; Kahan, D. S.; Pi, X.; Asmar, S. W.; Mannucci, A. J.

    2015-10-01

    A series of three crosslink occultation experiments have been acquired between the Mars Odyssey and Mars Reconnaissance Orbiter spacecraft to probe the Martian atmosphere in 2007. While crosslink occultations between Earth-orbiting satellites have been used to profile the Earth's atmosphere and ionosphere since 1995, this represents the first demonstration of crosslink occultation measurements at another planet. These measurements leverage the proximity link telecommunication payloads on each orbiter, which are nominally used to provide relay communication and navigation services to Mars landers and rovers. Analysis of the observed Doppler shift on each crosslink measurement reveals a clear signature of the Martian atmosphere, primarily the ionosphere. Inversion of the observed Doppler data yields vertical profiles of the Martian refractivity and electron density. The electron density profiles show the presence of two layers with peak densities and peak heights that are consistent with empirical model results. Our study demonstrates the feasibility and future potential of the crosslink radio occultation technique in the exploration of planetary atmospheres.

  11. Purification, crystallization and preliminary X-ray crystallographic analysis of rice bifunctional α-amylase/subtilisin inhibitor from Oryza sativa

    SciTech Connect

    Lin, Yi-Hung; Peng, Wen-Yan; Huang, Yen-Chieh; Guan, Hong-Hsiang; Hsieh, Ying-Cheng; Liu, Ming-Yih; Chang, Tschining; Chen, Chun-Jung

    2006-08-01

    The crystallization of rice α-amylase/subtilisin bifunctional inhibitor is reported. Rice bifunctional α-amylase/subtilisin inhibitor (RASI) can inhibit both α-amylase from larvae of the red flour beetle (Tribolium castaneum) and subtilisin from Bacillus subtilis. The synthesis of RASI is up-regulated during the late milky stage in developing seeds. The 8.9 kDa molecular-weight RASI from rice has been crystallized using the hanging-drop vapour-diffusion method. According to 1.81 Å resolution X-ray diffraction data from rice RASI crystals, the crystal belongs to space group P2{sub 1}2{sub 1}2, with unit-cell parameters a = 79.99, b = 62.95, c = 66.70 Å. Preliminary analysis indicates two RASI molecules in an asymmetric unit with a solvent content of 44%.

  12. Spinel Mn-Co oxide in N-doped carbon nanotubes as a bifunctional electrocatalyst synthesized by oxidative cutting.

    PubMed

    Zhao, Anqi; Masa, Justus; Xia, Wei; Maljusch, Artjom; Willinger, Marc-Georg; Clavel, Guylhaine; Xie, Kunpeng; Schlögl, Robert; Schuhmann, Wolfgang; Muhler, Martin

    2014-05-28

    The notorious instability of non-precious-metal catalysts for oxygen reduction and evolution is by far the single unresolved impediment for their practical applications. We have designed highly stable and active bifunctional catalysts for reversible oxygen electrodes by oxidative thermal scission, where we concurrently rupture nitrogen-doped carbon nanotubes and oxidize Co and Mn nanoparticles buried inside them to form spinel Mn-Co oxide nanoparticles partially embedded in the nanotubes. Impressively high dual activity for oxygen reduction and evolution is achieved using these catalysts, surpassing those of Pt/C, RuO2, and IrO2 and thus raising the prospect of functional low-cost, non-precious-metal bifunctional catalysts in metal-air batteries and reversible fuel cells, among others, for a sustainable and green energy future. PMID:24815686

  13. N,P-Codoped Carbon Networks as Efficient Metal-free Bifunctional Catalysts for Oxygen Reduction and Hydrogen Evolution Reactions.

    PubMed

    Zhang, Jintao; Qu, Liangti; Shi, Gaoquan; Liu, Jiangyong; Chen, Jianfeng; Dai, Liming

    2016-02-01

    The high cost and scarcity of noble metal catalysts, such as Pt, have hindered the hydrogen production from electrochemical water splitting, the oxygen reduction in fuel cells and batteries. Herein, we developed a simple template-free approach to three-dimensional porous carbon networks codoped with nitrogen and phosphorus by pyrolysis of a supermolecular aggregate of self-assembled melamine, phytic acid, and graphene oxide (MPSA/GO). The pyrolyzed MPSA/GO acted as the first metal-free bifunctional catalyst with high activities for both oxygen reduction and hydrogen evolution. Zn-air batteries with the pyrolyzed MPSA/GO air electrode showed a high peak power density (310 W g(-1) ) and an excellent durability. Thus, the pyrolyzed MPSA/GO is a promising bifunctional catalyst for renewable energy technologies, particularly regenerative fuel cells. PMID:26709954

  14. Vanadium nanobelts coated nickel foam 3D bifunctional electrode with excellent catalytic activity and stability for water electrolysis.

    PubMed

    Yu, Yu; Li, Pei; Wang, Xiaofang; Gao, Wenyu; Shen, Zongxu; Zhu, Yanan; Yang, Shuliang; Song, Weiguo; Ding, Kejian

    2016-05-19

    Pursuit of highly active, stable and low-cost electrocatalysts for hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) is the key point for large-scale water splitting. A vanadium nanobelts coating on a nickel foam (V/NF) is proposed as an excellent 3D bifunctional electrode for water electrolysis here, which exhibits high activities with overpotentials of 292 and 176 mV at 10 mA cm(-2) for OER and HER, respectively. When employed as a bifunctional electrocatalyst in an alkaline water electrolyzer, a cell voltage of 1.80 V was required to achieve 20 mA cm(-2) with a slight increase during a 24 h durability test. The existence of the appropriate amount of nitrogen and oxygen elements in the surface region of vanadium nanobelts is regarded to be responsible for the electrocatalytic activity. PMID:27152646

  15. MOFs as multifunctional catalysts: one-pot synthesis of menthol from citronellal over a bifunctional MIL-101 catalyst.

    PubMed

    Cirujano, F G; Llabrés i Xamena, F X; Corma, A

    2012-04-14

    A bifunctional MOF catalyst containing coordinatively unsaturated Cr(3+) sites and palladium nanoparticles (Pd@MIL-101) has been used for the cyclization of citronellal to isopulegol and for the one-pot tandem isomerization/hydrogenation of citronellal to menthol. The MOF was found to be stable under the reaction conditions used, and the results obtained indicate that the performance of this bifunctional solid catalyst is comparable with other state-of-the-art materials for the tandem reaction: Full citronellal conversion was attained over Pd@MIL-101 in 18 h, with 86% selectivity to menthols and a diastereoselectivity of 81% to the desired (-)-menthol, while up to 30 h were necessary for attaining similar values over Ir/H-beta under analogous reaction conditions. PMID:22382815

  16. Vertically integrated translational studies of PDX1 as a therapeutic target for pancreatic cancer via a novel bifunctional RNAi platform.

    PubMed

    Wu, J; Liu, S; Yu, J; Zhou, G; Rao, D; Jay, C M; Kumar, P; Sanchez, R; Templeton, N; Senzer, N; Maples, P; Nemunaitis, J; Brunicardi, F C

    2014-02-01

    RNA interference (RNAi) represents a powerful, new tool for scientific investigation as well as a promising new form of targeted gene therapy, with applications currently in clinical trials. Bifunctional short hairpin RNA (shRNA) are synthetic RNAi molecules, engineered to utilize multiple endogenous RNAi pathways to specifically silence target genes. Pancreatic and duodenal homeobox 1 (PDX1) is a key regulator of pancreatic development, β-cell differentiation, normal β-cell function and pancreatic cancer. Our aim is to review the process of identifying PDX1 as a specific, potential RNAi target in pancreatic cancer, as well as the underlying mechanisms and various forms of RNAi, with subsequent testing and development of PDX1-targeted bifunctional shRNA therapy. PMID:24457987

  17. Dual-Doped Molybdenum Trioxide Nanowires: A Bifunctional Anode for Fiber-Shaped Asymmetric Supercapacitors and Microbial Fuel Cells.

    PubMed

    Yu, Minghao; Cheng, Xinyu; Zeng, Yinxiang; Wang, Zilong; Tong, Yexiang; Lu, Xihong; Yang, Shihe

    2016-06-01

    A novel in situ N and low-valence-state Mo dual doping strategy was employed to significantly improve the conductivity, active-site accessibility, and electrochemical stability of MoO3 , drastically boosting its electrochemical properties. Consequently, our optimized N-MoO3-x nanowires exhibited exceptional performances as a bifunctional anode material for both fiber-shaped asymmetric supercapacitors (ASCs) and microbial fuel cells (MFCs). The flexible fiber-shaped ASC and MFC device based on the N-MoO3-x anode could deliver an unprecedentedly high energy density of 2.29 mWh cm(-3) and a remarkable power density of 0.76 μW cm(-1) , respectively. Such a bifunctional fiber-shaped N-MoO3-x electrode opens the way to integrate the electricity generation and storage for self-powered sources. PMID:27097987

  18. Metal Chelating Crosslinkers Form Nanogels with High Chelation Stability.

    PubMed

    Lux, Jacques; Chan, Minnie; Elst, Luce Vander; Schopf, Eric; Mahmoud, Enas; Laurent, Sophie; Almutairi, Adah

    2013-12-14

    We present a series of hydrogel nanoparticles (nanogels) incorporating either acyclic or cyclic metal chelates as crosslinkers. These crosslinkers are used to formulate polyacrylamide-based nanogels (diameter 50 to 85 nm) yielding contrast agents with enhanced relaxivities (up to 6-fold greater than Dotarem®), because this nanogel structure slows the chelator's tumbling frequency and allows fast water exchange. Importantly, these nanogels also stabilize Gd(3+) within the chelator thermodynamically and kinetically against metal displacement through transmetallation, which should reduce toxicity associated with release of free Gd(3+). This chelation stability suggests that the chelate crosslinker strategy may prove useful for other applications of metal-chelating nanoparticles in medicine, including other imaging modalities and radiotherapy. PMID:24505553

  19. Metal Chelating Crosslinkers Form Nanogels with High Chelation Stability

    PubMed Central

    Elst, Luce Vander; Schopf, Eric; Mahmoud, Enas; Laurent, Sophie; Almutairi, Adah

    2013-01-01

    We present a series of hydrogel nanoparticles (nanogels) incorporating either acyclic or cyclic metal chelates as crosslinkers. These crosslinkers are used to formulate polyacrylamide-based nanogels (diameter 50 to 85 nm) yielding contrast agents with enhanced relaxivities (up to 6-fold greater than Dotarem®), because this nanogel structure slows the chelator's tumbling frequency and allows fast water exchange. Importantly, these nanogels also stabilize Gd3+ within the chelator thermodynamically and kinetically against metal displacement through transmetallation, which should reduce toxicity associated with release of free Gd3+. This chelation stability suggests that the chelate crosslinker strategy may prove useful for other applications of metal-chelating nanoparticles in medicine, including other imaging modalities and radiotherapy. PMID:24505553

  20. Crossbar nanoarchitectonics of the crosslinked self-assembled monolayer

    PubMed Central

    2014-01-01

    A bottom-up approach was devised to build a crossbar device using the crosslinked SAM of the 5,5′-bis (mercaptomethyl)-2,2′-bipyridine-Ni2+ (BPD- Ni2+) on a gold surface. To avoid metal diffusion through the organic film, the author used (i) nanoscale bottom electrodes to reduce the probability of defects on the bottom electrodes and (ii) molecular crosslinked technology to avoid metal diffusion through the SAMs. The properties of the crosslinked self-assembled monolayer were determined by XPS. I-V characteristics of the device show thermally activated hopping transport. The implementation of this type of architecture will open up new vistas for a new class of devices for transport, storage, and computing. PMID:24994952

  1. Effect of different polysaccharides and crosslinkers on echium oil microcapsules.

    PubMed

    Comunian, Talita A; Gomez-Estaca, Joaquin; Ferro-Furtado, Roselayne; Conceição, Gelson José Andrade; Moraes, Izabel Cristina Freitas; de Castro, Inar Alves; Favaro-Trindade, Carmen S

    2016-10-01

    Microencapsulation by complex coacervation using gelatin and arabic gum (AG) as wall materials and transglutaminase for crosslinking is commonly used. However, AG is only produced in a few countries and transglutaminase is expensive. This work aimed to evaluate the encapsulation of echium oil by complex coacervation using gelatin and cashew gum (CG) as wall materials and sinapic acid (S) as crosslinker. Treatments were analyzed in relation to morphology, particle size, circularity, accelerated oxidation and submitted to different stress conditions. Rounded microcapsules were obtained for treatments with AG (45.45μm) and microcapsules of undefined format were obtained for treatments with CG (22.06μm). The S incorporation for 12h improved the oil stability by three fold compared to oil encapsulated without crosslinkers. Treatments with CG and S were resistant to different stress conditions similar to treatments with AG and transglutaminase, making this an alternative for delivery/application of compounds in food products. PMID:27312643

  2. Photo-crosslinkable polymers for fabrication of photonic multilayer sensors

    NASA Astrophysics Data System (ADS)

    Chiappelli, Maria; Hayward, Ryan C.

    2013-03-01

    We have used photo-crosslinkable polymers to fabricate photonic multilayer sensors. Benzophenone is utilized as a covalently incorporated pendent photo-crosslinker, providing a convenient means of fabricating multilayer films by sequential spin-coating and crosslinking processes. Colorimetric temperature sensors were designed from thermally-responsive, low-refractive index poly(N-isopropylacrylamide) (PNIPAM) and high-refractive index poly(para-methyl styrene) (P pMS). Copolymer chemistries and layer thicknesses were selected to provide robust multilayer sensors which show color changes across nearly the full visible spectrum due to changes in temperature of the hydrated film stack. We have characterized the uniformity and interfacial broadening within the multilayers, the kinetics of swelling and de-swelling, and the reversibility over multiple hydration/dehydration cycles. We also describe how the approach can be extended to alternative sensor designs through the ability to tailor each layer independently, as well as to additional stimuli by selecting alternative copolymer chemistries.

  3. Photonic multilayer sensors from photo-crosslinkable polymer films

    NASA Astrophysics Data System (ADS)

    Chiappelli, Maria; Hayward, Ryan C.

    2012-02-01

    Photo-crosslinkable copolymers containing pendent benzophenone (BP) groups provide a convenient means to fabricate multilayer polymer films. We describe the preparation of alternating multilayers of photo-crosslinkable poly(N-isopropylacrylamide) (PNIPAM), a water-swellable, temperature sensitive polymer, and poly(para-methylstyrene) (PpMS), a non-swellable polymer, by sequential spin-coating and photo-crosslinking. This route provides well-defined layered structures with minimal interfacial broadening between layers and uniformity of thickness from layer to layer as determined by dynamic secondary ion mass spectrometry (d-SIMS). Appropriate choices of layer thicknesses yield 1-D photonic gel sensors. The reflectance peak is shifted through the visible spectrum upon swelling or de-swelling of the PNIPAM layers in water, providing an accessible means for colorimetric temperature sensing.

  4. Polyvinyl alcohol cross-linked with two aldehydes

    NASA Technical Reports Server (NTRS)

    Sheibley, D. W.; Rieker, L. L.; Hsu, L. C.; Manzo, M. A. (Inventor)

    1982-01-01

    A film forming polyvinyl alcohol resin is admixed, in aqueous solution, with a dialdehyde crosslinking agent which is capable of crosslinking the polyvinyl alcohol resin and a water soluble acid aldehyde containing a reactive aldehyde group capable of reacting with hydroxyl groups in the polyvinyl alcohol resin and an ionizable acid hydrogen atom. The dialdehyde is present in an amount sufficient to react with from 1 to 20% by weight of the theoretical amount required to react with all of the hydroxyl groups of the polyvinyl alcohol. The amount of acid aldehyde is from 1 to 50% by weight, same basis, and is sufficient to reduce the pH of the aqueous admixture to 5 or less. The admixture is then formed into a desired physical shape, such as by casting a sheet or film, and the shaped material is then heated to simultaneously dry and crosslink the article.

  5. Design of naltrexone-loaded hydrolyzable crosslinked nanoparticles

    PubMed Central

    Yin, Wusheng; Akala, Emmanuel O.; Taylor, Robert E.

    2010-01-01

    A hydrolyzable crosslinker (N,O-dimethacryloylhydroxylamine (MANHOMA)) was synthesized by a modified method and was characterized using 1H-NMR, FTIR, and melting point determination. Naltrexone-loaded nanoparticles were prepared by copolymerization of poly(ethylene glycol)1000 monomethyl ether mono methacrylate (PEO-MA), methyl methacrylate (MMA) and N,O-dimethacryloylhydroxylamine (MANHOMA) in 0.4% poly(vinyl alcohol) aqueous solution. The nanoparticles were characterized by FTIR, particle size determination and transmission electron microscope (TEM). The TEM photomicrographs of the nanoparticles show a crosslinked core surrounded by a ring formed by the polyethylene glycol tail of PEO-MA. The loading efficiency of the nanoparticles and in vitro drug availability from the nanoparticles were investigated. The naltrexone-loaded hydrolyzable crosslinked nanoparticles were able to sustain the release of naltrexone for different periods of time, depending on the monomer feed composition. PMID:12204561

  6. T-CrAsH: a heterologous chemical crosslinker.

    PubMed

    Rutkowska, Anna; Plass, Tilman; Hoffmann, Jan-Erik; Yushchenko, Dmytro A; Feng, Suihan; Schultz, Carsten

    2014-08-18

    Copper-free click chemistry is currently the most promising and most rapidly developing technology for performing tailored chemical reactions inside intact living cells and animals. Its potential is particularly intensely explored in the field of live cell imaging, for both proteins and metabolites. Here we expand the application spectrum of click reactions to the chemical crosslinking of two proteins of choice in living cells. By combining strain-promoted Diels-Alder cycloaddition with FlAsH-based labeling of peptidic tetracysteine motifs, we developed the membrane-permeating reversible crosslinker T-CrAsH. We demonstrate the feasibility of the method both in vitro and inside cells. The biggest advantage of this new tool is the small size of the crosslinkable groups; this significantly decreases the risk of functional interference. PMID:25045107

  7. Synthesis, characterization, and evaluation of a novel bifunctional chelating agent for the lead isotopes 203Pb and 212Pb.

    PubMed

    Chappell, L L; Dadachova, E; Milenic, D E; Garmestani, K; Wu, C; Brechbiel, M W

    2000-01-01

    Radioisotopes of Pb(II) have been of some interest in radioimmunotherapy and radioimmunoimaging (RII). However, the absence of a kinetically stable bifunctional chelating agent for Pb(II) has hampered its use for these applications. 203Pb (T(1/2) = 52.02 h) has application potential in RII, with a gamma-emission that is ideal for single photon emission computerized tomography, whereas 212Pb (T(1/2) = 10 h) is a source of highly cytotoxic alpha-particles via its decay to its 212Bi (T(1/2) = 60 min) daughter. The synthesis of the novel bifunctional chelating agent 2-(4-isothiocyanotobenzyl)-1,4,7,10-tetraaza-1,4,7,10-tetra- (2-carbamoyl methyl)-cyclododecane (4-NCS-Bz-TCMC) is reported herein. The Pb[TCMC]2+ complex was less labile to metal ion release than Pb[DOTA]2- at pH 3.5 and below in isotopic exchange experiments. In addition to increased stability to Pb2+ ion release at low pH, the bifunctional TCMC ligand was found to have many other advantages over the bifunctional 1,4,7,10-tetraazacyclodocane-1,4,7,10-tetraacetic acid (DOTA) ligand. These include a shorter and more straightforward synthetic route, a more efficient conjugation reaction to a monoclonal antibody (mAb), with a higher chelate to protein ratio, a higher percent immuroreactivity, and a more efficient radiolabeling reaction of the mAb-ligand conjugate with 203Pb. PMID:10755652

  8. Synergistic bifunctional catalyst design based on perovskite oxide nanoparticles and intertwined carbon nanotubes for rechargeable zinc-air battery applications.

    PubMed

    Lee, Dong Un; Park, Hey Woong; Park, Moon Gyu; Ismayilov, Vugar; Chen, Zhongwei

    2015-01-14

    Advanced morphology of intertwined core-corona structured bifunctional catalyst (IT-CCBC) is introduced where perovskite lanthanum nickel oxide nanoparticles (LaNiO3 NP) are encapsulated by high surface area network of nitrogen-doped carbon nanotubes (NCNT) to produce highly active and durable bifunctional catalyst for rechargeable metal-air battery applications. The unique composite morphology of IT-CCBC not only enhances the charge transport property by providing rapid electron-conduction pathway but also facilitates in diffusion of hydroxyl and oxygen reactants through the highly porous framework. Confirmed by electrochemical half-cell testing, IT-CCBC in fact exhibits very strong synergy between LaNiO3 NP and NCNT demonstrating bifunctionality with significantly improved catalytic activities of oxygen reduction reaction (ORR) and oxygen evolution reaction (OER). Furthermore, when compared to the state-of-art catalysts, IT-CCBC outperforms Pt/C and Ir/C in terms of ORR and OER, respectively, and shows improved electrochemical stability compared to them after cycle degradation testing. The practicality of the catalyst is corroborated by testing in a realistic rechargeable zinc-air battery utilizing atmospheric air in ambient conditions, where IT-CCBC demonstrates superior charge and discharge voltages and long-term cycle stability with virtually no battery voltage fading. These improved electrochemical properties of the catalyst are attributed to the nanosized dimensions of LaNiO3 NP controlled by simple hydrothermal technique, which enables prolific growth of and encapsulation by highly porous NCNT network. The excellent electrochemical results presented in this study highlight IT-CCBC as highly efficient and commercially viable bifunctional catalyst for rechargeable metal-air battery applications. PMID:25494945

  9. Highly active and durable core-corona structured bifunctional catalyst for rechargeable metal-air battery application.

    PubMed

    Chen, Zhu; Yu, Aiping; Higgins, Drew; Li, Hui; Wang, Haijiang; Chen, Zhongwei

    2012-04-11

    A new class of core-corona structured bifunctional catalyst (CCBC) consisting of lanthanum nickelate centers supporting nitrogen-doped carbon nanotubes (NCNT) has been developed for rechargeable metal-air battery application. The nanostructured design of the catalyst allows the core and corona to catalyze the oxygen evolution reaction (OER) and oxygen reduction reaction (ORR), respectively. These materials displayed exemplary OER and ORR activity through half-cell testing, comparable to state of the art commercial lanthanum nickelate (LaNiO(3)) and carbon-supported platinum (Pt/C), with added bifunctional capabilities allowing metal-air battery rechargeability. LaNiO(3) and Pt/C are currently the most accepted benchmark electrocatalyst materials for the OER and ORR, respectively; thus with comparable activity toward both of these reactions, CCBC are presented as a novel, inexpensive catalyst component for the cathode of rechargeable metal-air batteries. Moreover, after full-range degradation testing (FDT) CCBC retained excellent activity, retaining 3 and 13 times greater ORR and OER current upon comparison to state of the art Pt/C. Zinc-air battery performances of CCBC is in good agreement with the half-cell experiments with this bifunctional electrocatalyst displaying high activity and stability during battery discharge, charge, and cycling processes. Owing to its outstanding performance toward both the OER and ORR, comparable with the highest performing commercial catalysts to date for each of the respective reaction, coupled with high stability and rechargeability, CCBC is presented as a novel class of bifunctional catalyst material that is very applicable to future generation rechargeable metal-air batteries. PMID:22372510

  10. Dynamic Kinetic Resolution of Biaryl Lactones via a Chiral Bifunctional Amine Thiourea-Catalyzed Highly Atropo-enantioselective Transesterification.

    PubMed

    Yu, Chenguang; Huang, He; Li, Xiangmin; Zhang, Yueteng; Wang, Wei

    2016-06-01

    A solution to the unmet synthetic challenge of achieving highly atropo-enantioselective transesterification of Bringmann's lactones has been realized, employing a chiral bifunctional amine thiourea as promoter. The synergistic activation of the lactones and alcohols/phenols by the respective thiourea and amine groups is crucial for achieving the highly enantioselective, high-yielding dynamic kinetic resolution process. This protocol gives highly optically pure, axially chiral biaryl compounds with a broad substrate scope under mild reaction conditions. PMID:27218264

  11. Vanadium nanobelts coated nickel foam 3D bifunctional electrode with excellent catalytic activity and stability for water electrolysis

    NASA Astrophysics Data System (ADS)

    Yu, Yu; Li, Pei; Wang, Xiaofang; Gao, Wenyu; Shen, Zongxu; Zhu, Yanan; Yang, Shuliang; Song, Weiguo; Ding, Kejian

    2016-05-01

    Pursuit of highly active, stable and low-cost electrocatalysts for hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) is the key point for large-scale water splitting. A vanadium nanobelts coating on a nickel foam (V/NF) is proposed as an excellent 3D bifunctional electrode for water electrolysis here, which exhibits high activities with overpotentials of 292 and 176 mV at 10 mA cm-2 for OER and HER, respectively. When employed as a bifunctional electrocatalyst in an alkaline water electrolyzer, a cell voltage of 1.80 V was required to achieve 20 mA cm-2 with a slight increase during a 24 h durability test. The existence of the appropriate amount of nitrogen and oxygen elements in the surface region of vanadium nanobelts is regarded to be responsible for the electrocatalytic activity.Pursuit of highly active, stable and low-cost electrocatalysts for hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) is the key point for large-scale water splitting. A vanadium nanobelts coating on a nickel foam (V/NF) is proposed as an excellent 3D bifunctional electrode for water electrolysis here, which exhibits high activities with overpotentials of 292 and 176 mV at 10 mA cm-2 for OER and HER, respectively. When employed as a bifunctional electrocatalyst in an alkaline water electrolyzer, a cell voltage of 1.80 V was required to achieve 20 mA cm-2 with a slight increase during a 24 h durability test. The existence of the appropriate amount of nitrogen and oxygen elements in the surface region of vanadium nanobelts is regarded to be responsible for the electrocatalytic activity. Electronic supplementary information (ESI) available: More SEM, TEM images, XRD patterns, LSV curves, XPS spectra. See DOI: 10.1039/c6nr02395a

  12. Iterative Coupling of Two Different Enones by Nitromethane Using Bifunctional Thiourea Organocatalysts. Stereocontrolled Assembly of Cyclic and Acyclic Structures.

    PubMed

    Varga, Szilárd; Jakab, Gergely; Csámpai, Antal; Soós, Tibor

    2015-09-18

    An organocatalytic iterative assembly line has been developed in which nitromethane was sequentially coupled with two different enones using a combination of pseudoenantiomeric cinchona-based thiourea catalysts. Application of unsaturated aldehydes and ketones in the second step of the iterative sequence allows the construction of cyclic syn-ketols and acyclic compounds with multiple contiguous stereocenters. The combination of the multifunctional substrates and ambident electrophiles rendered some organocatalytic transformations possible that have not yet been realized in bifunctional noncovalent organocatalysis. PMID:26301563

  13. Pros and cons of bifunctional platinum(IV) antitumor prodrugs: two are (not always) better than one.

    PubMed

    Gabano, Elisabetta; Ravera, Mauro; Osella, Domenico

    2014-07-14

    This article evaluates the efficacy and applicability of bifunctional prodrugs consisting of a six-coordinate Pt(iv) octahedral core and one or more bioactive molecules. The platinum(iv) complexes release upon reduction the corresponding cytotoxic Pt(ii) agents and the bioactive molecules, able to inhibit some biochemical mechanisms of cancer growth and/or prevent the deactivation of the Pt(ii) metabolites. PMID:24874896

  14. Guest-host crosslinked polyimides for integrated optics

    SciTech Connect

    Kowalczyk, T.C.; Kosc, T.Z.; Singer, K.D.; Beuhler, A.J.; Wargowski, D.A.; Cahill, P.A.; Seager, C.H.; Meinhardt, M.B.

    1995-07-01

    We report on the optical and electrical characterization of aromatic, fluorinated, fully imidized, organic soluble, thermally and photochemically, crosslinkable, guest-host polyimides for integrated optics. Refractive indices and optical losses were measured to evaluate the performance of these materials for passive applications. Materials were doped with two high temperature nonlinear optical chromophores, and poled during crosslinking to produce nonlinear optical materials. Measurements of electro-optic coefficient, macroscopic second order susceptibility, and conductivity were performed to assess these materials as potential candidates for active devices.

  15. Structure of psoralen-crosslinked ribosomal RNA from Drosophila melanogaster.

    PubMed Central

    Wollenzien, P L; Youvan, D C; Hearst, J E

    1978-01-01

    Ribosomal RNA from Drosophila melanogaster photoreacted with hydroxymethyltrioxsalen has been examined by electron microscopy. Reproducible patterns of hairpins were found in both the 26S and 18S RNA. The frequency of these hairpins and the amount of incorporated drug were dependent upon the conditions under which the crosslinking was performed. A prominent central hairpin occurs in the 26S RNA and the break that interrupts the continuity of the RNA chain is located within it. In addition to several small hairpins, the crosslinked 18S RNA contains a large open loop. Images PMID:417342

  16. Preparation of crosslinked 1,2,4-oxadiazole polymer

    NASA Technical Reports Server (NTRS)

    Rosser, R. W.; Shalhoub, I. M.; Kwong, H. (Inventor)

    1981-01-01

    New crosslinked 1,2,4-oxadiazole elastomers were prepared by thermally condensing a monomer having the formula H2N(HON)C-R-Q, wherein Q is a triazine ring-forming group such as nitrile or amidine or a mixture of such group with amidoxime, or a mixture of said monomer with R C(NOH)NH2 sub 2 with R in these formulas standing for a bivalent organic radical. In the monomer charge, the overall proportions of amidoxime groups to triazine ring-forming groups varies depending on the extent of crosslinking desired in the final polymer.

  17. Viscoelasticity of reversibly crosslinked networks of semiflexible polymers

    NASA Astrophysics Data System (ADS)

    Plagge, Jan; Fischer, Andreas; Heussinger, Claus

    2016-06-01

    We present a theoretical framework for the linear and nonlinear viscoelastic properties of reversibly crosslinked networks of semiflexible polymers. In contrast to affine models where network strain couples to the polymer end-to-end distance, in our model strain rather serves to locally distort the network structure. This induces bending modes in the polymer filaments, the properties of which are slaved to the surrounding network structure. Specifically, we investigate the frequency-dependent linear rheology, in particular in combination with crosslink binding-unbinding processes. We also develop schematic extensions to describe the nonlinear response during creep measurements as well as during constant strain-rate ramps.

  18. Constitutive models for rubber networks undergoing simultaneous crosslinking and scission.

    SciTech Connect

    Thompson, Aidan Patrick; Curro, John G.; Rottach, Dana R.; Grest, Gary Stephen; Budzien, Joanne L.; Lo, David Chi S.

    2006-01-01

    Constitutive models for chemically reacting networks are formulated based on a generalization of the independent network hypothesis. These models account for the coupling between chemical reaction and strain histories, and have been tested by comparison with microscopic molecular dynamics simulations. An essential feature of these models is the introduction of stress transfer functions that describe the interdependence between crosslinks formed and broken at various strains. Efforts are underway to implement these constitutive models into the finite element code Adagio. Preliminary results are shown that illustrate the effects of changing crosslinking and scission rates and history.

  19. Bi-functional air electrodes for metal-air batteries. Final report, September 15, 1993--December 14, 1994

    SciTech Connect

    Swette, L.L.; Manoukian, M.; LaConti, A.B.

    1995-12-01

    The program was directed to the need for development of bifunctional air electrodes for Zn-Air batteries for the consumer market. The Zn-Air system, widely used as a primary cell for hearing-aid batteries and as a remote-site power source in industrial applications, has the advantage of high energy density, since it consumes oxygen from the ambient air utilizing a thin, efficient fuel-cell-type gas-diffusion electrode, and is comparatively low in cost. The disadvantages of the current technology are a relatively low rate capability, and the lack of simple reversibility. {open_quotes}Secondary{close_quotes} Zn-Air cells require a third electrode for oxygen evolution or mechanical replacement of the Zinc anodes; thus the development of a bifunctional air electrode (i.e., an electrode that can alternately consume and evolve oxygen) would be a significant advance in Zn-Air cell technology. Evaluations of two carbon-free non-noble metal perovskite-type catalyst systems, La{sub 1-x}CA{sub x}CoO{sub 3} as bifunctional catalysts for potential application in Zn-air batteries were carried out. The technical objectives were to develop higher-surface-area materials and to fabricate reversible electrodes by modifying the hydrophobic/hydrophilic balance of the catalyst-binder structures.

  20. Construction and evaluation of a novel bifunctional phenylalanine-formate dehydrogenase fusion protein for bienzyme system with cofactor regeneration.

    PubMed

    Jiang, Wei; Fang, Bai-Shan

    2016-05-01

    Phenylalanine dehydrogenase (PheDH) plays an important role in enzymatic synthesis of L-phenylalanine for aspartame (sweetener) and detection of phenylketonuria (PKU), suggesting that it is important to obtain a PheDH with excellent characteristics. Gene fusion of PheDH and formate dehydrogenase (FDH) was constructed to form bifunctional multi-enzymes for bioconversion of L-phenylalanine coupled with coenzyme regeneration. Comparing with the PheDH monomer from Microbacterium sp., the bifunctional PheDH-FDH showed noteworthy stability under weakly acidic and alkaline conditions (pH 6.5-9.0). The bifunctional enzyme can produce 153.9 mM L-phenylalanine with remarkable performance of enantiomers choice by enzymatic conversion with high molecular conversion rate (99.87 %) in catalyzing phenylpyruvic acid to L-phenylalanine being 1.50-fold higher than that of the separate expression system. The results indicated the potential application of the PheDH and PheDH-FDH with coenzyme regeneration for phenylpyruvic acid analysis and L-phenylalanine biosynthesis in medical diagnosis and pharmaceutical field. PMID:26819086

  1. Gold nanoparticle immobilization on ZnO nanorods via bi-functional monolayers: A facile method to tune interface properties

    NASA Astrophysics Data System (ADS)

    Jayaraman, Sundaramurthy; Suresh Kumar, P.; Mangalaraj, D.; Dharmarajan, Rajarathnam; Ramakrishna, Seeram; P Srinivasan, M.

    2015-11-01

    We demonstrated the functionalization of one dimensional (1-D) zinc oxide nanorods (ZnO NRs) using bi-functional organic molecules to create hybrid structures with surface functionalities and tuneable organic/inorganic interface. Bi-functional molecules with carboxylic acid, thiol and silane end groups and amine termination had been employed to functionalize the NRs by forming carboxylate, thiolate and hydroxylation bonds, respectively, with ZnO. The surface textures of NRs were preserved even after functionalization. The functionalized NRs were decorated with gold nanoparticles (AuNPs) and the hybrid structures exhibited a quenched blue shift ultraviolet emission which depended on the distance between the ZnO surface and the AuNPs. The NR functionalization with bi-functional molecules and decoration of NPs, and surface morphologies were analyzed using x-ray photoelectron spectroscopy, field emission scanning electron microscopy and transmission electron spectroscopy. These hybrid structures can play a vital role in tuning the interface properties and have potential applications in future photovoltaics, chemical sensors, biomarkers, and wavelength based biosensors.

  2. Molecular and biochemical characterization of bifunctional pyruvate decarboxylases and pyruvate ferredoxin oxidoreductases from Thermotoga maritima and Thermotoga hypogea.

    PubMed

    Eram, Mohammad S; Wong, Alton; Oduaran, Erica; Ma, Kesen

    2015-12-01

    Hyperthermophilic bacteria Thermotoga maritima and Thermotoga hypogea produce ethanol as a metabolic end product, which is resulted from acetaldehyde reduction catalysed by an alcohol dehydrogenase (ADH). However, the enzyme that is involved in the production of acetaldehyde from pyruvate is not well characterized. An oxygen sensitive and coenzyme A-dependent pyruvate decarboxylase (PDC) activity was found to be present in cell free extracts of T. maritima and T. hypogea. Both enzymes were purified and found to have pyruvate ferredoxin oxidoreductase (POR) activity, indicating their bifunctionality. Both PDC and POR activities from each of the purified enzymes were characterized in regards to their optimal assay conditions including pH dependency, oxygen sensitivity, thermal stability, temperature dependency and kinetic parameters. The close relatedness of the PORs that was shown by sequence analysis could be an indication of the presence of such bifunctionality in other hyperthermophilic bacteria. This is the first report of a bifunctional PDC/POR enzyme in hyperthermophilic bacteria. The PDC and the previously reported ADHs are most likely the key enzymes catalysing the production of ethanol from pyruvate in bacterial hyperthermophiles. PMID:26032540

  3. Effects of Collagen Crosslinking on Bone Material Properties in Health and Disease.

    PubMed

    Saito, Mitsuru; Marumo, Keishi

    2015-09-01

    Data have accumulated to show that various types of collagen crosslinking are implicated in the health of individuals, as well as in a number of disease states, such as osteoporosis, diabetes mellitus, chronic kidney disease, inflammatory bowel disease, or in conditions of mild hyperhomocysteinemia, or when glucocorticoid use is indicated. Collagen crosslinking is a posttranslational modification of collagen molecules and plays important roles in tissue differentiation and in the mechanical properties of collagenous tissue. The crosslinking of collagen in the body can form via two mechanisms: one is enzymatic crosslinking and the other is nonenzymatic crosslinking. Lysyl hydroxylases and lysyl oxidases regulate tissue-specific crosslinking patterns and quantities. Enzymatic crosslinks initially form via immature divalent crosslinking, and a portion of them convert into mature trivalent forms such as pyridinoline and pyrrole crosslinks. Nonenzymatic crosslinks form as a result of reactions which create advanced glycation end products (AGEs), such as pentosidine and glucosepane. These types of crosslinks differ in terms of their mechanisms of formation and function. Impaired enzymatic crosslinking and/or an increase of AGEs have been proposed as a major cause of bone fragility associated with aging and numerous disease states. This review focuses on the effects of collagen crosslinking on bone material properties in health and disease. PMID:25791570

  4. Hexadentate bispidine derivatives as versatile bifunctional chelate agents for copper(II) radioisotopes.

    PubMed

    Juran, Stefanie; Walther, Martin; Stephan, Holger; Bergmann, Ralf; Steinbach, Jörg; Kraus, Werner; Emmerling, Franziska; Comba, Peter

    2009-02-01

    The preparation and use of bispidine derivatives (3,7-diazabicyclo[3.3.1]nonane) as chelate ligands for radioactive copper isotopes for diagnosis (64Cu) or therapy (67Cu) are reported. Starting from the hexadentate bispidine-based bis(amine)tetrakis(pyridine) ligand 1 with a keto and two ester substituents, the corresponding mono-ol 2 and two dicarboxylic acid derivatives 3 and 5 have been synthesized. A range of techniques, including single-crystal X-ray structure analysis, UV/vis spectroscopy, cyclic voltammetry, thin-layer- (TLC), and high-performance liquid chromatography (HPLC), have been used to characterize the structure and stability of the copper(II)-bispidine complexes. A rapid formation (within 1 min) of stable copper(II)-bispidine complexes under mild conditions (ambient temperature, aqueous solution) has been observed. Challenge experiments of these complexes in the presence of a high excess of competing ligands, such as glutathione, cyclam, or superoxide dismutase (SOD), as well as in rat plasma, gave no evidence of demetalation or transchelation. The bifunctional bispidine derivative 5 can be readily functionalized with biologically active molecules at the pendant carboxylate groups. The coupling of a bombesin analogue betahomo-Glu-betaAla-betaAla-[Cha(13),Nle(14)]BBN(7-14), by condensation of a carboxylate of the bispidine backbone with the N-terminus of the peptide produced the bifunctional ligand 6. The radiocopper(II) complex of this bombesin-bispidine conjugate has a considerable hydrophilicity (log D(o/w) < -2.4), and this leads to a very fast blood clearance (blood: 0.28 +/- 0.02 SUV, 1 h p.i.), low liver tissue accumulation (liver: 1.20 +/- 0.27 SUV, 1 h p.i.), and rapid renal-urinary excretion (kidneys: 6.06 +/- 2.96 SUV, 1 h p.i.) as shown by biodistribution studies of 64Cu-6 in Wistar rats. Preliminary in vivo studies of 64Cu-6 in NMRI nu/nu mice, bearing the human prostate tumor PC-3 showed an accumulation of the conjugate in the tumor (2

  5. Thiol-exchange in DTSSP crosslinked peptides is proportional to cysteine content and precisely controlled in crosslink detection by two-step LC-MALDI MSMS

    PubMed Central

    Lambert, Wietske; Söderberg, Christopher A G; Rutsdottir, Gudrun; Boelens, Wilbert C; Emanuelsson, Cecilia

    2011-01-01

    The lysine-specific crosslinker 3,3′-dithiobis(sulfosuccinimidylpropionate) (DTSSP) is commonly used in the structural characterization of proteins by chemical crosslinking and mass spectrometry and we here describe an efficient two-step LC-MALDI-TOF/TOF procedure to detect crosslinked peptides. First MS data are acquired, and the properties of isotope-labeled DTSSP are used in data analysis to identify candidate crosslinks. MSMS data are then acquired for a restricted number of precursor ions per spot for final crosslink identification. We show that the thiol-catalyzed exchange between crosslinked peptides, which is due to the disulfide bond in DTSSP and known to possibly obscure data, can be precisely quantified using isotope-labeled DTSSP. Crosslinked peptides are recognized as 8 Da doublet peaks and a new isotopic peak with twice the intensity appears in the middle of the doublet as a consequence of the thiol-exchange. False-positive crosslinks, formed exclusively by thiol-exchange, yield a 1:2:1 isotope pattern, whereas true crosslinks, formed by two lysine residues within crosslinkable distance in the native protein structure, yield a 1:0:1 isotope pattern. Peaks with a 1:X:1 isotope pattern, where 0 < X < 2, can be trusted as true crosslinks, with a defined proportion of the signal [2X/(2 + X)] being noise from the thiol-exchange. The thiol-exchange was correlated with the protein cysteine content and was minimized by shortening the trypsin incubation time, and for two molecular chaperone proteins with known structure all crosslinks fitted well to the structure data. The thiol-exchange can thus be controlled and isotope-labeled DTSSP safely used to detect true crosslinks between lysine residues in proteins. PMID:21780214

  6. Load transfer mechanisms in cross-linked DWNT fibers

    NASA Astrophysics Data System (ADS)

    Filleter, T.; Naraghi, M.; Moravsky, A.; Bernal, R.; Loutfy, R. O.; Espinosa, H. D.

    2011-03-01

    The application of carbon nanotubes (CNT) to macroscopic composite fibers has been limited by weak shear interfaces between adjacent CNT shells and composite matrix elements. A fundamental understanding of load transfer at multiple length-scales is needed to identify how the exceptional mechanical properties of CNTs can be scaled to produce high-performance fibers. Through in-situ electron microscopy tensile testing we have elucidated load transfer mechanisms across multiple scales of cross-linked double-walled nanotube (DWNT) fibers. A low density of polymer cross-links is found to increase the total energy dissipated at failure and ductility of fibers by 5 and 10X, respectively, without reducing strength. This mutiscale approach has identified a need to enhance shear interactions between individual DWNTs within the hierarchical DWNT fiber structures. Through in-situ TEM electron irradiation studies we have shown that load can be effectively transferred to inner DWNTs within bundles by covalently cross-linking the interfaces of adjacent DWNTs and shells. We have observed order of magnitude increases in strength and modulus and identified their dependence on irradiation dose. In future a combined approach of irradiation induced covalent and polymer cross-linking may lead to high-performance DWNT-based fibers and composites with tunable mechanical properties.

  7. Kinetics of Microphase Separation in Crosslinked Polymer Blend

    SciTech Connect

    Bettachy, A.; Benhamou, M.; Derouiche, A.; Fazni, A.

    2009-04-19

    The solvent effect on the early kinetics of the microphase separation (MPS) in binary crosslinked polymer was studied. In the presence of a good solvent, calculations were done using first the random phase approximation method and second an extended blob model, where a crosslinked chain is viewed as a sequence having blobs as new units. Kinetics were studied through the variation of the relaxation rate, {tau}{sub q}, upon the wave number, q, in the region around the spinodal temperature. When the temperature is changed from an initial value, T{sub i}, toward the final value, T{sub f}, very close to the critical point, the only motion allowed to the crosslinked chains is of Rouse type because of the presence of the crosslinks. The swelling effect on the MPS leads to a multiplicative renormalization of critical parameters of the molten state by factors as power of the overall monomer volume fraction, {phi}. The characteristic frequency, {omega}{sub (q)}, inverse of {tau}{sub q}, scales as {omega}(q) congruent with q{sup 6}{epsilon}{sup 3}, where {epsilon} stands for the traditional screening length. The study of kinetics of MPS is then extended in the presence of a theta solvent.

  8. New crosslinkers for electrospun chitosan fibre mats. I. Chemical analysis

    PubMed Central

    Austero, Marjorie S.; Donius, Amalie E.; Wegst, Ulrike G. K.; Schauer, Caroline L.

    2012-01-01

    Chitosan (CS), the deacetylated form of chitin, the second most abundant, natural polysaccharide, is attractive for applications in the biomedical field because of its biocompatibility and resorption rates, which are higher than chitin. Crosslinking improves chemical and mechanical stability of CS. Here, we report the successful utilization of a new set of crosslinkers for electrospun CS. Genipin, hexamethylene-1,6-diaminocarboxysulphonate (HDACS) and epichlorohydrin (ECH) have not been previously explored for crosslinking of electrospun CS. In this first part of a two-part publication, we report the morphology, determined by field emission scanning electron microscopy (FESEM), and chemical interactions, determined by Fourier transform infrared microscopy, respectively. FESEM revealed that CS could successfully be electrospun from trifluoroacetic acid with genipin, HDACS and ECH added to the solution. Diameters were 267 ± 199 nm, 644 ± 359 nm and 896 ± 435 nm for CS–genipin, CS–HDACS and CS–ECH, respectively. Short- (15 min) and long-term (72 h) dissolution tests (T600) were performed in acidic, neutral and basic pHs (3, 7 and 12). Post-spinning activation by heat and base to enhance crosslinking of CS–HDACS and CS–ECH decreased the fibre diameters and improved the stability. In the second part of this publication, we report the mechanical properties of the fibres. PMID:22628209

  9. SAXS Study of Reversibly Crosslinked Isotactic Polypropylene/clay Nanocomposites

    SciTech Connect

    Bouhelal, S.; Cagiao, M; Benachour, D; Djellouli, B; Rong, L; Hsiao, B; Baltá-Calleja, F

    2010-01-01

    A new route based on reversibly crosslinking reactive extrusion is applied for the development of iPP/clay nanocomposites. Analysis of small-angle X-ray scattering (SAXS) reflections of isotactic polypropylene (iPP)/clay nanocomposites, prepared by two different mixing and chemical crosslinking methods (i.e., conventional and in situ), is presented and results are compared with preceding wide-angle X-ray diffraction (WAXD) results. It is shown that the presence of clay significantly affects the value of long spacing in iPP, as well as the coherence length of lamellar stacks. Results show that the size of the coherently diffracting nanodomains decreases in two stages, first rapidly and then slowly as a function of increasing clay content. This can be attributed to the influence of confined iPP lamellae under the effect of rising number of clay particles. The appearance of the {gamma}-crystalline form in the crosslinked iPP/clay nanocomposites is related with the difficulty in chain folding of iPP chains introduced by the chemical crosslinking process, as well as by the presence of clay particles.

  10. Molecular mechanisms in deformation of cross-linked hydrogel nanocomposite.

    PubMed

    Mathesan, Santhosh; Rath, Amrita; Ghosh, Pijush

    2016-02-01

    The self-folding behavior in response to external stimuli observed in hydrogels is potentially used in biomedical applications. However, the use of hydrogels is limited because of its reduced mechanical properties. These properties are enhanced when the hydrogels are cross-linked and reinforced with nanoparticles. In this work, molecular dynamics (MD) simulation is applied to perform uniaxial tension and pull out tests to understand the mechanism contributing towards the enhanced mechanical properties. Also, nanomechanical characterization is performed using quasi static nanoindentation experiments to determine the Young's modulus of hydrogels in the presence of nanoparticles. The stress-strain responses for chitosan (CS), chitosan reinforced with hydroxyapatite (HAP) and cross-linked chitosan are obtained from uniaxial tension test. It is observed that the Young's modulus and maximum stress increase as the HAP content increases and also with cross-linking process. Load displacement plot from pullout test is compared for uncross-linked and cross-linked chitosan chains on hydroxyapatite surface. MD simulation reveals that the variation in the dihedral conformation of chitosan chains and the evolution of internal structural variables are associated with mechanical properties. Additional results reveal that the formation of hydrogen bonds and electrostatic interactions is responsible for the above variations in different systems. PMID:26652360

  11. A Traceless Cross-linker for Photo-Cleavable Bioconjugation

    PubMed Central

    Wang, Rong; Yan, Funing; Qiu, Dengli; Jeong, Jae-Sun; Jin, Qiaoling; Kim, Tae-Young; Chen, Liaohai

    2012-01-01

    Photo-responsive bioconjugation empowers the development of novel methods for drug discovery, disease diagnosis, and high-throughput screening, among the others. In this paper, we report on the characteristics of a traceless photo-cleavable cross-linker, di 6-(3-succinimidyl carbonyloxymethyl-4-nitro-phenoxy)-hexanoic acid disulfide diethanol ester (SCNE). The traceless feature and the biocompatibility of this photo-cleavable cross-linking reagent were corroborated. Consequently, we demonstrated its application in reversible phage particle immobilization that could provide a platform for direct single phage screening. We also applied it in protein-photoprinting, where SCNE acts as a “photo-eraser” to remove the cross-linked protein molecules at a desired region in a simple, clean and light-controllable fashion. We further demonstrated the two-tier atomic force microscopic (AFM) method that uses SCNE to carry out two subsequent AFM tasks in situ. The approach allows guided protein delivery and subsequent high-resolution imaging at the same local area, thus opens up the possibility of monitoring protein functions in live cells. The results imply that SCNE is a versatile cross-linker that can be used for a wide range of applications where photo-cleavage ensures clean and remote-controllable release of biological molecules from a substrate. PMID:22432929

  12. 21 CFR 177.1211 - Cross-linked polyacrylate copolymers.

    Code of Federal Regulations, 2011 CFR

    2011-04-01

    ... weight of aqueous sodium chloride solution at 20 °C for 24 hours. The low molecular weight extractives... applied mass). The solvent used shall be at least 60 milliliters aqueous sodium chloride solution per gram... polyacrylate copolymers consist of: (1) The grafted copolymer of cross-linked sodium polyacrylate identified...

  13. 21 CFR 177.1211 - Cross-linked polyacrylate copolymers.

    Code of Federal Regulations, 2013 CFR

    2013-04-01

    ... weight of aqueous sodium chloride solution at 20 °C for 24 hours. The low molecular weight extractives... applied mass). The solvent used shall be at least 60 milliliters aqueous sodium chloride solution per gram... polyacrylate copolymers consist of: (1) The grafted copolymer of cross-linked sodium polyacrylate identified...

  14. 21 CFR 177.1211 - Cross-linked polyacrylate copolymers.

    Code of Federal Regulations, 2010 CFR

    2010-04-01

    ... weight of aqueous sodium chloride solution at 20 °C for 24 hours. The low molecular weight extractives... applied mass). The solvent used shall be at least 60 milliliters aqueous sodium chloride solution per gram... polyacrylate copolymers consist of: (1) The grafted copolymer of cross-linked sodium polyacrylate identified...

  15. 21 CFR 177.1211 - Cross-linked polyacrylate copolymers.

    Code of Federal Regulations, 2014 CFR

    2014-04-01

    ...). The solvent used shall be at least 60 milliliters aqueous sodium chloride solution per gram of... grafted copolymer of cross-linked sodium polyacrylate identified as 2-propenoic acid, polymers with N,N-di-2-propenyl-2-propen-1-amine and hydrolyzed polyvinyl acetate, sodium salts, graft (CAS Reg....

  16. 21 CFR 177.1211 - Cross-linked polyacrylate copolymers.

    Code of Federal Regulations, 2012 CFR

    2012-04-01

    ... weight of aqueous sodium chloride solution at 20 °C for 24 hours. The low molecular weight extractives... applied mass). The solvent used shall be at least 60 milliliters aqueous sodium chloride solution per gram... polyacrylate copolymers consist of: (1) The grafted copolymer of cross-linked sodium polyacrylate identified...

  17. Femtosecond laser collagen cross-linking without traditional photosensitizers

    NASA Astrophysics Data System (ADS)

    Guo, Yizang; Wang, Chao; Celi, Nicola; Vukelic, Sinisa

    2015-03-01

    Collagen cross-linking in cornea has the capability of enhancing its mechanical properties and thereby providing an alternative treatment for eye diseases such as keratoconus. Currently, riboflavin assisted UVA light irradiation is a method of choice for cross-link induction in eyes. However, ultrafast pulsed laser interactions may be a powerful alternative enabling in-depth treatment while simultaneously diminishing harmful side effects such as, keratocyte apoptosis. In this study, femtosecond laser is utilized for treatment of bovine cornea slices. It is hypothesized that nonlinear absorption of femtosecond laser pulses plays a major role in the maturation of immature cross-links and the promotion of their growth. Targeted irradiation with tightly focused laser pulses allows for the absence of a photosensitizing agent. Inflation test was conducted on half treated porcine cornea to identify the changes of mechanical properties due to laser treatment. Raman spectroscopy was utilized to study subtle changes in the chemical composition of treated cornea. The effects of treatment are analyzed by observing shifts in Amide I and Amide III bands, which suggest deformation of the collagen structure in cornea due to presence of newly formed cross-links.

  18. Optimization model for UV-Riboflavin corneal cross-linking

    NASA Astrophysics Data System (ADS)

    Schumacher, S.; Wernli, J.; Scherrer, S.; Bueehler, M.; Seiler, T.; Mrochen, M.

    2011-03-01

    Nowadays UV-cross-linking is an established method for the treatment of keraectasia. Currently a standardized protocol is used for the cross-linking treatment. We will now present a theoretical model which predicts the number of induced crosslinks in the corneal tissue, in dependence of the Riboflavin concentration, the radiation intensity, the pre-treatment time and the treatment time. The model is developed by merging the difussion equation, the equation for the light distribution in dependence on the absorbers in the tissue and a rate equation for the polymerization process. A higher concentration of Riboflavin solution as well as a higher irradiation intensity will increase the number of induced crosslinks. However, performed stress-strain experiments which support the model showed that higher Riboflavin concentrations (> 0.125%) do not result in a further increase in stability of the corneal tissue. This is caused by the inhomogeneous distribution of induced crosslinks throughout the cornea due to the uneven absorption of the UV-light. The new model offers the possibility to optimize the treatment individually for every patient depending on their corneal thickness in terms of efficiency, saftey and treatment time.

  19. Improved Composites Using Crosslinked, Surface-Modified Carbon Nanotube Materials

    NASA Technical Reports Server (NTRS)

    Baker, James Stewart

    2014-01-01

    Individual carbon nanotubes (CNTs) exhibit exceptional tensile strength and stiffness; however, these properties have not translated well to the macroscopic scale. Premature failure of bulk CNT materials under tensile loading occurs due to the relatively weak frictional forces between adjacent CNTs, leading to poor load transfer through the material. When used in polymer matrix composites (PMCs), the weak nanotube-matrix interaction leads to the CNTs providing less than optimal reinforcement.Our group is examining the use of covalent crosslinking and surface modification as a means to improve the tensile properties of PMCs containing carbon nanotubes. Sheet material comprised of unaligned multi-walled carbon nanotubes (MWCNT) was used as a drop-in replacement for carbon fiber in the composites. A variety of post-processing methods have been examined for covalently crosslinking the CNTs to overcome the weak inter-nanotube shear interactions, resulting in improved tensile strength and modulus for the bulk sheet material. Residual functional groups from the crosslinking chemistry may have the added benefit of improving the nanotube-matrix interaction. Composites prepared using these crosslinked, surface-modified nanotube sheet materials exhibit superior tensile properties to composites using the as received CNT sheet material.

  20. 21 CFR 177.2420 - Polyester resins, cross-linked.

    Code of Federal Regulations, 2012 CFR

    2012-04-01

    ... 21 Food and Drugs 3 2012-04-01 2012-04-01 false Polyester resins, cross-linked. 177.2420 Section 177.2420 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES (CONTINUED) FOOD FOR HUMAN CONSUMPTION (CONTINUED) INDIRECT FOOD ADDITIVES: POLYMERS Substances for Use Only as Components of Articles Intended for...

  1. 21 CFR 177.2420 - Polyester resins, cross-linked.

    Code of Federal Regulations, 2010 CFR

    2010-04-01

    ... 21 Food and Drugs 3 2010-04-01 2009-04-01 true Polyester resins, cross-linked. 177.2420 Section 177.2420 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES (CONTINUED) FOOD FOR HUMAN CONSUMPTION (CONTINUED) INDIRECT FOOD ADDITIVES: POLYMERS Substances for Use Only as Components of Articles Intended for...

  2. 21 CFR 177.2420 - Polyester resins, cross-linked.

    Code of Federal Regulations, 2014 CFR

    2014-04-01

    ... 21 Food and Drugs 3 2014-04-01 2014-04-01 false Polyester resins, cross-linked. 177.2420 Section 177.2420 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES (CONTINUED) INDIRECT FOOD ADDITIVES: POLYMERS Substances for Use Only as Components of Articles Intended for Repeated Use § 177.2420 Polyester...

  3. Viscoelastic Nanomechanics of Ionically Cross-linked Polyelectrolyte Networks

    NASA Astrophysics Data System (ADS)

    Han, Biao; Lee, Daeyeon; Han, Lin

    2015-03-01

    Understanding the mechanics of ionic polyelectrolyte networks is critical for applications where nm-to-um mechanics is the key to success. This study aims to reveal the roles of ionic cross-links and fixed charges in the viscoelasticity of layer-by-layer poly(allylamine hydrochloride)/poly(acrylic acid) microfilms, PAH/PAA, a complex held by pH-sensitive amine-carboxyl links. AFM-nanoindentation and force relaxation (tip R =12.5um) was performed at ionic strength(IS) =0.01-1.0M, pH =5.5-2.0 (pKa of PAA =2.3). When pH changes from 5.5 to 2.0, the films swell for 4x from densely linked, net neutral state to loosely linked, positively charged one. A >100x reduction in indentation modulus was observed at all IS, suggesting the dominance of decrease in cross-link density. In most states, more than 90% force relaxation was observed, where cross-link breaking/reformation likely dominates viscoelasticity. However, at pH =2.5 and IS =0.01M, when electrical double layer repulsion is important (Debye length =3nm), relaxation was about 60%, highlighting the contribution of fixed charges. In summary, this study revealed unique viscoelastic behaviors of PAH/PAA due to the pH- and IS-dependent cross-link and charge densities.

  4. Epoxy-crosslinked sulfonated poly (phenylene) copolymer proton exchange membranes

    DOEpatents

    Hibbs, Michael; Fujimoto, Cy H.; Norman, Kirsten; Hickner, Michael A.

    2010-10-19

    An epoxy-crosslinked sulfonated poly(phenylene) copolymer composition used as proton exchange membranes, methods of making the same, and their use as proton exchange membranes (PEM) in hydrogen fuel cells, direct methanol fuel cell, in electrode casting solutions and electrodes, and in sulfur dioxide electrolyzers. These improved membranes are tougher, have higher temperature capability, and lower SO.sub.2 crossover rates.

  5. Crosslink Radio Occultation for the Remote Sensing of Planetary Atmospheres

    NASA Astrophysics Data System (ADS)

    Mannucci, A. J.; Ao, C. O.; Asmar, S.; Edwards, C. D.; Kahan, D. S.; Paik, M.; Pi, X.; Williamson, W.

    2015-12-01

    Radio occultation utilizing deep space telecommunication signals has been used with great success in the profiling of planetary atmospheres and ionospheres since the 1960s. A shortcoming of this technique, however, is the limited temporal and spatial sampling that it provides. We consider a different approach where radio occultation measurements are taken between two spacecraft orbiting an extra-terrestrial body. Such "crosslink" radio occultations between the Global Positioning System satellites and low-earth orbiting spacecraft have been routinely acquired to provide global observations of the Earth's atmosphere and ionosphere that are used for weather forecast, climate analysis, and space weather applications. The feasibility of applying this concept to other planets has recently been demonstrated for the first time, where crosslink occultation measurements have been acquired between the Mars Odyssey and Mars Reconnaissance Orbiter spacecraft. These measurements leverage the proximity link telecommunication payloads on each orbiter, which are nominally used to provide relay communication and navigation services to Mars landers and rovers. In this presentation, we will describe the Mars crosslink experiments and the corresponding data analysis in detail. In addition, we will discuss how the crosslink occultation concepts can be effectively applied in future space exploration missions.

  6. Probing RNA tertiary structure: interhelical crosslinking of the hammerhead ribozyme.

    PubMed Central

    Sigurdsson, S T; Tuschl, T; Eckstein, F

    1995-01-01

    Distinct structural models for the hammerhead ribozyme derived from single-crystal X-ray diffraction and fluorescence resonance energy transfer (FRET) measurements have been compared. Both models predict the same overall geometry, a wishbone shape with helices II and III nearly colinear and helix I positioned close to helix II. However, the relative orientations of helices I and II are different. To establish whether one of the models represents a kinetically active structure, a new crosslinking procedure was developed in which helices I and II of hammerhead ribozymes were disulfide-crosslinked via the 2' positions of specific sugar residues. Crosslinking residues on helices I and II that are close according to the X-ray structure did not appreciably reduce the catalytic efficiency. In contrast, crosslinking residues closely situated according to the FRET model dramatically reduced the cleavage rate by at least three orders of magnitude. These correlations between catalytic efficiencies and spatial proximities are consistent with the X-ray structure. PMID:7489517

  7. Crosslinking-Induced Endocytosis of Acetylcholine Receptors by Quantum Dots

    PubMed Central

    Geng, Lin; Peng, H. Benjamin

    2014-01-01

    In a majority of patients with myasthenia gravis (MG), anti-acetylcholine receptor (AChR) antibodies target postsynaptic AChR clusters and thus compromise the membrane integrity of neuromuscular junctions (NMJs) and lead to muscle weakness. Antibody-induced endocytosis of AChRs in the postsynaptic membrane represents the initial step in the pathogenesis of MG; however, the molecular mechanisms underlying AChR endocytosis remain largely unknown. Here, we developed an approach to mimic the pathogenic antibodies for inducing the crosslinking and internalization of AChRs from the postsynaptic membrane. Using biotin-α-bungarotoxin and quantum dot (QD)-streptavidin, cell-surface and internalized AChRs could be readily distinguished by comparing the size, fluorescence intensity, trajectory, and subcellular localization of the QD signals. QD-induced AChR endocytosis was mediated by clathrin-dependent and caveolin-independent mechanisms, and the trafficking of internalized AChRs in the early endosomes required the integrity of microtubule structures. Furthermore, activation of the agrin/MuSK (muscle-specific kinase) signaling pathway strongly suppressed QD-induced internalization of AChRs. Lastly, QD-induced AChR crosslinking potentiated the dispersal of aneural AChR clusters upon synaptic induction. Taken together, our results identify a novel approach to study the mechanisms of AChR trafficking upon receptor crosslinking and endocytosis, and demonstrate that agrin-MuSK signaling pathways protect against crosslinking-induced endocytosis of AChRs. PMID:24587270

  8. Tunable photonic multilayer sensors from photo-crosslinkable polymers

    NASA Astrophysics Data System (ADS)

    Chiappelli, Maria; Hayward, Ryan

    2014-03-01

    The fabrication of tunable photonic multilayer sensors from stimuli-responsive, photo-crosslinkable polymers will be described. Benzophenone is covalently incorporated as a pendent photo-crosslinker, allowing for facile preparation of multilayer films by sequential spin-coating and crosslinking processes. Copolymer chemistries and layer thicknesses are selected to provide robust multilayer sensors which can show color changes across nearly the full visible spectrum due to the specific stimulus-responsive nature of the hydrated film stack. We will describe how this approach is extended to alternative sensor designs by tailoring the thickness and chemistry of each layer independently, allowing for the preparation of sensors which depend not only on the shift in wavelength of a reflectance peak, but also on the transition between Bragg mirrors and filters. Device design is optimized by photo-patterning sensor arrays on a single substrate, providing more efficient fabrication time as well as multi-functional sensors. Finally, radiation-sensitive multilayers, designed by choosing polymers which will preferentially degrade or crosslink under ionizing radiation, will also be described.

  9. In situ crosslinkable hyaluronan hydrogels for tissue engineering.

    PubMed

    Zheng Shu, Xiao; Liu, Yanchun; Palumbo, Fabio S; Luo, Yi; Prestwich, Glenn D

    2004-01-01

    We describe the development of an injectable, cell-containing hydrogel that supports cell proliferation and growth to permit in vivo engineering of new tissues. Two thiolated hyaluronan (HA) derivatives were coupled to four alpha,beta-unsaturated ester and amide derivatives of poly(ethylene glycol) (PEG) 3400. The relative chemical reactivity with cysteine decreased in the order PEG-diacrylate (PEGDA)>PEG-dimethacrylate>PEG-diacrylamide>PEG-dimethacrylamide. The 3-thiopropanoyl hydrazide derivative (HA-DTPH) was more reactive than the 4-thiobutanoyl hydrazide, HA-DTBH. The crosslinking of HA-DTPH with PEGDA in a molar ratio of 2:1 occurred in approximately 9 min, suitable for an in situ crosslinking applications. The in vitro cytocompatibility and in vivo biocompatibility were evaluated using T31 human tracheal scar fibroblasts, which were suspended in medium in HA-DTPH prior to addition of the PEGDA solution. The majority of cells survived crosslinking and the cell density increased tenfold during the 4-week culture period in vitro. Cell-loaded hydrogels were also implanted subcutaneously in the flanks of nude mice, and after immunohistochemistry showed that the encapsulated cells retained the fibroblast phenotype and secreted extracellular matrix in vivo. These results confirm the potential utility of the HA-DTPH-PEGDA hydrogel as an in situ crosslinkable, injectable material for tissue engineering. PMID:14643608

  10. Recycling tires? Reversible crosslinking of poly(butadiene).

    PubMed

    Trovatti, Eliane; Lacerda, Talita M; Carvalho, Antonio J F; Gandini, Alessandro

    2015-04-01

    Furan-modified poly(butadiene) prepared by the thiol-ene click reaction is crosslinked with bismaleimides through the Diels-Alder reaction, giving rise to a novel recyclable elastomer. This is possible because of the thermal reversibility of the adducts responsible for the formation of the network. The use of this strategy provides the possibility to produce recyclable tires. PMID:25689366

  11. Polyimide Aerogels with Three-Dimensional Cross-Linked Structure

    NASA Technical Reports Server (NTRS)

    Meador, Mary Ann B. (Inventor)

    2016-01-01

    A method for creating a three dimensional cross-linked polyimide structure includes dissolving a diamine, a dianhydride, and a triamine in a solvent, imidizing a polyamic acid gel by heating the gel, extracting the gel in a second solvent, supercritically drying the gel, and removing the solvent to create a polyimide aerogel.

  12. Specific covalent immobilization of proteins through dityrosine cross-links.

    PubMed

    Endrizzi, Betsy J; Huang, Gang; Kiser, Patrick F; Stewart, Russell J

    2006-12-19

    Dityrosine cross-links are widely observed in nature in structural proteins such as elastin and silk. Natural oxidative cross-linking between tyrosine residues is catalyzed by a diverse group of metalloenzymes. Dityrosine formation is also catalyzed in vitro by metal-peptide complexes such as Gly-Gly-His-Ni(II). On the basis of these observations, a system was developed to specifically and covalently surface immobilize proteins through dityrosine cross-links. Methacrylate monomers of the catalytic peptide Gly-Gly-His-Tyr-OH (GGHY) and the Ni(II)-chelating group nitrilotriacetic acid (NTA) were copolymerized with acrylamide into microbeads. Green fluorescent protein (GFP), as a model protein, was genetically tagged with a tyrosine-modified His6 peptide on its carboxy terminus. GFP-YGH6, specifically associated with the NTA-Ni(II) groups, was covalently coupled to the bead surface through dityrosine bond formation catalyzed by the colocalized GGHY-Ni(II) complex. After extensive washing with EDTA to disrupt metal coordination bonds, we observed that up to 75% of the initially bound GFP-YGH6 remained covalently bound to the bead while retaining its structure and activity. Dityrosine cross-linking was confirmed by quenching the reaction with free tyrosine. The method may find particular utility in the construction and optimization of protein microarrays. PMID:17154619

  13. Porous Cross-Linked Polyimide-Urea Networks

    NASA Technical Reports Server (NTRS)

    Meador, Mary Ann B. (Inventor); Nguyen, Baochau N. (Inventor)

    2015-01-01

    Porous cross-linked polyimide-urea networks are provided. The networks comprise a subunit comprising two anhydride end-capped polyamic acid oligomers in direct connection via a urea linkage. The oligomers (a) each comprise a repeating unit of a dianhydride and a diamine and a terminal anhydride group and (b) are formulated with 2 to 15 of the repeating units. The subunit was formed by reaction of the diamine and a diisocyanate to form a diamine-urea linkage-diamine group, followed by reaction of the diamine-urea linkage-diamine group with the dianhydride and the diamine to form the subunit. The subunit has been cross-linked via a cross-linking agent, comprising three or more amine groups, at a balanced stoichiometry of the amine groups to the terminal anhydride groups. The subunit has been chemically imidized to yield the porous cross-linked polyimide-urea network. Also provided are wet gels, aerogels, and thin films comprising the networks, and methods of making the networks.

  14. Ionic liquid crosslinkers for chiral imprinted nanoGUMBOS.

    PubMed

    Hamdan, Suzana; Moore, Leonard; Lejeune, Jason; Hasan, Farhana; Carlisle, Trevor K; Bara, Jason E; Gin, D L; LaFrate, Andrew L; Noble, R D; Spivak, David A; Warner, Isiah M

    2016-02-01

    Molecularly imprinted polymers (MIPs) are an important class of selective materials for molecular specific sensors and separations. Molecular imprinting using non-covalent interactions in aqueous conditions still remains a difficult challenge due to interruption of hydrogen-bonding or electrostatic interactions water. Newly developed crosslinking ionic liquids are demonstrated herein to overcome problems of synthesizing aqueous MIPs, adding to previous examples of ionic liquids used as monomers in non-aqueous conditions or used as MIP solvents. Vinylimidazole ionic liquid crosslinkers were synthesized and subsequently explored as matrix supports for fabrication of molecularly imprinted polymeric nanoGUMBOS (nanoparticles derived from a group of uniform materials based on organic salts). Each of the four crosslinkers incorporated a unique functional spacer between the vinylimidazole groups, and the performance of the corresponding molecularly imprinted polymers was evaluated using chiral recognition as the diagnostic. High uptake values for l-tryptophan were found in the 13-87μmol/g range; and chiral recognition was determined via binding ratios of l-tryptophan over d-tryptophan that ranged from 5:1 to 13:1 for polymers made using different crosslinkers. Not only are these materials good for chiral recognition, but the results highlight the utility of these materials for imprinting aqueous templates such as biological targets for theranostic agents. PMID:26513734

  15. Selective permeability of PVA membranes. I - Radiation-crosslinked membranes

    NASA Technical Reports Server (NTRS)

    Katz, M. G.; Wydeven, T., Jr.

    1981-01-01

    The water and salt transport properties of ionizing radiation crosslinked poly(vinyl alcohol) (PVA) membranes were investigated. The studied membranes showed high permeabilities and low selectivities for both water and salt. The results were found to be in accord with a modified solution-diffusion model for transport across the membranes, in which pressure-dependent permeability coefficients are employed.

  16. Selective Permeability of PVA Membranes. I: Radiation-Crosslinked Membranes

    NASA Technical Reports Server (NTRS)

    Katz, Moshe G.; Wydeven, Theodore, Jr.

    1981-01-01

    The water and salt transport properties of ionizing radiation crosslinked poly(vinyl alcohol) (PVA) membranes were investigated. The studied membranes showed high permeabilities and low selectivities for both water and salt. The results were found to be in accord with a modified solution-diffusion model for transport across the membranes, in which pressure-dependent permeability coefficients are employed.

  17. Synergistic effects in the processes of crosslinking of elastomers

    NASA Astrophysics Data System (ADS)

    Głuszewski, Wojciech; Zagórski, Zbigniew P.; Rajkiewicz, Maria

    2014-01-01

    Radiation crosslinking of elastomers is an example of the modification of polymers by ionizing radiation. In practice, often parallel both traditional crosslinking (with peroxide) and radiation treatment is applied (Bik et al., 2003, 2004). Elastomers can be irradiated both before and/or after vulcanization products. The aim of this study was to investigate the system of the mixed radiation/peroxide and peroxide/radiation crosslinking of selected elastomers (Engage 8200, HNBR). In particular, attention was directed to the influence of the protective effects of aromatic additives in elastomers (peroxides, thermal- and light stabilizers) on the phenomenon of crosslinking and postradiation oxidation. Aromatic peroxides may undergo modifications during the preirradiation, which affect the subsequent processes of vulcanization. In this way the method of gas chromatography (GC) was applied for determination of hydrogen and oxidation effects, never described before for Engage 8200. Using that approach, radiation efficiency of hydrogen evolution and oxygen absorption efficiency of the polymers has been identified. To describe the phenomena of postradiation oxidation of elastomers, the method of Diffuse Reflection Spectrophotometry (DRS) was also applied.

  18. Characterization of crosslinked polystyrene(PS) beads in SBR matrix

    SciTech Connect

    Cha, Yoon-Jong; Choe, Soonja

    1995-12-01

    Monodisperse sized crosslinked polystyrene(PS) beads were prepared by a reaction of semibatch emulsion polymerization with styrene monomer, divinylbenzene(DVB) crosslinking agent and potassium persulfate(K{sub 2}S{sub 2}O{sub 9}) initiator in the absence of emulsifier. The glass transition temperature(T{sub g}) and the mean diameter of the beads were increased from 100{degrees}C to 135{degrees}C and from 402 nm to 532 nm, respectively, for an incorporation of 2 to 10 mol% DVB. Crosslinking density was also linearly increased with DVB content. SEM microphotographs of SBR composite filled with various contents of PS beads revealed that PS beads are relatively well dispersed without changing the spherical shape of the beads in all range of compositions. In stress-strain analysis, elongation at break and tensile strength of SBR composite were increased with the bead content. Applicability of the PS beads as a filler in SBR matrix is tested by plotting Mooney-Rivlin or Guth-Smallwood equations. However, mechanical properties of the composite with the beads were not so excellent as those of the composite with carbon black. Crosslinked PS beads are still tentative as a white color reinforcing filler on SBR matrix.

  19. Separation of the phenylthiocarbamyl derivatives of collagen crosslinks

    SciTech Connect

    Banes, A.J.; Link, G.W.

    1986-05-01

    The purpose of the study was to separate and quantitate the phenylthiocarbamyl (PTC) derivatives of the reduced difunctional collagen crosslinks, HLNL, hydroxylysinonorleucine and DHLNL, dihydroxylysinonorleucine and respective precursors, hydroxynorleucine, HNL, and dihydroxynorleucine, DHNL. Collagens from dentin, rat tail tendon, cartilage and the nonmineralized and mineralized compartments of bone were prepared by pulverization, reduction with NaB/sup 3/H/sub 4/ and acid hydrolysis. Samples, up to 1 mg, were derivatized with PITC, reconstituted in 20 mM acetate buffer, pH 5.7 and applied to a DuPont Reliance reversed phase column. Amino acids and crosslinks were eluted with a gradient of 7 to 36% B, in 20 minutes at 50C at a flow rate of 1.5 ml/minute; A, 0.15M sodium acetate pH 5.7, 700 ..mu..l TEA/l; B, acetonitrile. Effluent was monitored at 254nm and for radioactivity. PTC-HNL eluted with proline at 7 minutes; PTC-DHNL, 10.5 minutes; PTC-HLNL, with lysine at 15 minutes; PTC-DHLNL, 17 minutes, post-lysine. Specific tissues yielded crosslink standards: dentin-DHLNL and DHNL; rat tail tendon-HLNL and HNL; bone yielded both crosslinks. This technique requires the least time yet reported for the separation of these compounds.

  20. Adding an appropriate amino acid during crosslinking results in more stable crosslinked enzyme aggregates.

    PubMed

    Mukherjee, Joyeeta; Majumder, Abir Baran; Gupta, Munishwar Nath

    2016-08-15

    Carrier free immobilization, especially crosslinked enzyme aggregates (CLEAs), has become an important design for biocatalysis in several areas. Adding amino acids during formation of CLEAs was found to give biocatalysts more stable at 55 °C and in the presence of 60% acetonitrile. The half-lives of CLEAs prepared with and without Arg addition were 21 and 15 h (subtilisin) and 4 and 1.6 h (α-chymotrypsin) at 55 °C, respectively. The corresponding half-lives during acetonitrile presence were 4.1 and 3.0 h (subtilisin) and 39 and 22 min (α-chymotrypsin), respectively. CLEAs made with Arg had higher percentages of alpha helix. CLEAs made by adding Lys, Ala, or Asp also were more stable. In the case of Thermomyces lanuginosus lipase (TLL), CLEA with Ala was even more stable than CLEA with Arg. The addition of a suitable amino acid, thus, enhances CLEA stabilities. The results are discussed in the light of earlier results on chemical modification of proteins and the observation that the Arg/Lys ratio is invariably high in the case of enzymes from thermophiles. PMID:27237371

  1. A Study into the Collision-induced Dissociation (CID) Behavior of Cross-Linked Peptides*

    PubMed Central

    Giese, Sven H.; Fischer, Lutz; Rappsilber, Juri

    2016-01-01

    Cross-linking/mass spectrometry resolves protein–protein interactions or protein folds by help of distance constraints. Cross-linkers with specific properties such as isotope-labeled or collision-induced dissociation (CID)-cleavable cross-linkers are in frequent use to simplify the identification of cross-linked peptides. Here, we analyzed the mass spectrometric behavior of 910 unique cross-linked peptides in high-resolution MS1 and MS2 from published data and validate the observation by a ninefold larger set from currently unpublished data to explore if detailed understanding of their fragmentation behavior would allow computational delivery of information that otherwise would be obtained via isotope labels or CID cleavage of cross-linkers. Isotope-labeled cross-linkers reveal cross-linked and linear fragments in fragmentation spectra. We show that fragment mass and charge alone provide this information, alleviating the need for isotope-labeling for this purpose. Isotope-labeled cross-linkers also indicate cross-linker-containing, albeit not specifically cross-linked, peptides in MS1. We observed that acquisition can be guided to better than twofold enrich cross-linked peptides with minimal losses based on peptide mass and charge alone. By help of CID-cleavable cross-linkers, individual spectra with only linear fragments can be recorded for each peptide in a cross-link. We show that cross-linked fragments of ordinary cross-linked peptides can be linearized computationally and that a simplified subspectrum can be extracted that is enriched in information on one of the two linked peptides. This allows identifying candidates for this peptide in a simplified database search as we propose in a search strategy here. We conclude that the specific behavior of cross-linked peptides in mass spectrometers can be exploited to relax the requirements on cross-linkers. PMID:26719564

  2. Processing of targeted psoralen cross-links in Xenopus oocytes.

    PubMed Central

    Segal, D J; Faruqi, A F; Glazer, P M; Carroll, D

    1997-01-01

    Psoralen cross-links have been shown to be both mutagenic and recombinagenic in bacterial, yeast, and mammalian cells. Double-strand breaks (DSBs) have been implicated as intermediates in the removal of psoralen cross-links. Recent work has suggested that site-specific mutagenesis and recombination might be achieved through the use of targeted psoralen adducts. The fate of plasmids containing psoralen adducts was evaluated in Xenopus oocytes, an experimental system that has well-characterized recombination capabilities and advantages in the analysis of intermediates in DNA metabolism. Psoralen adducts were delivered to a specific site by a triplex-forming oligonucleotide. These lesions are clearly recognized and processed in oocytes, since mutagenesis was observed at the target site. The spectrum of induced mutations was compared with that found in similar studies in mammalian cells. Plasmids carrying multiple random adducts were preferentially degraded, perhaps due to the introduction of DSBs. However, when DNAs carrying site-specific adducts were examined, no plasmid loss was observed and removal of cross-links was found to be very slow. Sensitive assays for DSB-dependent homologous recombination were performed with substrates with one or two cross-link sites. No adduct-stimulated recombination was observed with a single lesion, and only very low levels were observed with paired lesions, even when a large proportion of the cross-links was removed by the oocytes. We conclude that DSBs or other recombinagenic structures are not efficiently formed at psoralen adducts in Xenopus oocytes. While psoralen is not a promising reagent for stimulating site-specific recombination, it is effective in inducing targeted mutations. PMID:9343428

  3. Modeling mechanophore activation within a crosslinked glassy matrix

    NASA Astrophysics Data System (ADS)

    Silberstein, Meredith N.; Min, Kyoungmin; Cremar, Lee D.; Degen, Cassandra M.; Martinez, Todd J.; Aluru, Narayana R.; White, Scott R.; Sottos, Nancy R.

    2013-07-01

    Mechanically induced reactivity is a promising means for designing self-reporting materials. Mechanically sensitive chemical groups called mechanophores are covalently linked into polymers in order to trigger specific chemical reactions upon mechanical loading. These mechanophores can be linked either within the backbone or as crosslinks between backbone segments. Mechanophore response is sensitive to both the matrix properties and placement within the matrix, providing two avenues for material design. A model framework is developed to describe reactivity of mechanophores located as crosslinks in a glassy polymer matrix. Simulations are conducted at the molecular and macromolecular scales in order to develop macroscale constitutive relations. The model is developed specifically for the case of spiropyran (SP) in lightly crosslinked polymethylmethacrylate (PMMA). This optically trackable mechanophore (fluorescent when activated) allows the model to be assessed in terms of observed experimental behavior. The force modified potential energy surface (FMPES) framework is used in conjunction with ab initio steered molecular dynamics (MD) simulations of SP to determine the mechanophore kinetics. MD simulations of the crosslinked PMMA structure under shear deformation are used to determine the relationship between macroscale stress and local force on the crosslinks. A continuum model implemented in a finite element framework synthesizes these mechanochemical relations with the mechanical behavior. The continuum model with parameters taken directly from the FMPES and MD analyses under predicts stress-driven activation relative to experimental data. The continuum model, with the physically motivated modification of force fluctuations, provides an accurate prediction for monotonic loading across three decades of strain rate and creep loading, suggesting that the fundamental physics are captured.

  4. Newly identified interfibrillar collagen crosslinking suppresses cell proliferation and remodelling.

    PubMed

    Marelli, Benedetto; Le Nihouannen, Damien; Hacking, S Adam; Tran, Simon; Li, Jingjing; Murshed, Monzur; Doillon, Charles J; Ghezzi, Chiara E; Zhang, Yu Ling; Nazhat, Showan N; Barralet, Jake E

    2015-06-01

    Copper is becoming recognised as a key cation in a variety of biological processes. Copper chelation has been studied as a potential anti-angiogenic strategy for arresting tumour growth. Conversely the delivery of copper ions and complexes in vivo can elicit a pro-angiogenic effect. Previously we unexpectedly found that copper-stimulated intraperitoneal angiogenesis was accompanied by collagen deposition. Here, in hard tissue, not only was healing accelerated by copper, but again enhanced deposition of collagen was detected at 2 weeks. Experiments with reconstituted collagen showed that addition of copper ions post-fibrillogenesis rendered plastically-compressed gels resistant to collagenases, enhanced their mechanical properties and increased the denaturation temperature of the protein. Unexpectedly, this apparently interfibrillar crosslinking was not affected by addition of glucose or ascorbic acid, which are required for crosslinking by advanced glycation end products (AGEs). Fibroblasts cultured on copper-crosslinked gels did not proliferate, whereas those cultured with an equivalent quantity of copper on either tissue culture plastic or collagen showed no effect compared with controls. Although non-proliferative, fibroblasts grown on copper-cross-linked collagen could migrate, remained metabolically active for at least 14 days and displayed a 6-fold increase in Mmps 1 and 3 mRNA expression compared with copper-free controls. The ability of copper ions to crosslink collagen fibrils during densification and independently of AGEs or Fenton type reactions is previously unreported. The effect on MMP susceptibility of collagen and the dramatic change in cell behaviour on this crosslinked ECM may contribute to shedding some light on unexplained phenomena as the apparent benefit of copper complexation in fibrotic disorders or the enhanced collagen deposition in response to localised copper delivery. PMID:25907046

  5. cncRNAs: Bi-functional RNAs with protein coding and non-coding functions

    PubMed Central

    Kumari, Pooja; Sampath, Karuna

    2015-01-01

    For many decades, the major function of mRNA was thought to be to provide protein-coding information embedded in the genome. The advent of high-throughput sequencing has led to the discovery of pervasive transcription of eukaryotic genomes and opened the world of RNA-mediated gene regulation. Many regulatory RNAs have been found to be incapable of protein coding and are hence termed as non-coding RNAs (ncRNAs). However, studies in recent years have shown that several previously annotated non-coding RNAs have the potential to encode proteins, and conversely, some coding RNAs have regulatory functions independent of the protein they encode. Such bi-functional RNAs, with both protein coding and non-coding functions, which we term as ‘cncRNAs’, have emerged as new players in cellular systems. Here, we describe the functions of some cncRNAs identified from bacteria to humans. Because the functions of many RNAs across genomes remains unclear, we propose that RNAs be classified as coding, non-coding or both only after careful analysis of their functions. PMID:26498036

  6. GST-TAT-SOD: Cell Permeable Bifunctional Antioxidant Enzyme-A Potential Selective Radioprotector.

    PubMed

    Pan, Jianru; He, Huocong; Su, Ying; Zheng, Guangjin; Wu, Junxin; Liu, Shutao; Rao, Pingfan

    2016-01-01

    Superoxide dismutase (SOD) fusion of TAT was proved to be radioprotective in our previous work. On that basis, a bifunctional recombinant protein which was the fusion of glutathione S-transferase (GST), SOD, and TAT was constructed and named GST-TAT-SOD. Herein we report the investigation of the cytotoxicity, cell-penetrating activity, and in vitro radioprotective effect of GST-TAT-SOD compared with wild SOD, single-function recombinant protein SOD-TAT, and amifostine. We demonstrated that wild SOD had little radioprotective effect on irradiated L-02 and Hep G2 cells while amifostine was protective to both cell lines. SOD-TAT or GST-TAT-SOD pretreatment 3 h prior to radiation protects irradiated normal liver cells against radiation damage by eliminating intracellular excrescent superoxide, reducing cellular MDA level, enhancing cellular antioxidant ability and colony formation ability, and reducing apoptosis rate. Compared with SOD-TAT, GST-TAT-SOD was proved to have better protective effect on irradiated normal liver cells and minimal effect on irradiated hepatoma cells. Besides, GST-TAT-SOD was safe for normal cells and effectively transduced into different organs in mice, including the brain. The characteristics of this protein suggest that it may be a potential radioprotective agent in cancer therapy better than amifostine. Fusion of two antioxidant enzymes and cell-penetrating peptides is potentially valuable in the development of radioprotective agent. PMID:27313832

  7. Role of bifunctional ammonia-lyase in grass cell wall biosynthesis.

    PubMed

    Barros, Jaime; Serrani-Yarce, Juan C; Chen, Fang; Baxter, David; Venables, Barney J; Dixon, Richard A

    2016-01-01

    L-Phenylalanine ammonia-lyase (PAL) is the first enzyme in the biosynthesis of phenylpropanoid-derived plant compounds such as flavonoids, coumarins and the cell wall polymer lignin. The cell walls of grasses possess higher proportions of syringyl (S)-rich lignins and high levels of esterified coumaric acid compared with those of dicotyledonous plants, and PAL from grasses can also possess tyrosine ammonia-lyase (TAL) activity, the reason for which has remained unclear. Using phylogenetic, transcriptomic and in vitro biochemical analyses, we identified a single homotetrameric bifunctional ammonia-lyase (PTAL) among eight BdPAL enzymes in the model grass species Brachypodium distachyon. (13)C isotope labelling experiments along with BdPTAL1-downregulation in transgenic plants showed that the TAL activity of BdPTAL1 can provide nearly half of the total lignin deposited in Brachypodium, with a preference for S-lignin and wall-bound coumarate biosynthesis, indicating that PTAL function is linked to the characteristic features of grass cell walls. Furthermore, isotope dilution experiments suggest that the pathways to lignin from L-phenylalanine and L-tyrosine are distinct beyond the formation of 4-coumarate, supporting the organization of lignin synthesis enzymes in one or more metabolons. PMID:27255834

  8. GST-TAT-SOD: Cell Permeable Bifunctional Antioxidant Enzyme—A Potential Selective Radioprotector

    PubMed Central

    Pan, Jianru; He, Huocong; Su, Ying; Zheng, Guangjin; Wu, Junxin; Liu, Shutao; Rao, Pingfan

    2016-01-01

    Superoxide dismutase (SOD) fusion of TAT was proved to be radioprotective in our previous work. On that basis, a bifunctional recombinant protein which was the fusion of glutathione S-transferase (GST), SOD, and TAT was constructed and named GST-TAT-SOD. Herein we report the investigation of the cytotoxicity, cell-penetrating activity, and in vitro radioprotective effect of GST-TAT-SOD compared with wild SOD, single-function recombinant protein SOD-TAT, and amifostine. We demonstrated that wild SOD had little radioprotective effect on irradiated L-02 and Hep G2 cells while amifostine was protective to both cell lines. SOD-TAT or GST-TAT-SOD pretreatment 3 h prior to radiation protects irradiated normal liver cells against radiation damage by eliminating intracellular excrescent superoxide, reducing cellular MDA level, enhancing cellular antioxidant ability and colony formation ability, and reducing apoptosis rate. Compared with SOD-TAT, GST-TAT-SOD was proved to have better protective effect on irradiated normal liver cells and minimal effect on irradiated hepatoma cells. Besides, GST-TAT-SOD was safe for normal cells and effectively transduced into different organs in mice, including the brain. The characteristics of this protein suggest that it may be a potential radioprotective agent in cancer therapy better than amifostine. Fusion of two antioxidant enzymes and cell-penetrating peptides is potentially valuable in the development of radioprotective agent. PMID:27313832

  9. Purification, characterization, and identification of a novel bifunctional catalase-phenol oxidase from Scytalidium thermophilum.

    PubMed

    Sutay Kocabas, Didem; Bakir, Ufuk; Phillips, Simon E V; McPherson, Michael J; Ogel, Zumrut B

    2008-06-01

    A novel bifunctional catalase with an additional phenol oxidase activity was isolated from a thermophilic fungus, Scytalidium thermophilum. This extracellular enzyme was purified ca. 10-fold with 46% yield and was biochemically characterized. The enzyme contains heme and has a molecular weight of 320 kDa with four 80 kDa subunits and an isoelectric point of 5.0. Catalase and phenol oxidase activities were most stable at pH 7.0. The activation energies of catalase and phenol oxidase activities of the enzyme were found to be 2.7 +/- 0.2 and 10.1 +/- 0.4 kcal/mol, respectively. The pure enzyme can oxidize o-diphenols such as catechol, caffeic acid, and L-DOPA in the absence of hydrogen peroxide and the highest oxidase activity is observed against catechol. No activity is detected against tyrosine and common laccase substrates such as ABTS and syringaldazine with the exception of weak activity with p-hydroquinone. Common catechol oxidase inhibitors, salicylhydroxamic acid and p-coumaric acid, inhibit the oxidase activity. Catechol oxidation activity was also detected in three other catalases tested, from Aspergillus niger, human erythrocyte, and bovine liver, suggesting that this dual catalase-phenol oxidase activity may be a common feature of catalases. PMID:18369615

  10. 6-Methyluracil Derivatives as Bifunctional Acetylcholinesterase Inhibitors for the Treatment of Alzheimer's Disease.

    PubMed

    Semenov, Vyacheslav E; Zueva, Irina V; Mukhamedyarov, Marat A; Lushchekina, Sofya V; Kharlamova, Alexandra D; Petukhova, Elena O; Mikhailov, Anatoly S; Podyachev, Sergey N; Saifina, Lilya F; Petrov, Konstantin A; Minnekhanova, Oksana A; Zobov, Vladimir V; Nikolsky, Evgeny E; Masson, Patrick; Reznik, Vladimir S

    2015-11-01

    Novel 6-methyluracil derivatives with ω-(substituted benzylethylamino)alkyl chains at the nitrogen atoms of the pyrimidine ring were designed and synthesized. The numbers of methylene groups in the alkyl chains were varied along with the electron-withdrawing substituents on the benzyl rings. The compounds are mixed-type reversible inhibitors of cholinesterases, and some of them show remarkable selectivity for human acetylcholinesterase (hAChE), with inhibitory potency in the nanomolar range, more than 10,000-fold higher than that for human butyrylcholinesterase (hBuChE). Molecular modeling studies indicate that these compounds are bifunctional AChE inhibitors, spanning the enzyme active site gorge and binding to its peripheral anionic site (PAS). In vivo experiments show that the 6-methyluracil derivatives are able to penetrate the blood-brain barrier (BBB), inhibiting brain-tissue AChE. The most potent AChE inhibitor, 3 d (1,3-bis[5-(o-nitrobenzylethylamino)pentyl]-6-methyluracil), was found to improve working memory in scopolamine and transgenic APP/PS1 murine models of Alzheimer's disease, and to significantly decrease the number and area of β-amyloid peptide plaques in the brain. PMID:26412714

  11. Bifunctional polyacrylonitrile fiber-mediated conversion of sucrose to 5-hydroxymethylfurfural in mixed-aqueous systems.

    PubMed

    Shi, Xian-Lei; Zhang, Min; Lin, Huikun; Tao, Minli; Li, Yongdan; Zhang, Wenqin

    2015-03-01

    A highly efficient catalytic system composed of a bifunctional polyacrylonitrile fiber (PANF-PA[BnBr]) and a metal chloride was employed to produce 5-hydroxymethylfurfural (HMF) from sucrose in mixed-aqueous systems. The promoter of PANF-PA[BnBr] incorporates protonic acid groups that promote the hydrolysis of the glycosidic bond to convert sucrose into glucose and fructose, and then catalyzes fructose dehydration to HMF, while the ammonium moiety may promote synergetically with the metal chloride the isomerization of glucose to fructose and transfer HMF from the aqueous to the organic phase. The detailed characterization by elemental analysis, FTIR spectroscopy, and SEM confirmed the rangeability of the fiber promoter during the modification and utilization processes. Excellent results in terms of high yield (72.8%) of HMF, superior recyclability (6 cycles) of the process, and effective scale-up and simple separation procedures of the catalytic system were obtained. Moreover, the prominent features (high strength, good flexibility, etc.) of the fibers are very attractive for fix-bed reactor. PMID:25573698

  12. BIFUNCTIONAL CATALYSTS FOR THE SELECTIVE CATALYTIC REDUCTION OF NO BY HYDROCARBONS

    SciTech Connect

    Neylon, M; Castagnola, M; Kropf, A.; Marshall, C

    2003-08-24

    Novel bifunctional catalysts combining two active phases, typically Cu-ZSM-5 and a modifier, were prepared and tested for the selective catalytic reduction of nitrogen oxides using propylene in order to overcome the hindering effects of water typically seen for single-phase catalysts such as Cu-ZSM-5. The catalysts were made by typical preparation techniques, but parameters could be varied to influence the catalyst. The physical characterization of the materials showed that the modification phase was added strictly to the external surface of the zeolite without hindering any internal surface area. Chemical characterization by temperature programmed reactions, DRIFTS and x-ray absorption spectroscopy indicated strong interaction between the two phases, primarily producing materials that exhibited lower reduction temperatures. Two improvements in NOx reduction activity (1000 ppm NO, 1000 ppm C3H6, 2% O2, 30,000 hr-1 GHSV) were seen for these catalysts compared with Cu- ZSM-5: a lower temperature of maximum NOx conversion activity (as low at 250 C), and an enhancement of activity when water was present in the system. The use of a second phase provides a way to further tune the properties of the catalyst in order to achieve mechanistic conditions necessary to maximize NOx remediation.

  13. Uncommon Pyrazoyl-Carboxyl Bifunctional Ligand-Based Microporous Lanthanide Systems: Sorption and Luminescent Sensing Properties.

    PubMed

    Li, Gao-Peng; Liu, Ge; Li, Yong-Zhi; Hou, Lei; Wang, Yao-Yu; Zhu, Zhonghua

    2016-04-18

    Seven new isostructural lanthanide metal-organic frameworks (Ln-MOFs), [Ln(Hpzbc)2(NO3)]·H2O (1-Ln, Ln = Nd(3+), Sm(3+), Eu(3+), Gd(3+), Tb(3+), Er(3+), and Yb(3+) ions, H2pzbc = 3-(1H-pyrazol-3-yl) benzoic acid), with one-dimensional (1D) channels decorated by nitrate anions and pyrazoyl groups have been constructed. 1-Ln, as revealed by structural analysis, represent uncommon microporous 3D Ln-pyrazoyl-carboxyl systems using pyrazoyl-carboxyl bifunctional ligands as bridges. The luminescent investigations show that 1-Eu is an excellent MOF-based fluorescent probe, with high sensitivity, selectivity, and simple regeneration, for environmentally relevant Fe(3+) and Cr2O7(2-) ions. 1-Eu also presents highly selective capture for CO2 over N2 and CH4 due to the multiple binding sites for CO2 molecules, which were supported by Grand Canonical Monte Carlo (GCMC) simulations. PMID:27022691

  14. Chrysanthemyl Diphosphate Synthase Operates in Planta as a Bifunctional Enzyme with Chrysanthemol Synthase Activity*

    PubMed Central

    Yang, Ting; Gao, Liping; Hu, Hao; Stoopen, Geert; Wang, Caiyun; Jongsma, Maarten A.

    2014-01-01

    Chrysanthemyl diphosphate synthase (CDS) is the first pathway-specific enzyme in the biosynthesis of pyrethrins, the most widely used plant-derived pesticide. CDS catalyzes c1′-2-3 cyclopropanation reactions of two molecules of dimethylallyl diphosphate (DMAPP) to yield chrysanthemyl diphosphate (CPP). Three proteins are known to catalyze this cyclopropanation reaction of terpene precursors. Two of them, phytoene and squalene synthase, are bifunctional enzymes with both prenyltransferase and terpene synthase activity. CDS, the other member, has been reported to perform only the prenyltransferase step. Here we show that the NDXXD catalytic motif of CDS, under the lower substrate conditions prevalent in plants, also catalyzes the next step, converting CPP into chrysanthemol by hydrolyzing the diphosphate moiety. The enzymatic hydrolysis reaction followed conventional Michaelis-Menten kinetics, with a Km value for CPP of 196 μm. For the chrysanthemol synthase activity, DMAPP competed with CPP as substrate. The DMAPP concentration required for half-maximal activity to produce chrysanthemol was ∼100 μm, and significant substrate inhibition was observed at elevated DMAPP concentrations. The N-terminal peptide of CDS was identified as a plastid-targeting peptide. Transgenic tobacco plants overexpressing CDS emitted chrysanthemol at a rate of 0.12–0.16 μg h−1 g−1 fresh weight. We propose that CDS should be renamed a chrysanthemol synthase utilizing DMAPP as substrate. PMID:25378387

  15. Bifunctional silica nanoparticles for the exploration of biofilms of Pseudomonas aeruginosa.

    PubMed

    Mauline, L; Gressier, M; Roques, C; Hammer, P; Ribeiro, S J L; Caiut, J M A; Menu, M-J

    2013-01-01

    Luminescent silica nanoparticles are frequently employed for biotechnology applications mainly because of their easy functionalization, photo-stability, and biocompatibility. Bifunctional silica nanoparticles (BSNPs) are described here as new efficient tools for investigating complex biological systems such as biofilms. Photoluminescence is brought about by the incorporation of a silylated ruthenium(II) complex. The surface properties of the silica particles were designed by reaction with amino-organosilanes, quaternary ammonium-organosilanes, carboxylate-organosilanes and hexamethyldisilazane. BSNPs were characterized extensively by DRIFT, (13)C and (29)Si solid state NMR, XPS, and photoluminescence. Zeta potential and contact angle measurements exhibited various surface properties (hydrophilic/hydrophobic balance and electric charge) according to the functional groups. Confocal laser scanning microscopy (CLSM) measurements showed that the spatial distribution of these nanoparticles inside a biofilm of Pseudomonas aeruginosa PAO1 depends more on their hydrophilic/hydrophobic characteristics than on their size. CLSM observations using two nanosized particles (25 and 68 nm) suggest that narrow diffusion paths exist through the extracellular polymeric substances matrix. PMID:23805884

  16. Bifunctional polyacrylamide based polymers for the specific binding of hexahistidine tagged proteins on gold surfaces.

    PubMed

    Thompson, Lucas B; Mack, Nathan H; Nuzzo, Ralph G

    2010-05-01

    We describe a modified bifunctional analogue of polyacrylamide that spontaneously forms self-assembled polymeric thin films on Au surfaces. The film is engineered to specifically bind histidine tagged proteins (6His), while simultaneously remaining inherently resistant to the non-specific adsorption of proteins in solution. The backbone of a polyacrylamide-co-n-acryloxysuccinimide copolymer is functionalized via tandem active ester (NHS) couplings with 3-(methylthio)propylamine (MTP) and nitrilotriacetic acid (NTA). The resulting functionalized polymers form stable and exceptionally hydrophilic thin films that are approximately 2-5 nm thick, a mass coverage that varies with the MTP graft density. These films are characterized using a variety of techniques (X-ray photoelectron spectroscopy (XPS), reflection absorption infrared spectroscopy (RAIRS), ellipsometry, surface plasmon resonance (SPR), and matrix assisted laser desorption ionization (MALDI)) to establish their structure and function. The protein resistance of the films, as demonstrated by their exposure to solutions of bovine serum albumin (BSA), can be modulated by the amount of MTP grafted to the polymer, which in turn, affects their mass coverage. We show that it is possible to specifically capture hexahistidine tagged proteins with low incidences of nonspecific adsorption using these materials, a discrimination quantified using surface plasmon resonance (SPR) at concentrations down to approximately 20 nM. These polymers also bind strongly to the surfaces of Au nanoparticles, stabilizing them against aggregation, providing them with a similar capacity to selectively bind 6His tagged proteins that can then be speciated using MALDI. PMID:20407699

  17. Bifunctional Luminomagnetic Rare-Earth Nanorods for High-Contrast Bioimaging Nanoprobes.

    PubMed

    Gupta, Bipin Kumar; Singh, Satbir; Kumar, Pawan; Lee, Yean; Kedawat, Garima; Narayanan, Tharangattu N; Vithayathil, Sajna Antony; Ge, Liehui; Zhan, Xiaobo; Gupta, Sarika; Martí, Angel A; Vajtai, Robert; Ajayan, Pulickel M; Kaipparettu, Benny Abraham

    2016-01-01

    Nanoparticles exhibiting both magnetic and luminescent properties are need of the hour for many biological applications. A single compound exhibiting this combination of properties is uncommon. Herein, we report a strategy to synthesize a bifunctional luminomagnetic Gd2-xEuxO3 (x = 0.05 to 0.5) nanorod, with a diameter of ~20 nm and length in ~0.6 μm, using hydrothermal method. Gd2O3:Eu(3+) nanorods have been characterized by studying its structural, optical and magnetic properties. The advantage offered by photoluminescent imaging with Gd2O3:Eu(3+) nanorods is that this ultrafine nanorod material exhibits hypersensitive intense red emission (610 nm) with good brightness (quantum yield more than 90%), which is an essential parameter for high-contrast bioimaging, especially for overcoming auto fluorescent background. The utility of luminomagnetic nanorods for biological applications in high-contrast cell imaging capability and cell toxicity to image two human breast cancer cell lines T47D and MDA-MB-231 are also evaluated. Additionally, to understand the significance of shape of the nanostructure, the photoluminescence and paramagnetic characteristic of Gd2O3:Eu(3+) nanorods were compared with the spherical nanoparticles of Gd2O3:Eu(3+). PMID:27585638

  18. The determination of the rate of conjugation immunoglobuline with bifunctional chelator

    NASA Astrophysics Data System (ADS)

    Málek, Z.; Miler, V.; Budský, F.

    2006-01-01

    The work was performed under the GACR project: "Technology of preparation of radionuclides and their labelled compounds for nuclear medicine and pharmacy with the use of the reactor LVR-15" reg. no. 104/03/0499. Imaging of cell’s antigens with the use of labelled immunoglobulines allows imaging of specific receptors on cell membrane and specific tumours. It is necessary to carry out the labelling of the immunoglobulines with radionuclides of suitable physical properties, which form cations (e.g., 111In, 90Y, 177Lu) that form very strong chelates of sufficiently high stability constant preventing the dissociation of complexes or the radionuclide under “in-vivo” conditions. The immunoglobuline must be conjugated with the bifunctional chelator (BCH), which contains both chelating unit and reactive group for binding to the immunoglobuline. In our laboratory we have conjugated human IgG and monoclonal antibody CD20 with diethylenetriamine pentaacetic acid dianhydride (cDTPAA). Radionuclides 90Y and 177Lu prepared on the LVR-15 reactor in NRI Rez were used for labelling. After conjugation and labelling the yields in relation to the amount of isotopic carrier have been determined.

  19. The rigid bi-functional sail, new concept concerning the reduction of the drag of ships

    NASA Astrophysics Data System (ADS)

    Țicu, I.; Popa, I.; Ristea, M.

    2015-11-01

    The policy of the European Union in the energy field, for the period to follow until 2020, is based on three fundamental objectives: sustainability, competitiveness and safety in energy supply. The “Energy - Climate Changes” program sets out a number of objectives for the EU for the year 2020, known as the “20-20-20 objectives”, namely: the reduction of greenhouse gas emissions by at least 20% from the level of those of 1990, a 20% increase in the share of renewable energy sources out of the total energy consumption as well as a target of 10% biofuels in the transports energy consumption. In this context, in order to produce or save a part of the propulsive power produced by the main propulsion machinery, by burning fossil fuels, we suggest the equipping of vessels designed for maritime transport with a bi-functional rigid sail. We consider that this device may have both the role of trapping wind energy and the role of acting as a deflector for reducing the resistance of the vessel's proceeding through the water by conveniently using the bow air current, as a result of the vessel's heading through the water with significant advantage in reducing the energy consumption for propulsion insurance.

  20. Facile Preparation of Bifunctional Monodisperse Nanospheres with Tunable Size and Luminescence.

    PubMed

    Ge, Yuqing; Wang, Ping; Mao, Hongju; Jin, Qinghui; Zhao, Jianlong

    2015-08-01

    Nanotechnology has found wide use in biomedical applications and the food and bioprocessing industry. In this light, we demonstrate a facile strategy to prepare bifunctional monodisperse silica nanospheres encapsulating chitosan-coated magnetic nanoparticles and CdTe quantum dots. The size of these composite spheres can be adjusted from 90 nm to 500 nm by varying the concentration of ammonia, water, tetraethyl orthosilicate, and the ratio of the chitosan-coated magnetic nanoparticles and CdTe quantum dots. The composite spheres are characterized using scanning electron microscope analyses, transmission electron microscope analyses, energy-dispersed spectrum studies, Malvern Zetasizer, vibrating sample magnetometer, and fluorescence microscopy. The spheres exhibit good monodispersion and favorable superparamagnetic and fluorescent properties. The luminescence of the spheres can be varied by using different types of coated quantum dots. Such composite spheres with tunable characteristics allow for external manipulation of research systems by magnetic fields together with the real-time fluorescent monitoring of multiple samples. The abovementioned properties can potentially be exploited for application in the biomedical and biosensing fields. PMID:26369198

  1. Efficient refolding of the bifunctional therapeutic fusion protein VAS-TRAIL by a triple agent solution.

    PubMed

    Fan, Jiying; Wang, Zhanqing; Huang, Liying; Shen, Yaling

    2016-09-01

    VAS-TRAIL is a bifunctional fusion protein that combines anti-angiogenic activity with tumor-selective apoptotic activity for enhanced anti-tumor efficacy. VAS-TRAIL is expressed as inclusion body in Escherichia coli, but protein refolding is difficult to achieve and results in low yields of bioactive protein. In this study, we describe an efficient method for VAS-TRAIL refolding. The solubilization of aggregated VAS-TRAIL was achieved by a triple agent solution, which consists of an alkaline solution (pH 11.5) containing 0.4M l-arginine and 2M urea. The solubilized protein showed high purity and preserved secondary structure according to fluorescence properties. VAS-TRAIL refolding was performed through stepwise dialysis and resulted in more than 50% recovery of the soluble protein. The function of l-arginine was additive with alkaline pH, as shown by the significant improvement in refolding yield (≈30%) by l-arginine-containing solubilization solutions compared with alkaline solubilization solutions without l-arginine. The refolded VAS-TRAIL also showed β-sheet structures and the propensity for oligomerization. Bioassays showed that the refolded fusion protein exhibited the expected activities, including its apoptotic activities toward tumor and endothelial cells, which proposed its promising therapeutic potential. PMID:26358405

  2. New bifunctional antioxidant/σ1 agonist ligands: Preliminary chemico-physical and biological evaluation.

    PubMed

    Arena, Emanuela; Cacciatore, Ivana; Cerasa, Laura S; Turkez, Hasan; Pittalà, Valeria; Pasquinucci, Lorella; Marrazzo, Agostino; Parenti, Carmela; Di Stefano, Antonio; Prezzavento, Orazio

    2016-07-15

    We previously reported bifunctional sigma-1 (σ1) ligands endowed with antioxidant activity (1 and 2). In the present paper, pure enantiomers (R)-1 and (R)-2 along with the corresponding p-methoxy (6, 11), p-fluoro derivatives (7, 12) were synthesized. σ1 and σ2 affinities, antioxidant properties, and chemico-physical profiles were evaluated. Para derivatives, while maintaining strong σ1 affinity, displayed improved σ1 selectivity compared to the parent compounds 1 and 2. In vivo evaluation of compounds 1, 2, (R)-1, 7, and 12 showed σ1 agonist pharmacological profile. Chemico-physical studies revealed that amides 2, 11 and 12 were more stable than corresponding esters 1, 6 and 7 under our experimental conditions. Antioxidant properties were exhibited by fluoro derivatives 7 and 12 being able to increase total antioxidant capacity (TAC). Our results underline that p-substituents have an important role on σ1 selectivity, TAC, chemical and enzymatic stabilities. In particular, our data suggest that new very selective compounds 7 and 12 could be promising tools to investigate the disorders in which σ1 receptor dysfunction and oxidative stress are contemporarily involved. PMID:27262426

  3. Bifunctional Luminomagnetic Rare-Earth Nanorods for High-Contrast Bioimaging Nanoprobes

    PubMed Central

    Gupta, Bipin Kumar; Singh, Satbir; Kumar, Pawan; Lee, Yean; Kedawat, Garima; Narayanan, Tharangattu N.; Vithayathil, Sajna Antony; Ge, Liehui; Zhan, Xiaobo; Gupta, Sarika; Martí, Angel A.; Vajtai, Robert; Ajayan, Pulickel M.; Kaipparettu, Benny Abraham

    2016-01-01

    Nanoparticles exhibiting both magnetic and luminescent properties are need of the hour for many biological applications. A single compound exhibiting this combination of properties is uncommon. Herein, we report a strategy to synthesize a bifunctional luminomagnetic Gd2−xEuxO3 (x = 0.05 to 0.5) nanorod, with a diameter of ~20 nm and length in ~0.6 μm, using hydrothermal method. Gd2O3:Eu3+ nanorods have been characterized by studying its structural, optical and magnetic properties. The advantage offered by photoluminescent imaging with Gd2O3:Eu3+ nanorods is that this ultrafine nanorod material exhibits hypersensitive intense red emission (610 nm) with good brightness (quantum yield more than 90%), which is an essential parameter for high-contrast bioimaging, especially for overcoming auto fluorescent background. The utility of luminomagnetic nanorods for biological applications in high-contrast cell imaging capability and cell toxicity to image two human breast cancer cell lines T47D and MDA-MB-231 are also evaluated. Additionally, to understand the significance of shape of the nanostructure, the photoluminescence and paramagnetic characteristic of Gd2O3:Eu3+ nanorods were compared with the spherical nanoparticles of Gd2O3:Eu3+. PMID:27585638

  4. Impedimetric and amperometric bifunctional glucose biosensor based on hybrid organic-inorganic thin films.

    PubMed

    Wang, Huihui; Ohnuki, Hitoshi; Endo, Hideaki; Izumi, Mitsuru

    2015-02-01

    A novel glucose biosensor with an immobilized mediator was studied using electrochemical impedance spectroscopy (EIS) and amperometry measurements. The biosensor has a characteristic ultrathin form and is composed of a self-assembled monolayer anchoring glucose oxidase (GOx) covered with Langmuir-Blodgett (LB) films of Prussian blue (PB). The immobilized PB in the LB films acts as a mediator and enables the biosensor to work under a low potential (0.0V vs. Ag/AgCl). In the EIS measurements, a dramatic decrease in charge transfer resistance (Rct) was observed with sequential addition of glucose, which can be attributed to enzymatic activity. The linearity of the biosensor response was observed by the variation of the sensor response (1/Rct) as a function of glucose concentration in the range 0 to 25mM. The sensor also showed linear amperometric response below 130mM glucose. The organic-inorganic system of GOx and PB nanoclusters demonstrated bifunctional sensing action, both amperometry and EIS modes, as well as long sensing stability for 4 days. PMID:25014167

  5. Mechanism of tetralin ring opening and contraction over bifunctional Ir/SiO₂-Al₂O₃ Catalysts.

    PubMed

    Piccolo, Laurent; Nassreddine, Salim; Toussaint, Guy; Geantet, Christophe

    2012-09-01

    The development of cleaner fuels from conventional resources requires the finding of new hydrotreatment processes able to improve the combustion performances of fuels and limit undesirable emissions. In the context of gas oil upgrading by selective ring opening, we have investigated the hydroconversion of tetralin over iridium nanoparticles supported on amorphous silica-alumina. The conversion of tetralin leads to hydrogenation, ring-contraction, and ring-opening products. The selectivity to ring-opening/-contraction products (ROCPs) increases linearly with the acid-metal site ratio and can be tuned by modifying the metal loading, the metal nanoparticle size, or the support composition. From the combination of catalytic tests at variable conversion and the products identification by two-dimensional gas chromatography, a mechanistic reaction scheme has been established. Aromatic ROCPs are formed through purely acidic steps, whereas the formation of saturated ROCPs mostly involves bifunctional reaction steps. Iridium-catalyzed hydrogenolysis appears to be a minor pathway with respect to iridium-catalyzed hydrogenation and Brønsted acid catalyzed isomerization. PMID:22949005

  6. Chrysanthemyl diphosphate synthase operates in planta as a bifunctional enzyme with chrysanthemol synthase activity.

    PubMed

    Yang, Ting; Gao, Liping; Hu, Hao; Stoopen, Geert; Wang, Caiyun; Jongsma, Maarten A

    2014-12-26

    Chrysanthemyl diphosphate synthase (CDS) is the first pathway-specific enzyme in the biosynthesis of pyrethrins, the most widely used plant-derived pesticide. CDS catalyzes c1'-2-3 cyclopropanation reactions of two molecules of dimethylallyl diphosphate (DMAPP) to yield chrysanthemyl diphosphate (CPP). Three proteins are known to catalyze this cyclopropanation reaction of terpene precursors. Two of them, phytoene and squalene synthase, are bifunctional enzymes with both prenyltransferase and terpene synthase activity. CDS, the other member, has been reported to perform only the prenyltransferase step. Here we show that the NDXXD catalytic motif of CDS, under the lower substrate conditions prevalent in plants, also catalyzes the next step, converting CPP into chrysanthemol by hydrolyzing the diphosphate moiety. The enzymatic hydrolysis reaction followed conventional Michaelis-Menten kinetics, with a Km value for CPP of 196 μm. For the chrysanthemol synthase activity, DMAPP competed with CPP as substrate. The DMAPP concentration required for half-maximal activity to produce chrysanthemol was ∼100 μm, and significant substrate inhibition was observed at elevated DMAPP concentrations. The N-terminal peptide of CDS was identified as a plastid-targeting peptide. Transgenic tobacco plants overexpressing CDS emitted chrysanthemol at a rate of 0.12-0.16 μg h(-1) g(-1) fresh weight. We propose that CDS should be renamed a chrysanthemol synthase utilizing DMAPP as substrate. PMID:25378387

  7. Discovery of a bifunctional acyltransferase responsible for ornithine lipid synthesis in Serratia proteamaculans.

    PubMed

    Vences-Guzmán, Miguel Ángel; Guan, Ziqiang; Escobedo-Hinojosa, Wendy Itzel; Bermúdez-Barrientos, José Roberto; Geiger, Otto; Sohlenkamp, Christian

    2015-05-01

    Ornithine lipids (OLs) are phosphorus-free membrane lipids that can be formed by many bacteria but that are absent from archaea and eukaryotes. A function for OLs in stress conditions and in host-bacteria interactions has been shown in some bacteria. Some bacterial species have been described that can form OLs, but lack the known genes (olsBA) involved in its biosynthesis, which implied the existence of a second pathway. Here we describe the bifunctional protein OlsF from Serratia proteamaculans involved in OL formation. Expression of OlsF and its homologue from Flavobacterium johnsoniae in Escherichia coli causes OL formation. Deletion of OlsF in S. proteamaculans caused the absence of OL formation. Homologues of OlsF are widely distributed among γ-, δ- and ε-Proteobacteria and in the Cytophaga-Flavobacterium-Bacteroidetes group of bacteria, including several well-studied pathogens for which the presence of OLs has not been suspected, such as for example Vibrio cholerae and Klebsiella pneumonia. Using genomic data, we predict that about 50% of bacterial species can form OLs. PMID:25040623

  8. Highly Active and Durable Nanocrystal-Decorated Bifunctional Electrocatalyst for Rechargeable Zinc-Air Batteries.

    PubMed

    Lee, Dong Un; Park, Moon Gyu; Park, Hey Woong; Seo, Min Ho; Wang, Xiaolei; Chen, Zhongwei

    2015-09-21

    A highly active and durable bifunctional electrocatalyst that consists of cobalt oxide nanocrystals (Co3 O4 NC) decorated on the surface of N-doped carbon nanotubes (N-CNT) is introduced as effective electrode material for electrically rechargeable zinc-air batteries. This active hybrid catalyst is synthesized by a facile surfactant-assisted method to produce Co3 O4 NC that are then decorated on the surface of N-CNT through hydrophobic attraction. Confirmed by half-cell testing, Co3 O4 NC/N-CNT demonstrates superior oxygen reduction and oxygen evolution catalytic activities and has a superior electrochemical stability compared to Pt/C and Ir/C. Furthermore, rechargeable zinc-air battery testing of Co3 O4 NC/N-CNT reveals superior galvanodynamic charge and discharge voltages with a significantly extended cycle life of over 100 h, which suggests its potential as a replacement for precious-metal-based catalysts for electric vehicles and grid energy storage applications. PMID:26373363

  9. Purification and Characterization of the Bifunctional Enzyme Lysine-Ketoglutarate Reductase-Saccharopine Dehydrogenase from Maize.

    PubMed Central

    Goncalves-Butruille, M.; Szajner, P.; Torigoi, E.; Leite, A.; Arruda, P.

    1996-01-01

    The first enzyme of the lysine degradation pathway in maize (Zea mays L.), lysine-ketoglutarate reductase, condenses lysine and [alpha]-ketoglutarate into saccharopine using NADPH as a cofactor, whereas the second, saccharopine dehydrogenase, converts saccharopine to [alpha]-aminoadipic-[delta]-semialdehyde and glutamic acid using NAD+ or NADP+ as a cofactor. The reductase and dehydrogenase activities are optimal at pH 7.0 and 9.0, respectively. Both enzyme activities, co-purified on diethylaminoethyl-cellulose and gel filtration columns, were detected on nondenaturing polyacrylamide gels as single bands with identical electrophoretic mobilities and share tissue specificity for the endosperm. The highly purified preparation containing the reductase and dehydrogenase activities showed a single polypeptide band of 125 kD on sodium dodecyl sulfate-polyacrylamide gel electrophoresis. The native form of the enzyme is a dimer of 260 kD. Limited proteolysis with elastase indicated that lysine-ketoglutarate reductase and saccharopine dehydrogenase from maize endosperm are located in two functionally independent domains of a bifunctional polypeptide. PMID:12226216

  10. Structure and Function of Fusicoccadiene Synthase, a Hexameric Bifunctional Diterpene Synthase.

    PubMed

    Chen, Mengbin; Chou, Wayne K W; Toyomasu, Tomonobu; Cane, David E; Christianson, David W

    2016-04-15

    Fusicoccin A is a diterpene glucoside phytotoxin generated by the fungal pathogen Phomopsis amygdali that causes the plant disease constriction canker, first discovered in New Jersey peach orchards in the 1930s. Fusicoccin A is also an emerging new lead in cancer chemotherapy. The hydrocarbon precursor of fusicoccin A is the tricyclic diterpene fusicoccadiene, which is generated by a bifunctional terpenoid synthase. Here, we report X-ray crystal structures of the individual catalytic domains of fusicoccadiene synthase: the C-terminal domain is a chain elongation enzyme that generates geranylgeranyl diphosphate, and the N-terminal domain catalyzes the cyclization of geranylgeranyl diphosphate to form fusicoccadiene. Crystal structures of each domain complexed with bisphosphonate substrate analogues suggest that three metal ions and three positively charged amino acid side chains trigger substrate ionization in each active site. While in vitro incubations reveal that the cyclase domain can utilize farnesyl diphosphate and geranyl diphosphate as surrogate substrates, these shorter isoprenoid diphosphates are mainly converted into acyclic alcohol or hydrocarbon products. Gel filtration chromatography and analytical ultracentrifugation experiments indicate that full-length fusicoccadiene synthase adopts hexameric quaternary structure, and small-angle X-ray scattering data yield a well-defined molecular envelope illustrating a plausible model for hexamer assembly. PMID:26734760

  11. Mimivirus Collagen Is Modified by Bifunctional Lysyl Hydroxylase and Glycosyltransferase Enzyme*

    PubMed Central

    Luther, Kelvin B.; Hülsmeier, Andreas J.; Schegg, Belinda; Deuber, Stefan A.; Raoult, Didier; Hennet, Thierry

    2011-01-01

    Collagens, the most abundant proteins in animals, are modified by hydroxylation of proline and lysine residues and by glycosylation of hydroxylysine. Dedicated prolyl hydroxylase, lysyl hydroxylase, and collagen glycosyltransferase enzymes localized in the endoplasmic reticulum mediate these modifications prior to the formation of the collagen triple helix. Whereas collagen-like proteins have been described in some fungi, bacteria, and viruses, the post-translational machinery modifying collagens has never been described outside of animals. We demonstrate that the L230 open reading frame of the giant virus Acanthamoeba polyphaga mimivirus encodes an enzyme that has distinct lysyl hydroxylase and collagen glycosyltransferase domains. We show that mimivirus L230 is capable of hydroxylating lysine and glycosylating the resulting hydroxylysine residues in a native mimivirus collagen acceptor substrate. Whereas in animals from sponges to humans the transfer of galactose to hydroxylysine in collagen is conserved, the mimivirus L230 enzyme transfers glucose to hydroxylysine, thereby defining a novel type of collagen glycosylation in nature. The presence of hydroxylysine in mimivirus proteins was confirmed by amino acid analysis of mimivirus recovered from A. polyphaga cultures. This work shows for the first time that collagen post-translational modifications are not confined to the domains of life. The utilization of glucose instead of the galactose found throughout animals as well as a bifunctional enzyme rather than two separate enzymes may represent a parallel evolutionary track in collagen biology. These results suggest that giant viruses may have contributed to the evolution of collagen biology. PMID:22045808

  12. Bifunctional impedimetric sensors based on azodicarboxamide supported on modified graphene nanosheets.

    PubMed

    Azadbakht, Azadeh; Roushani, Mahmoud; Abbasi, Amir Reza; Derikvand, Zohreh; Menati, Saeid

    2016-12-01

    Herein, gold-coated graphene oxide nanosheets hybrid material (GO/AuNPs) with exceptional physical and chemical properties has been utilized as a novel platform for electrode modification. The synthetic method of GO/AuNPs involves anon-covalent functionalization of exfoliated GO with AuNPs based on the reduction of the Au(III) complex by sodium citrate. The prepared GO/AuNPs hybrid exhibits the dispersion of high density AuNPs which were densely decorated on the large surface area of GO. The GO/AuNPs modified glassy carbon (GC) electrode was employed as a sensing platform to immobilize azodicarboxamide (ACA). The morphology, structure and electrochemical performance of the sensor were characterized by scanning electron microscopy (SEM), cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS). The results indicate that the modified electrode has a notable bifunctional catalytic activity. Electrocatalytic oxidations of cysteine and electrocatalytic reduction of iodate at the surface of modified electrode were investigated with different technique. PMID:27612707

  13. Structure of the E. Coli Bifunctional GlmU Acetyltransferase Active Site with Substrates and Products

    SciTech Connect

    Olsen,L.; Vetting, M.; Roderick, S.

    2007-01-01

    The biosynthesis of UDP-GlcNAc in bacteria is carried out by GlmU, an essential bifunctional uridyltransferase that catalyzes the CoA-dependent acetylation of GlcN-1-PO{sub 4} to form GlcNAc-1-PO{sub 4} and its subsequent condensation with UTP to form pyrophosphate and UDP-GlcNAc. As a metabolite, UDP-GlcNAc is situated at a branch point leading to the biosynthesis of lipopolysaccharide and peptidoglycan. Consequently, GlmU is regarded as an important target for potential antibacterial agents. The crystal structure of the Escherichia coli GlmU acetyltransferase active site has been determined in complexes with acetyl-CoA, CoA/GlcN-1-PO{sub 4}, and desulpho-CoA/GlcNAc-1-PO{sub 4}. These structures reveal the enzyme groups responsible for binding the substrates. A superposition of these complex structures suggests that the 2-amino group of GlcN-1-PO{sub 4} is positioned in proximity to the acetyl-CoA to facilitate direct attack on its thioester by a ternary complex mechanism.

  14. Herinase: a novel bi-functional fibrinolytic protease from the monkey head mushroom, Hericium erinaceum.

    PubMed

    Choi, Bong-Suk; Sapkota, Kumar; Choi, Jun-Hui; Shin, Chang-ho; Kim, Seung; Kim, Sung-Jun

    2013-06-01

    Herinase, a new bi-functional fibrinolytic metalloprotease, was purified from a medicinal and edible mushroom Hericium erinaceum. The enzyme was monomeric with a molecular mass of 51 kDa. Analysis of fibrin zymography showed an active band with a similar molecular mass. The N-terminal sequence of herinase VPSSFRTTITDAQLRG was highly distinguished from known fibrinolytic enzymes. Moreover, the enzyme activity was strongly inhibited by EDTA and EGTA, indicating that herinase is a metalloprotease. Herinase exhibited high specificity for the substrate t-PA followed by plasmin. The K(m) and V(max) values for H-D-Ile-Pro-Arg-PNA were found to be 4.7 mg and 26.7 U/ml respectively. Similarly, fibrin plate assays revealed that it was able to degrade fibrin clot directly and also able to activate plasminogen. Herinase provoked a rapid degradation of fibrin and fibrinogen α chains and slower degradation of γ chains. It had no activity on the β chains of fibrin and fibrinogen. This result suggests that herinase could possibly contain higher amount of α-fibrinogenase. The activity of herinase was stimulated by metal ions such as Ca(2+), Mg(2+), and Mn(2+), but inhibited by Cu(2+), Fe(2+), and Zn(2+). Herinase exhibited maximum activity at 30 °C and pH 7.0. These results demonstrate that herinase could be a novel fibrinolytic enzyme. PMID:23564433

  15. Bifunctional electro-optical nanoprobe to real-time detect local biochemical processes in single cells.

    PubMed

    Zheng, Xin Ting; Hu, Weihua; Wang, Houxiao; Yang, Hongbin; Zhou, Wei; Li, Chang Ming

    2011-07-15

    A bifunctional electro-optical nanoprobe with integrated nanoring electrode and optical nanotip was fabricated and investigated to simultaneously detect both electrical and optical signals in real-time with high spatial resolution. Concurrent measurements of the oxidant generation and the intracellular antioxidant levels in single cells correlate the stronger oxidant generation with an altered initial antioxidant response in the breast cancer cells in comparison to the normal ones suggesting that the cell malignancy is associated with the strength of oxidative stress, and the higher antioxidant level may be the cause of the drug resistance. While the optical detection indicates the fluctuation of the intracellular redox homeostasis, the chronoamperometric signals allow quantitative real-time detection of the H₂O₂ release and decay. Furthermore, the nanoscale probe enables localized simultaneous detections thus discovering that activated enzymes responsible for the oxidative stress target at specific membrane regions. This method promises applications in study of the dynamics of important physiological processes, and provides the opportunity to unravel the interplay of various signaling pathways. PMID:21632233

  16. A new bifunctional hybrid nanostructure as an active platform for photothermal therapy and MR imaging.

    PubMed

    Khafaji, Mona; Vossoughi, Manouchehr; Hormozi-Nezhad, M Reza; Dinarvand, Rassoul; Börrnert, Felix; Irajizad, Azam

    2016-01-01

    As a bi-functional cancer treatment agent, a new hybrid nanostructure is presented which can be used for photothermal therapy by exposure to one order of magnitude lower laser powers compared to similar nanostructures in addition to substantial enhancment in magnetic resonance imaging (MRI) contrast. This gold-iron oxide hybrid nanostructure (GIHN) is synthesized by a cost-effective and high yield water-based approach. The GIHN is sheilded by PEG. Therefore, it shows high hemo and biocompatibility and more than six month stability. Alongside earlier nanostructures, the heat generation rate of GIHN is compareable with surfactnat-capped gold nanorods (GNRs). Two reasons are behind this enhancement: Firstly the distance between GNRs and SPIONs is adjusted in a way that the surface plasmon resonance of the new nanostructure is similar to bare GNRs and secondly the fraction of GNRs is raised in the hybrid nanostructure. GIHN is then applied as a photothermal agent using laser irradiation with power as low as 0.5 W.cm(-2) and only 32% of human breast adenocarcinoma cells could survive. The GIHN also acts as a dose-dependent transvers relaxation time (T2) MRI contrast agent. The results show that the GINH can be considered as a good candidate for multimodal photothermal therapy and MRI. PMID:27297588

  17. Purification and characterisation of a bifunctional alginate lyase from novel Isoptericola halotolerans CGMCC 5336.

    PubMed

    Dou, Wenfang; Wei, Dan; Li, Hui; Li, Heng; Rahman, Muhammad Masfiqur; Shi, Jinsong; Xu, Zhenghong; Ma, Yanhe

    2013-11-01

    A novel halophilic alginate-degrading microorganism was isolated from rotten seaweed and identified as Isoptericola halotolerans CGMCC5336. The lyase from the strain was purified to homogeneity by combining of ammonium sulfate fractionation and anion-exchange chromatography with a specific activity of 8409.19 U/ml and a recovery of 25.07%. This enzyme was a monomer with a molecular mass of approximately 28 kDa. The optimal temperature and pH were 50 °C and pH 7.0, respectively. The lyase maintained stability at neutral pH (7.0-8.0) and temperatures below 50 °C. Metal ions including Na(+), Mg(2+), Mn(2+), and Ca(2+) notably increased the activity of the enzyme. With sodium alginate as the substrate, the Km and Vmax were 0.26 mg/ml and 1.31 mg/ml min, respectively. The alginate lyase had substrate specificity for polyguluronate and polymannuronate units in alginate molecules, indicating its bifunctionality. These excellent characteristics demonstrated the potential applications in alginate oligosaccharides production with low polymerisation degrees. PMID:24053829

  18. Biological channeling of a reactive intermediate in the bifunctional enzyme DmpFG.

    PubMed

    Smith, Natalie E; Vrielink, Alice; Attwood, Paul V; Corry, Ben

    2012-02-22

    It has been hypothesized that the bifunctional enzyme DmpFG channels its intermediate, acetaldehyde, from one active site to the next using a buried intermolecular channel identified in the crystal structure. This channel appears to switch between an open and a closed conformation depending on whether the coenzyme NAD(+) is present or absent. Here, we applied molecular dynamics and metadynamics to investigate channeling within DmpFG in both the presence and absence of NAD(+). We found that substrate channeling within this enzyme is energetically feasible in the presence of NAD(+) but was less likely in its absence. Tyr-291, a proposed control point at the channel's entry, does not appear to function as a molecular gate. Instead, it is thought to orientate the substrate 4-hydroxy-2-ketovalerate in DmpG before reaction occurs, and may function as a proton shuttle for the DmpG reaction. Three hydrophobic residues at the channel's exit appear to have an important role in controlling the entry of acetaldehyde into the DmpF active site. PMID:22385858

  19. Construction of three different recombinant scorpion fusion proteins with bifunctional activity.

    PubMed

    Cui, Y; Guo, G L; Liu, Y F; Mao, Y Z; Zhang, R; Wu, C F; Zhang, J H

    2011-06-01

    This is the first report of three different fusion proteins with an antitumor-analgesic peptide obtained from Chinese scorpion Buthus martensii Karsch (BmKAGAP). The fusion proteins were constructed in the form of chimeric toxins, aiming to obtain bifunctional analgesic and antitumor activity. The fusion proteins consisted of luteinizing hormone-releasing hormone (LHRH), three different types of flexible linkers (L1, Ser-Ser-His-His-His-His-His-His-Ser-Ser-Gly-Leu-Val-Pro-Arg-Gly-Ser-His-Met; L2, Gly-Gly-Gly-Ser-Gly-Gly-Gly-Ser; L3, Ser-Gly-Gly-Ser-Gly-Gly-Ser-Gly-Gly-Gly-Ser-Ser-Gly-Gly-Ser-Gly-Gly-Gly-Gly-Ser-Gly-Gly-Gly-Gly-Ser), and BmKAGAP. The genes coding three fusion proteins were cloned and expressed in E. coli in soluble form. Following two successive column chromatographic separations, purified fusion proteins were obtained. These fusion proteins exhibited analgesic activity in mice and were cytotoxic to a hepatocellular carcinoma cell line Hep3B. PMID:21793303

  20. Three crystal forms of the bifunctional enzyme proline utilization A (PutA) from Bradyrhizobium japonicum.

    PubMed

    Schuermann, Jonathan P; White, Tommi A; Srivastava, Dhiraj; Karr, Dale B; Tanner, John J

    2008-10-01

    Proline utilization A proteins (PutAs) are large (1000-1300 residues) membrane-associated bifunctional flavoenzymes that catalyze the two-step oxidation of proline to glutamate by the sequential action of proline dehydrogenase and Delta(1)-pyrroline-5-carboxylate dehydrogenase domains. Here, the first successful crystallization efforts for a PutA protein are described. Three crystal forms of PutA from Bradyrhizobium japonicum are reported: apparent tetragonal, hexagonal and centered monoclinic. The apparent tetragonal and hexagonal crystals were grown in the presence of PEG 3350 and sodium formate near pH 7. The apparent tetragonal form diffracted to 2.7 A resolution and exhibited pseudo-merohedral twinning such that the true space group is P2(1)2(1)2(1) with four molecules in the asymmetric unit. The hexagonal form diffracted to 2.3 A resolution and belonged to space group P6(2)22 with one molecule in the asymmetric unit. Centered monoclinic crystals were grown in ammonium sulfate, diffracted to 2.3 A resolution and had two molecules in the asymmetric unit. Removing the histidine tag was important in order to obtain the C2 crystal form. PMID:18931443

  1. Three crystal forms of the bifunctional enzyme proline utilization A (PutA) from Bradyrhizobium japonicum

    PubMed Central

    Schuermann, Jonathan P.; White, Tommi A.; Srivastava, Dhiraj; Karr, Dale B.; Tanner, John J.

    2008-01-01

    Proline utilization A proteins (PutAs) are large (1000–1300 residues) membrane-associated bifunctional flavoenzymes that catalyze the two-step oxidation of proline to glutamate by the sequential action of proline dehydrogenase and Δ1-pyrroline-5-carboxylate dehydrogenase domains. Here, the first successful crystallization efforts for a PutA protein are described. Three crystal forms of PutA from Bradyrhizobium japonicum are reported: apparent tetragonal, hexagonal and centered monoclinic. The apparent tetragonal and hexagonal crystals were grown in the presence of PEG 3350 and sodium formate near pH 7. The apparent tetragonal form diffracted to 2.7 Å resolution and exhibited pseudo-merohedral twinning such that the true space group is P212121 with four molecules in the asymmetric unit. The hexagonal form diffracted to 2.3 Å resolution and belonged to space group P6222 with one molecule in the asymmetric unit. Centered monoclinic crystals were grown in ammonium sulfate, diffracted to 2.3 Å resolution and had two molecules in the asymmetric unit. Removing the histidine tag was important in order to obtain the C2 crystal form. PMID:18931443

  2. Crystal structure of the bifunctional proline utilization A flavoenzyme from Bradyrhizobium japonicum

    PubMed Central

    Srivastava, Dhiraj; Schuermann, Jonathan P.; White, Tommi A.; Krishnan, Navasona; Sanyal, Nikhilesh; Hura, Greg L.; Tan, Anmin; Henzl, Michael T.; Becker, Donald F.; Tanner, John J.

    2010-01-01

    The bifunctional proline catabolic flavoenzyme, proline utilization A (PutA), catalyzes the oxidation of proline to glutamate via the sequential activities of FAD-dependent proline dehydrogenase (PRODH) and NAD+-dependent Δ1-pyrroline-5-carboxylate dehydrogenase (P5CDH) domains. Although structures for some of the domains of PutA are known, a structure for the full-length protein has not previously been solved. Here we report the 2.1 Å resolution crystal structure of PutA from Bradyrhizobium japonicum, along with data from small-angle x-ray scattering, analytical ultracentrifugation, and steady-state and rapid-reaction kinetics. PutA forms a ring-shaped tetramer in solution having a diameter of 150 Å. Within each protomer, the PRODH and P5CDH active sites face each other at a distance of 41 Å and are connected by a large, irregularly shaped cavity. Kinetics measurements show that glutamate production occurs without a lag phase, suggesting that the intermediate, Δ1-pyrroline-5-carboxylate, is preferably transferred to the P5CDH domain rather than released into the bulk medium. The structural and kinetic data imply that the cavity serves both as a microscopic vessel for the hydrolysis of Δ1-pyrroline-5-carboxylate to glutamate semialdehyde and a protected conduit for the transport of glutamate semialdehyde to the P5CDH active site. PMID:20133651

  3. Crystal structure of the bifunctional proline utilization A flavoenzyme from Bradyrhizobium japonicum

    SciTech Connect

    Srivastava, Dhiraj; Schuermann, Jonathan P.; White, Tommi A.; Krishnan, Navasona; Sanyal, Nikhilesh; Hura, Greg L.; Tan, Anmin; Henzl, Michael T.; Becker, Donald F.; Tanner, John J.

    2010-04-26

    The bifunctional proline catabolic flavoenzyme, proline utilization A (PutA), catalyzes the oxidation of proline to glutamate via the sequential activities of FAD-dependent proline dehydrogenase (PRODH) and NAD{sup +}-dependent {Delta}{sup 1}-pyrroline-5-carboxylate dehydrogenase (P5CDH) domains. Although structures for some of the domains of PutA are known, a structure for the full-length protein has not previously been solved. Here we report the 2.1 {angstrom} resolution crystal structure of PutA from Bradyrhizobium japonicum, along with data from small-angle x-ray scattering, analytical ultracentrifugation, and steady-state and rapid-reaction kinetics. PutA forms a ring-shaped tetramer in solution having a diameter of 150 {angstrom}. Within each protomer, the PRODH and P5CDH active sites face each other at a distance of 41 {angstrom} and are connected by a large, irregularly shaped cavity. Kinetics measurements show that glutamate production occurs without a lag phase, suggesting that the intermediate, {Delta}{sup 1}-pyrroline-5-carboxylate, is preferably transferred to the P5CDH domain rather than released into the bulk medium. The structural and kinetic data imply that the cavity serves both as a microscopic vessel for the hydrolysis of {Delta}{sup 1}-pyrroline-5-carboxylate to glutamate semialdehyde and a protected conduit for the transport of glutamate semialdehyde to the P5CDH active site.

  4. Bifunctional nanoparticles for surface-enhanced Raman spectroscopy-based leukemia biomarker detection

    NASA Astrophysics Data System (ADS)

    Mehn, Dora; Morasso, Carlo; Vanna, Renzo; Schiumarini, Domitilla; Bedoni, Marzia; Ciceri, Fabio; Gramatica, Furio

    2014-03-01

    The Wilms tumor gene (WT1) is a biomarker overexpressed in more than 90% of acute myeloid leukemia patients. Fast and sensitive detection of the WT1 in blood samples would allow monitoring of the minimal residual disease during clinical remission and would permit early detection of a potential relapse in acute myeloid leukemia. In this work, Surface Enhanced Raman Spectroscopy (SERS) based detection of the WT1 sequence using bifunctional, magnetic core - gold shell nanoparticles is presented. The classical co-precipitation method was applied to generate magnetic nanoparticles which were coated with a gold shell after modification with aminopropyltriethoxy silane and subsequent deposition of gold nanoparticle seeds. Simple hydroquinone based reduction procedure was applied for the shell growing in water based reaction mixture at room temperature. Thiolated ssDNA probes of the WT1 sequence were immobilized as capture oligonucleotides on the gold surface. Malachite green was applied both for testing the amplification performance of the core-shell colloidal SERS substrate and also as label dye of the target DNA sequence. The SERS enhancer efficacy of the core-shell nanomaterial was compared with the efficacy of classical spherical gold particles produced using the conventional citrate reduction method. The core-shell particles were found not only to provide an opportunity for facile separation in a heterogeneous reaction system but also to be superior regarding robustness as SERS enhancers.

  5. Chromium(VI) removal via reduction-sorption on bi-functional silica adsorbents.

    PubMed

    Zaitseva, Nataliya; Zaitsev, Vladimir; Walcarius, Alain

    2013-04-15

    Organically-modified silica gels bearing mercaptopropyl and ethylenediaminetriacetate groups (SiO2-SH/ED3A) have been used for reduction and subsequent sequestration of Cr(VI) species. The uptake mechanism involves Cr(VI) reduction by thiol groups (SH) and further immobilization of the so-generated Cr(III) species via complexation to the ethylenediaminetriacetate moieties (ED3A). The most appropriate pH range (1-3) for complete Cr(VI) reduction-sorption by SiO2-SH/ED3A originates from the balance between full reduction of Cr(VI) by SH, requiring low pH values, and quantitative complexation of Cr(III) by ED3A, which is favored in less acidic media. Such bi-functional adsorbents are considerably more effective at removal of Cr(VI) than those simply modified with thiol groups alone. The whole reduction-sorption process was characterized by fast kinetics, thus permitting efficient use of the SiO2-SH/ED3A adsorbent in dynamic conditions (column experiments). Monitoring the amount of immobilized chromium species on the solid was achieved using X-ray fluorescence spectroscopy and UV-vis spectroscopy. Studying the influence of ionic strength and presence of heavy metals revealed few interference on Cr(VI) removal. PMID:23500426

  6. Novel Bifunctional Cyclic Chelator for 89Zr Labeling–Radiolabeling and Targeting Properties of RGD Conjugates

    PubMed Central

    2015-01-01

    Within the last years 89Zr has attracted considerable attention as long-lived radionuclide for positron emission tomography (PET) applications. So far desferrioxamine B (DFO) has been mainly used as bifunctional chelating system. Fusarinine C (FSC), having complexing properties comparable to DFO, was expected to be an alternative with potentially higher stability due to its cyclic structure. In this study, as proof of principle, various FSC-RGD conjugates targeting αvß3 integrins were synthesized using different conjugation strategies and labeled with 89Zr. In vitro stability, biodistribution, and microPET/CT imaging were evaluated using [89Zr]FSC-RGD conjugates or [89Zr]triacetylfusarinine C (TAFC). Quantitative 89Zr labeling was achieved within 90 min at room temperature. The distribution coefficients of the different radioligands indicate hydrophilic character. Compared to [89Zr]DFO, [89Zr]FSC derivatives showed excellent in vitro stability and resistance against transchelation in phosphate buffered saline (PBS), ethylenediaminetetraacetic acid solution (EDTA), and human serum for up to 7 days. Cell binding studies and biodistribution as well as microPET/CT imaging experiments showed efficient receptor-specific targeting of [89Zr]FSC-RGD conjugates. No bone uptake was observed analyzing PET images indicating high in vivo stability. These findings indicate that FSC is a highly promising chelator for the development of 89Zr-based PET imaging agents. PMID:25941834

  7. First report of a bifunctional chitinase/lysozyme produced by Bacillus pumilus SG2.

    PubMed

    Ghasemi, Seyedhadi; Ahmadian, Gholamreza; Sadeghi, Mehdi; Zeigler, Daniel R; Rahimian, Heshmatollah; Ghandili, Soheila; Naghibzadeh, Neda; Dehestani, Ali

    2011-03-01

    Bacillus pumilus SG2 isolated from high salinity ecosystem in Iran produces two chitinases (ChiS and ChiL) and secretes them into the medium. In this study, chiS and chiL genes were cloned in pQE-30 expression vector and were expressed in the cytoplasm of Escherichia coli strain M15. The recombinant proteins were purified using Ni-NTA column. The optimum pH and optimum temperature for enzyme activity of ChiS were pH 6, 50°C; those of ChiL were pH 6.5, 40°C. The purified chitinases showed antifungal activity against Fusarium graminearum, Rhizoctonia solani, Magnaporthe grisea, Sclerotinia sclerotiorum, Trichoderma reesei, Botrytis cinerea and Bipolaris sp. Moreover, purified ChiS was identified as chitinase/lysozyme, which are capable of degrading the chitin component of fungal cell walls and the peptidoglycan component of cell walls with many kinds of bacteria (Xanthomonas translucens pv. hordei, Xanthomonas axonopodis pv. citri, Bacillus licheniformis, E. coli C600, E. coli TOP10, Pseudomonas aeruginosa and Pseudomonas putida). Strong homology was found between the three-dimensional structures of ChiS and a chitinase/lysozyme from Bacillus circulans WL-12. This is the first report of a bifunctional chitinase/lysozyme from B. pumilus. PMID:22112904

  8. Developmental Roles of D-bifunctional Protein-A Zebrafish Model of Peroxisome Dysfunction

    PubMed Central

    Kim, Yong-Il; Bhandari, Sushil; Lee, Joon No; Yoo, Kyeong-Won; Kim, Se-Jin; Oh, Gi-Su; Kim, Hyung-Jin; Cho, Meyoung; Kwak, Jong-Young; So, Hong-Seob; Park, Raekil; Choe, Seong-Kyu

    2014-01-01

    The peroxisome is an intracellular organelle that responds dynamically to environmental changes. Various model organisms have been used to study the roles of peroxisomal proteins in maintaining cellular homeostasis. By taking advantage of the zebrafish model whose early stage of embryogenesis is dependent on yolk components, we examined the developmental roles of the D-bifunctional protein (Dbp), an essential enzyme in the peroxisomal β-oxidation. The knockdown of dbp in zebrafish phenocopied clinical manifestations of its deficiency in human, including defective craniofacial morphogenesis, growth retardation, and abnormal neuronal development. Overexpression of murine Dbp rescued the morphological phenotypes induced by dbp knockdown, indicative of conserved roles of Dbp during zebrafish and mammalian development. Knockdown of dbp impaired normal development of blood, blood vessels, and most strikingly, endoderm-derived organs including the liver and pancreas - a phenotype not reported elsewhere in connection with peroxisome dysfunction. Taken together, our results demonstrate for the first time that zebrafish might be a useful model animal to study the role of peroxisomes during vertebrate development. PMID:24552713

  9. A new bifunctional hybrid nanostructure as an active platform for photothermal therapy and MR imaging

    PubMed Central

    Khafaji, Mona; Vossoughi, Manouchehr; Hormozi-Nezhad, M. Reza; Dinarvand, Rassoul; Börrnert, Felix; Irajizad, Azam

    2016-01-01

    As a bi-functional cancer treatment agent, a new hybrid nanostructure is presented which can be used for photothermal therapy by exposure to one order of magnitude lower laser powers compared to similar nanostructures in addition to substantial enhancment in magnetic resonance imaging (MRI) contrast. This gold-iron oxide hybrid nanostructure (GIHN) is synthesized by a cost-effective and high yield water-based approach. The GIHN is sheilded by PEG. Therefore, it shows high hemo and biocompatibility and more than six month stability. Alongside earlier nanostructures, the heat generation rate of GIHN is compareable with surfactnat-capped gold nanorods (GNRs). Two reasons are behind this enhancement: Firstly the distance between GNRs and SPIONs is adjusted in a way that the surface plasmon resonance of the new nanostructure is similar to bare GNRs and secondly the fraction of GNRs is raised in the hybrid nanostructure. GIHN is then applied as a photothermal agent using laser irradiation with power as low as 0.5 W.cm−2 and only 32% of human breast adenocarcinoma cells could survive. The GIHN also acts as a dose-dependent transvers relaxation time (T2) MRI contrast agent. The results show that the GINH can be considered as a good candidate for multimodal photothermal therapy and MRI. PMID:27297588

  10. Platinum-gold nanoparticles: a highly active bifunctional electrocatalyst for rechargeable lithium-air batteries.

    PubMed

    Lu, Yi-Chun; Xu, Zhichuan; Gasteiger, Hubert A; Chen, Shuo; Hamad-Schifferli, Kimberly; Shao-Horn, Yang

    2010-09-01

    PtAu nanoparticles (NPs) were shown to strongly enhance the kinetics of the oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) in rechargeable Li-O(2) cells. Li-O(2) cells with PtAu/C were found to exhibit the highest round-trip efficiency reported to date. During ORR via xLi(+) + O(2) + xe(-) --> Li(x)O(2), the discharge voltage with PtAu/C was considerably higher than that of pure carbon and comparable to that of Au/C. During OER via Li(x)O(2) --> xLi(+) + O(2) + xe(-), the charge voltages with PtAu/C fell in the range from 3.4 to 3.8 V(Li), which is slightly lower than obtained with Pt. It is hypothesized that PtAu NPs exhibit bifunctional catalytic activity, having surface Au and Pt atoms primarily responsible for ORR and OER kinetics in Li-O(2) cells, respectively. PMID:20527774

  11. Cobalt Phosphide Hollow Polyhedron as Efficient Bifunctional Electrocatalysts for the Evolution Reaction of Hydrogen and Oxygen.

    PubMed

    Liu, Mengjia; Li, Jinghong

    2016-01-27

    The development of efficient and low-cost hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) electrocatalysts for renewable-energy conversion techniques is highly desired. A kind of hollow polyhedral cobalt phosphide (CoP hollow polyhedron) is developed as efficient bifunctional electrocatalysts for HER and OER templated by Co-centered metal-organic frameworks. The as-prepared CoP hollow polyhedron, which have large specific surface area and high porosity providing rich catalytic active sites, show excellent electrocatalytic performances for both HER and OER in acidic and alkaline media, respectively, with onset overpotentials of 35 and 300 mV, Tafel slopes of 59 and 57 mV dec(-1), and a current density of 10 mA cm(-2) at overpotentials of 159 and 400 mV for HER and OER, respectively, which are remarkably superior to those of particulate CoP (CoP particles) and comparable to those of commercial noble-metal catalysts. In addition, the CoP hollow polyhedron also show good durability after long-term operations. PMID:26711014

  12. Engineering the robustness of Saccharomyces cerevisiae by introducing bifunctional glutathione synthase gene.

    PubMed

    Qiu, Zhiqi; Deng, Zujun; Tan, Hongming; Zhou, Shining; Cao, Lixiang

    2015-04-01

    Robust, high-yielding Saccharomyces cerevisiae is highly desirable for cost-effective cellulosic ethanol production. In this study, the bifunctional glutathione (GSH) synthetase genes GCSGS at high copy number was integrated into ribosomal DNA of S. cerevisiae by Cre-LoxP system. Threefold higher GSH contents (54.9 μmol/g dry weight) accumulated in the engineered strain BY-G compared to the reference strain. Tolerance of BY-G to H2O2 (3 mM), temperature (40 °C), furfural (10 mM), hydroxymethylfurfural (HMF, 10 mM) and 0.5 mM Cd(2+) increased compared to reference strain. Twofold higher ethanol concentration was obtained by BY-G in simultaneous saccharification and fermentation of corn stover compared to the reference strain. The results showed that intracellular GSH content of S. cerevisiae has an influence on robustness. The strategy is used to engineer S. cerevisiae strains adaptive to a combination of tolerance to inhibitors and raised temperature that may occur in high solid simultaneous saccharification and fermentation of lignocellulosic feedstocks. PMID:25561319

  13. Directed assembly of bifunctional silica-iron oxide nanocomposite with open shell structure.

    PubMed

    Che, Hui Xin; Yeap, Swee Pin; Osman, Mohamed Syazwan; Ahmad, Abdul Latif; Lim, JitKang

    2014-10-01

    The synthesis of nanocomposite with controlled surface morphology plays a key role for pollutant removal from aqueous environments. The influence of the molecular size of the polyelectrolyte in synthesizing silica-iron oxide core-shell nanocomposite with open shell structure was investigated by using dynamic light scattering, atomic force microscopy, and quartz crystal microbalance with dissipation (QCM-D). Here, poly(diallydimethylammonium chloride) (PDDA) was used to promote the attachment of iron oxide nanoparticles (IONPs) onto the silica surface to assemble a nanocomposite with magnetic and catalytic bifunctionality. High molecular weight PDDA tended to adsorb on silica colloid, forming a more extended conformation layer than low molecular weight PDDA. Subsequent attachment of IONPs onto this extended PDDA layer was more randomly distributed, forming isolated islands with open space between them. By taking amoxicillin, an antibiotic commonly found in pharmaceutical waste, as the model system, better removal was observed for silica-iron oxide nanocomposite with a more extended open shell structure. PMID:25198872

  14. Effects of processing conditions on the reliability of cross-linked polyethylene cable insulation. Progress report

    SciTech Connect

    Phillips, P.J.

    1981-03-01

    Crystallization and morphology were investigated in cross-linked PE. /sup 13/C NMR was used to quantify the cross-links. Production of cable is being studied. Dielectric constant and loss of cross-linked PE are being measured. (DLC)

  15. Chitosan-based membranes with different ionic crosslinking density for pharmaceutical and industrial applications.

    PubMed

    Gierszewska, Magdalena; Ostrowska-Czubenko, Jadwiga

    2016-11-20

    Chitosan membranes (Ch), ionically crosslinked with pentasodium tripolyphosphate (TPP), were prepared using chitosan of medium and high molecular weight of similar degree of deacetylation and different crosslinking conditions. An effect of synthesis conditions (pH of crosslinking TPP solution equal to 5.5 and 9.0) on molecular and supermolecular structure and on crosslinking density of Ch/TPP membranes was confirmed using Fourier transform infrared spectroscopy (FTIR), wide-angle X-ray diffraction (WAXD) method and energy dispersive X-ray (EDX) spectrometry. Atomic-force microscopy (AFM) and contact angle measurements indicated some differences in membrane roughness and hydrophilicity. The state of water in non-crosslinked and ionically crosslinked Ch membranes containing different amount of water was investigated by low temperature differential scanning calorimetry (DSC) measurements. DSC analysis confirmed presence of freezing and non-freezing water in non-crosslinked and ionically crosslinked membranes. The amount of non-freezing water generally decreased after Ch crosslinking and was affected by crosslinking conditions and crosslinking density. Molecular weight of Ch had only slight influence on all characterized properties of ionically crosslinked membranes. PMID:27561522

  16. Characterization and affinity cross-linking of receptors for human recombinant lymphotoxin (tumor necrosis factor-beta) on a human histiocytic lymphoma cell line, U-937

    SciTech Connect

    Stauber, G.B.; Aggarwal, B.B.

    1989-02-25

    Recombinant human lymphotoxin (rhLT) expressed in a mammalian cell line was purified and used to examine its receptors on the human histiocytic lymphoma cell line U-937. rhLT was radioiodinated by the IODO-GEN method to a specific activity of 60 microCi/micrograms; the labeled protein was biologically active in the cytolytic assay, and displaceable binding to U-937 cells was observed. The specific binding reached a plateau within 10, 60, and 180 min at 37, 23, and 4 degrees C, respectively. Scatchard analysis of the binding data revealed the presence of a single class of high affinity receptors with an apparent Kd of 0.6 nM and a capacity of 33,000 +/- 7,000 binding sites/cell. The binding of 125I-rhLT to U-937 cells could be inhibited by excess unlabeled rhLT or recombinant human tumor necrosis factor (rhTNF), suggesting a common receptor for both molecules. As competitive inhibitor of the binding, rhTNF was equal in its potency to rhLT. Bacterial derived rhLT lacking carbohydrate was also found equipotent to cell line-derived rhLT for cell binding, indicating that carbohydrate plays no significant role in receptor interaction. Additionally, 125I-rhLT was covalently attached to the cell surface via a bifunctional cross-linking reagent, ethylene glycol bis(succinimidyl succinate), solubilized, and analyzed by sodium dodecyl sulfate-polyacrylamide gel electrophoresis. The cross-linking of the receptor to rhLT revealed two distinct bands at approximate molecular masses of 100,000 and 120,000 daltons. Both bands were absent when unlabeled rhLT or rhTNF was used for competition, indicating the specificity. Affinity cross-linking of U-937 cells with 125I-rhTNF, however, provided only a single band with a molecular mass of about 100,000 daltons. These results suggest that the manner in which rhLT interacts with its receptor is perhaps somewhat different from that of rhTNF.

  17. Bifunctional anion-exchange resins with improved selectivity and exchange kinetics

    DOEpatents

    Alexandratos, Spiro D.; Brown, Gilbert M.; Bonnesen, Peter V.; Moyer, Bruce A.

    2000-01-01

    Disclosed herein are a class of anion exchange resins containing two different exchange sites with improved selectivity and sorptive capability for chemical species in solution, such as heptavalent technetium (as pertechnetate anion, TcO.sub.4.sup.-). The resins are prepared by first reacting haloalkylated crosslinked copolymer beads with a large tertiary amine in a solvent in which the resin beads can swell, followed by reaction with a second, smaller, tertiary amine to more fully complete the functionalization of the resin. The resins have enhanced selectivity, capacity, and exchange kinetics.

  18. Stress-relaxation behavior in gels with ionic and covalent crosslinks

    NASA Astrophysics Data System (ADS)

    Zhao, Xuanhe; Huebsch, Nathaniel; Mooney, David J.; Suo, Zhigang

    2010-03-01

    Long-chained polymers in alginate hydrogels can form networks by either ionic or covalent crosslinks. This paper shows that the type of crosslinks can markedly affect the stress-relaxation behavior of the gels. In gels with only ionic crosslinks, stress relaxes mainly through breaking and subsequent reforming of the ionic crosslinks, and the time scale of the relaxation is independent of the size of the sample. By contrast, in gels with only covalent crosslinks, stress relaxes mainly through migration of water, and the relaxation slows down as the size of the sample increases. Implications of these observations are discussed.

  19. Isotopically coded cleavable cross-linker for studying protein-protein interaction and protein complexes.

    PubMed

    Petrotchenko, Evgeniy V; Olkhovik, Vyacheslav K; Borchers, Christoph H

    2005-08-01

    An emerging approach for studying protein-protein interaction in complexes is the combination of chemical cross-linking and mass spectrometric analysis of the cross-linked peptides (cross-links) obtained after proteolysis of the complex. This approach, however, has several challenges and limitations, including the difficulty of detecting the cross-links, the potential interference from non-informative "cross-linked peptides" (dead end and intrapeptide cross-links), and unambiguous identification of the cross-links by mass spectrometry. Thus, we have synthesized an isotopically coded ethylene glycol bis(succinimidylsuccinate) derivate (D12-EGS), which contains 12 deuterium atoms for easy detection of cross-links when applied in a 1:1 mixture with its H12 counterpart and is also cleavable for releasing the cross-linked peptides allowing unambiguous identification by MS sequencing. Moreover, hydrolytic cleavage permits rapid distinguishing between different types of cross-links. Cleavage of a dead end cross-link produces a doublet with peaks 4.03 Da apart, with the lower peak appearing at a molecular mass 162 Da lower than the mass of the H12 form of the original cross-linked peptide. Cleavage of an intrapeptide cross-link leads to a doublet 8.05 Da apart and 62 Da lower than the molecular mass of the H12 form of the original cross-linked peptide. Cleavage of an interpeptide cross-link forms a pair of 4.03-Da doublets, with the lower mass member of each pair each shifted up from its unmodified molecular weight by 82 Da because of the attached portion of the cross-linker. All of this information has been incorporated into a software algorithm allowing automatic screening and detection of cross-links and cross-link types in matrix-assisted laser desorption/ionization mass spectra. In summary, the ease of detection of these species through the use of an isotopically coded cleavable cross-linker and our software algorithm, followed by mass spectrometric sequencing of the

  20. Bifunctional Inhibition of Human Immunodeficiency Virus Type 1 Reverse Transcriptase: Mechanism and Proof-of-Concept as a Novel Therapeutic Design Strategy

    PubMed Central

    Bailey, Christopher M.; Sullivan, Todd J.; Iyidogan, Pinar; Tirado-Rives, Julian; Chung, Raymond; Ruiz-Caro, Juliana; Mohamed, Ebrahim; Jorgensen, William; Hunter, Roger; Anderson, Karen S.

    2013-01-01

    Human immunodeficiency virus type 1 reverse transcriptase (HIV-1 RT) is a major target for currently approved anti-HIV drugs. These drugs are divided into two classes: nucleoside and non-nucleoside reverse transcriptase inhibitors (NRTIs and NNRTIs). This study illustrates the synthesis and biochemical evaluation of a novel bifunctional RT inhibitor utilizing d4T (NRTI) and a TMC-derivative (a diarylpyrimidine NNRTI) linked via a poly(ethylene glycol) (PEG) linker. HIV-1 RT successfully incorporates the triphosphate of d4T-4PEG-TMC bifunctional inhibitor in a base-specific manner. Moreover, this inhibitor demonstrates low nanomolar potency that has 4.3-fold and 4300-fold enhancement of polymerization inhibition in vitro relative to the parent TMC-derivative and d4T, respectively. This study serves as a proof-of-concept for the development and optimization of bifunctional RT inhibitors as potent inhibitors of HIV-1 viral replication. PMID:23659183