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Sample records for reversible covalent modification

  1. Covalent Surface Modifications of Carbon Nanotubes.

    Energy Technology Data Exchange (ETDEWEB)

    Pavia Sanders, Adriana [Sandia National Lab. (SNL-CA), Livermore, CA (United States); O' Bryan, Greg [Sandia National Lab. (SNL-CA), Livermore, CA (United States)

    2017-07-01

    A report meant to document the chemistries investigated by the author for covalent surface modification of CNTs. Oxidation, cycloaddition, and radical reactions were explored to determine their success at covalently altering the CNT surface. Characterization through infrared spectroscopy, Raman spectroscopy, and thermo gravimetric analysis was performed in order to determine the success of the chemistries employed. This report is not exhaustive and was performed for CNT surface modification exploration as it pertains to the "Next Gen" project.

  2. Protein covalent modification by biologically active quinones

    Directory of Open Access Journals (Sweden)

    MIROSLAV J. GASIC

    2004-11-01

    Full Text Available The avarone/avarol quinone/hydroquinone couple shows considerable antitumor activity. In this work, covalent modification of b-lactoglobulin by avarone and its derivatives as well as by the synthetic steroidal quinone 2,5(10-estradiene-1,4,17-trione and its derivatives were studied. The techniques for studying chemical modification of b-lactoglobulin by quinones were: UV/Vis spectrophotometry, SDS PAGE and isoelectrofocusing. SDS PAGE results suggest that polymerization of the protein occurs. It could be seen that the protein of 18 kD gives the bands of 20 kD, 36 kD, 40 kD, 45 kD, 64 kD and 128 kD depending on modification agent. The shift of the pI of the protein (5.4 upon modification toward lower values (from pI 5.0 to 5.3 indicated that lysine amino groups are the principal site of the reaction of b-lactoglobulin with the quinones.

  3. Cell Signalling Through Covalent Modification and Allostery

    Science.gov (United States)

    Johnson, Louise N.

    Phosphorylation plays essential roles in nearly every aspect of cell life. Protein kinases catalyze the transfer of the γ-phosphate of ATP to a serine, threonine or tyrosine residue in protein substrates. This covalent modification allows activation or inhibition of enzyme activity, creates recognition sites for other proteins and promotes order/disorder or disorder/order transitions. These properties regulate ­signalling pathways and cellular processes that mediate metabolism, transcription, cell cycle progression, differentiation, cytoskeleton arrangement and cell movement, apoptosis, intercellular communication, and neuronal and immunological functions. In this lecture I shall review the structural consequences of protein phosphorylation using our work on glycogen phosphorylase and the cell cycle cyclin dependent protein kinases as illustrations. Regulation of protein phosphorylation may be disrupted in the diseased state and protein kinases have become high profile targets for drug development. To date there are 11 compounds that have been approved for clinical use in the treatment of cancer.

  4. Covalent modification of platelet proteins by palmitate

    International Nuclear Information System (INIS)

    Muszbek, L.; Laposata, M.

    1989-01-01

    Covalent attachment of fatty acid to proteins plays an important role in association of certain proteins with hydrophobic membrane structures. In platelets, the structure of many membrane glycoproteins (GPs) has been examined in detail, but the question of fatty acid acylation of platelet proteins has not been addressed. In this study, we wished to determine (a) whether platelet proteins could be fatty acid acylated; and, if so, (b) whether these modified proteins were present in isolated platelet membranes and cytoskeletal fractions; and (c) if the pattern of fatty acid acylated proteins changed on stimulation of the platelets with the agonist thrombin. We observed that in platelets allowed to incorporate 3H-palmitate, a small percentage (1.37%) of radioactivity incorporated into the cells became covalently bound to protein. Selective cleavage of thioester, thioester plus O-ester, and amide-linked 3H-fatty acids from proteins, and their subsequent analysis by high-performance liquid chromatography (HPLC) indicated that the greatest part of 3H-fatty acid covalently bound to protein was thioester-linked 3H-palmitate. By sodium dodecyl sulfate-polyacrylamide gel electrophoresis (SDS-PAGE) and fluorography, at least ten major radiolabeled proteins were detected. Activation of platelets by thrombin greatly increased the quantity of 3H-palmitoylated proteins associated with the cytoskeleton. Nearly all radiolabeled proteins were recovered in the membrane fraction, indicating that these proteins are either integral or peripheral membrane proteins or proteins tightly associated to membrane constituents. Components of the GPIIb-IIIa complex were not palmitoylated. Thus, platelet proteins are significantly modified posttranslationally by 3H-palmitate, and incorporation of palmitoylated proteins into the cytoskeleton is a prominent component of the platelet response to thrombin stimulation

  5. Biofunctional Paper via Covalent Modification of Cellulose

    Science.gov (United States)

    Yu, Arthur; Shang, Jing; Cheng, Fang; Paik, Bradford A.; Kaplan, Justin M.; Andrade, Rodrigo B.; Ratner, Daniel M.

    2012-01-01

    Paper-based analytical devices are the subject of growing interest for the development of low-cost point-of-care diagnostics, environmental monitoring technologies and research tools for limited-resource settings. However, there are limited chemistries available for the conjugation of biomolecules to cellulose for use in biomedical applications. Herein, divinyl sulfone (DVS) chemistry was demonstrated to covalently immobilize small molecules, proteins and DNA onto the hydroxyl groups of cellulose membranes through nucleophilic addition. Assays on modified cellulose using protein-carbohydrate and protein-glycoprotein interactions as well as oligonucleotide hybridization showed that the membrane’s bioactivity was specific, dose-dependent, and stable over a long period of time. Use of an inkjet printer to form patterns of biomolecules on DVS-activated cellulose illustrates the adaptability of the DVS functionalization technique to pattern sophisticated designs, with potential applications in cellulose-based lateral flow devices. PMID:22708701

  6. Remendable Polymeric Materials Using Reversible Covalent Bonds

    Science.gov (United States)

    2008-12-01

    response in poly(ethylene-co-methacrylic acid ) copolymers. Journal of The Royal Society Interface, 4, 405-411. Kavitha, A. A., and N. K. Singha...2007: A tailor-made polymethacrylate bearing a reactive diene in reversible diels-alder reaction. J. Polym. Sci. A Polym. Chem., 45, 4441-4449

  7. Covalent modification and exfoliation of graphene oxide using ferrocene

    Science.gov (United States)

    Avinash, M. B.; Subrahmanyam, K. S.; Sundarayya, Y.; Govindaraju, T.

    2010-09-01

    Large scale preparation of single-layer graphene and graphene oxide is of great importance due to their potential applications. We report a simple room temperature method for the exfoliation of graphene oxide using covalent modification of graphene oxide with ferrocene to obtain single-layer graphene oxide sheets. The samples were characterized by FESEM, HRTEM, AFM, EDAX, FT-IR, Raman and Mössbauer spectroscopic studies. HRTEM micrograph of the covalently modified graphene oxide showed increased interlayer spacing of ~2.4 nm due to ferrocene intercalation. The presence of single-layer graphene oxide sheets were confirmed by AFM studies. The covalently modified ferrocene-graphene oxide composite showed interesting magnetic behavior.Large scale preparation of single-layer graphene and graphene oxide is of great importance due to their potential applications. We report a simple room temperature method for the exfoliation of graphene oxide using covalent modification of graphene oxide with ferrocene to obtain single-layer graphene oxide sheets. The samples were characterized by FESEM, HRTEM, AFM, EDAX, FT-IR, Raman and Mössbauer spectroscopic studies. HRTEM micrograph of the covalently modified graphene oxide showed increased interlayer spacing of ~2.4 nm due to ferrocene intercalation. The presence of single-layer graphene oxide sheets were confirmed by AFM studies. The covalently modified ferrocene-graphene oxide composite showed interesting magnetic behavior. Electronic supplementary information (ESI) available: Magnetic data; AFM images; TEM micrographs; and Mössbauer spectroscopic data. See DOI: 10.1039/c0nr00024h

  8. Reversible polymer networks containing covalent and hydrogen bonding interactions

    NARCIS (Netherlands)

    Araya-Hermosilla, R.; Broekhuis, A.A.; Picchioni, F.

    Thermally reversible polymers with relatively high glass transition temperatures (T-g) are difficult to prepare but very interesting from an application point of view. In this work we present a novel reversible thermoset with tunable T-g based on chemical modification of aliphatic polyketones (PM)

  9. Non-covalent and reversible functionalization of carbon nanotubes

    Directory of Open Access Journals (Sweden)

    Antonello Di Crescenzo

    2014-09-01

    Full Text Available Carbon nanotubes (CNTs have been proposed and actively explored as multipurpose innovative nanoscaffolds for applications in fields such as material science, drug delivery and diagnostic applications. Their versatile physicochemical features are nonetheless limited by their scarce solubilization in both aqueous and organic solvents. In order to overcome this drawback CNTs can be easily non-covalently functionalized with different dispersants. In the present review we focus on the peculiar hydrophobic character of pristine CNTs that prevent them to easily disperse in organic solvents. We report some interesting examples of CNTs dispersants with the aim to highlight the essential features a molecule should possess in order to act as a good carbon nanotube dispersant both in water and in organic solvents. The review pinpoints also a few examples of dispersant design. The last section is devoted to the exploitation of the major quality of non-covalent functionalization that is its reversibility and the possibility to obtain stimuli-responsive precipitation or dispersion of CNTs.

  10. Adaptive polymeric nanomaterials utilizing reversible covalent and hydrogen bonding

    Science.gov (United States)

    Neikirk, Colin

    Adaptive materials based on stimuli responsive and reversible bonding moieties are a rapidly developing area of materials research. Advances in supramolecular chemistry are now being adapted to novel molecular architectures including supramolecular polymers to allow small, reversible changes in molecular and nanoscale structure to affect large changes in macroscale properties. Meanwhile, dynamic covalent chemistry provides a complementary approach that will also play a role in the development of smart adaptive materials. In this thesis, we present several advances to the field of adaptive materials and also provide relevant insight to the areas of polymer nanocomposites and polymer nanoparticles. First, we have utilized the innate molecular recognition and binding capabilities of the quadruple hydrogen bonding group ureidopyrimidinone (UPy) to prepare supramolecular polymer nanocomposites based on supramolecular poly(caprolactone) which show improved mechanical properties, but also an increase in particle aggregation with nanoparticle UPy functionalization. We also present further insight into the relative effects of filler-filler, filler-matrix, and matrix-matrix interactions using a UPy side-chain functional poly(butyl acrylate). These nanocomposites have markedly different behavior depending on the amount of UPy sidechain functionality. Meanwhile, our investigations of reversible photo-response showed that coumarin functionality in polymer nanoparticles not only facilitates light mediated aggregation/dissociation behavior, but also provides a substantial overall reduction in particle size and improvement in nanoparticle stability for particles prepared by Flash NanoPrecipitation. Finally, we have combined these stimuli responsive motifs as a starting point for the development of multiresponsive adaptive materials. The synthesis of a library of multifunctional materials has provided a strong base for future research in this area, although our initial

  11. Covalent modification of graphene and graphite using diazonium chemistry: tunable grafting and nanomanipulation.

    Science.gov (United States)

    Greenwood, John; Phan, Thanh Hai; Fujita, Yasuhiko; Li, Zhi; Ivasenko, Oleksandr; Vanderlinden, Willem; Van Gorp, Hans; Frederickx, Wout; Lu, Gang; Tahara, Kazukuni; Tobe, Yoshito; Uji-I, Hiroshi; Mertens, Stijn F L; De Feyter, Steven

    2015-05-26

    We shine light on the covalent modification of graphite and graphene substrates using diazonium chemistry under ambient conditions. We report on the nature of the chemical modification of these graphitic substrates, the relation between molecular structure and film morphology, and the impact of the covalent modification on the properties of the substrates, as revealed by local microscopy and spectroscopy techniques and electrochemistry. By careful selection of the reagents and optimizing reaction conditions, a high density of covalently grafted molecules is obtained, a result that is demonstrated in an unprecedented way by scanning tunneling microscopy (STM) under ambient conditions. With nanomanipulation, i.e., nanoshaving using STM, surface structuring and functionalization at the nanoscale is achieved. This manipulation leads to the removal of the covalently anchored molecules, regenerating pristine sp(2) hybridized graphene or graphite patches, as proven by space-resolved Raman microscopy and molecular self-assembly studies.

  12. Tough Self-Healing Elastomers by Molecular Enforced Integration of Covalent and Reversible Networks.

    Science.gov (United States)

    Wu, Jinrong; Cai, Li-Heng; Weitz, David A

    2017-10-01

    Self-healing polymers crosslinked by solely reversible bonds are intrinsically weaker than common covalently crosslinked networks. Introducing covalent crosslinks into a reversible network would improve mechanical strength. It is challenging, however, to apply this concept to "dry" elastomers, largely because reversible crosslinks such as hydrogen bonds are often polar motifs, whereas covalent crosslinks are nonpolar motifs. These two types of bonds are intrinsically immiscible without cosolvents. Here, we design and fabricate a hybrid polymer network by crosslinking randomly branched polymers carrying motifs that can form both reversible hydrogen bonds and permanent covalent crosslinks. The randomly branched polymer links such two types of bonds and forces them to mix on the molecular level without cosolvents. This enables a hybrid "dry" elastomer that is very tough with fracture energy 13500 Jm -2 comparable to that of natural rubber. Moreover, the elastomer can self-heal at room temperature with a recovered tensile strength 4 MPa, which is 30% of its original value, yet comparable to the pristine strength of existing self-healing polymers. The concept of forcing covalent and reversible bonds to mix at molecular scale to create a homogenous network is quite general and should enable development of tough, self-healing polymers of practical usage. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  13. Biofunctional paper via the covalent modification of cellulose.

    Science.gov (United States)

    Yu, Arthur; Shang, Jing; Cheng, Fang; Paik, Bradford A; Kaplan, Justin M; Andrade, Rodrigo B; Ratner, Daniel M

    2012-07-31

    Paper-based analytical devices are the subject of growing interest for the development of low-cost point-of-care diagnostics, environmental monitoring technologies, and research tools for limited-resource settings. However, there are limited chemistries available for the conjugation of biomolecules to cellulose for use in biomedical applications. Herein, divinyl sulfone (DVS) chemistry was demonstrated to immobilize small molecules, proteins, and DNA covalently onto the hydroxyl groups of cellulose membranes through nucleophilic addition. Assays on modified cellulose using protein-carbohydrate and protein-glycoprotein interactions as well as oligonucleotide hybridization showed that the membrane's bioactivity was specific, dose-dependent, and stable over a long period of time. The use of an inkjet printer to form patterns of biomolecules on DVS-activated cellulose illustrates the adaptability of the DVS functionalization technique to pattern sophisticated designs, with potential applications in cellulose-based lateral flow devices.

  14. Chemical Strategies for the Covalent Modification of Filamentous Phage

    Directory of Open Access Journals (Sweden)

    Matthew B Francis

    2014-12-01

    Full Text Available Historically filamentous bacteriophage have been known to be the workhorse of phage display due to their ability to link genotype to phenotype. More recently, the filamentous phage scaffold has proved to be powerful outside the realms of phage display technology in fields such as molecular imaging, cancer research and materials and vaccine development. The ability of the virion to serve as a platform for a variety of applications heavily relies on the functionalization of the phage coat proteins with a wide variety of functionalities. Genetic modification of the coat proteins has been the most widely used strategy for functionalizing the virion; however complementary chemical modification strategies can help to diversify the range of materials that can be developed. This review emphasizes the recent advances that have been made in the chemical modification of filamentous phage as well as some of the challenges that are involved functionalizing the virion.

  15. Heparin/heparan sulfate analysis by covalently modified reverse polarity capillary zone electrophoresis-mass spectrometry.

    Science.gov (United States)

    Sanderson, Patience; Stickney, Morgan; Leach, Franklin E; Xia, Qiangwei; Yu, Yanlei; Zhang, Fuming; Linhardt, Robert J; Amster, I Jonathan

    2018-04-13

    Reverse polarity capillary zone electrophoresis coupled to negative ion mode mass spectrometry (CZE-MS) is shown to be an effective and sensitive tool for the analysis of glycosaminoglycan mixtures. Covalent modification of the inner wall of the separation capillary with neutral or cationic reagents produces a stable and durable surface that provides reproducible separations. By combining CZE-MS with a cation-coated capillary and a sheath flow interface, a rapid and reliable method has been developed for the analysis of sulfated oligosaccharides from dp4 to dp12. Several different mixtures have been separated and detected by mass spectrometry. The mixtures were selected to test the capability of this approach to resolve subtle differences in structure, such as sulfation position and epimeric variation of the uronic acid. The system was applied to a complex mixture of heparin/heparan sulfate oligosaccharides varying in chain length from dp3 to dp12 and more than 80 molecular compositions were identified by accurate mass measurement. Copyright © 2018 Elsevier B.V. All rights reserved.

  16. Structural modification of covalent-bonded networks: on some methodological resolutions for binary chalcogenide glasses

    Energy Technology Data Exchange (ETDEWEB)

    Shpotyuk, M; Shpotyuk, Ya; Shpotyuk, O, E-mail: shpotyukmy@yahoo.com [Lviv Scientific Research Institute of Materials of SRC ' Carat' , 212, Stryjska str., Lviv, 79031 (Ukraine)

    2011-04-01

    New methodology to estimate efficiency of externally-induced structural modification in chalcogenide glasses is developed. This approach is grounded on the assumption that externally-induced structural modification is fully associated with destruction-polymerization transformations, which reveal themselves as local misbalances in covalent bond distribution, normal atomic coordination and intrinsic electrical fields. The input of each of these components into the total value of structural modification efficiency was probed for quasibinary (As{sub 2}S{sub 3}){sub 100-x}(Sb{sub 2}S{sub 3}){sub x} ChG.

  17. Structural modification of covalent-bonded networks: on some methodological resolutions for binary chalcogenide glasses

    International Nuclear Information System (INIS)

    Shpotyuk, M; Shpotyuk, Ya; Shpotyuk, O

    2011-01-01

    New methodology to estimate efficiency of externally-induced structural modification in chalcogenide glasses is developed. This approach is grounded on the assumption that externally-induced structural modification is fully associated with destruction-polymerization transformations, which reveal themselves as local misbalances in covalent bond distribution, normal atomic coordination and intrinsic electrical fields. The input of each of these components into the total value of structural modification efficiency was probed for quasibinary (As 2 S 3 ) 100-x (Sb 2 S 3 ) x ChG.

  18. Dynamic Multi-Component Covalent Assembly for the Reversible Binding of Secondary Alcohols and Chirality Sensing

    Science.gov (United States)

    You, Lei; Berman, Jeffrey S.; Anslyn, Eric V.

    2011-01-01

    Reversible covalent bonding is often employed for the creation of novel supramolecular structures, multi-component assemblies, and sensing ensembles. In spite of remarkable success of dynamic covalent systems, the reversible binding of a mono-alcohol with high strength is challenging. Here we show that a strategy of carbonyl activation and hemiaminal ether stabilization can be embodied in a four-component reversible assembly that creates a tetradentate ligand and incorporates secondary alcohols with exceptionally high affinity. Evidence is presented that the intermediate leading to binding and exchange of alcohols is an iminium ion. Further, to demonstrate the use of this assembly process we explored chirality sensing and enantiomeric excess determinations. An induced twist in the ligand by a chiral mono-ol results in large Cotton effects in the circular dichroism spectra indicative of the alcohol’s handedness. The strategy revealed in this study should prove broadly applicable for the incorporation of alcohols into supramolecular architecture construction. PMID:22109274

  19. Modeling the role of covalent enzyme modification in Escherichia coli nitrogen metabolism

    International Nuclear Information System (INIS)

    Kidd, Philip B; Wingreen, Ned S

    2010-01-01

    In the bacterium Escherichia coli, the enzyme glutamine synthetase (GS) converts ammonium into the amino acid glutamine. GS is principally active when the cell is experiencing nitrogen limitation, and its activity is regulated by a bicyclic covalent modification cascade. The advantages of this bicyclic-cascade architecture are poorly understood. We analyze a simple model of the GS cascade in comparison to other regulatory schemes and conclude that the bicyclic cascade is suboptimal for maintaining metabolic homeostasis of the free glutamine pool. Instead, we argue that the lag inherent in the covalent modification of GS slows the response to an ammonium shock and thereby allows GS to transiently detoxify the cell, while maintaining homeostasis over longer times

  20. Merging constitutional and motional covalent dynamics in reversible imine formation and exchange processes.

    Science.gov (United States)

    Kovaříček, Petr; Lehn, Jean-Marie

    2012-06-06

    The formation and exchange processes of imines of salicylaldehyde, pyridine-2-carboxaldehyde, and benzaldehyde have been studied, showing that the former has features of particular interest for dynamic covalent chemistry, displaying high efficiency and fast rates. The monoimines formed with aliphatic α,ω-diamines display an internal exchange process of self-transimination type, inducing a local motion of either "stepping-in-place" or "single-step" type by bond interchange, whose rate decreases rapidly with the distance of the terminal amino groups. Control of the speed of the process over a wide range may be achieved by substituents, solvent composition, and temperature. These monoimines also undergo intermolecular exchange, thus merging motional and constitutional covalent behavior within the same molecule. With polyamines, the monoimines formed execute internal motions that have been characterized by extensive one-dimensional, two-dimensional, and EXSY proton NMR studies. In particular, with linear polyamines, nondirectional displacement occurs by shifting of the aldehyde residue along the polyamine chain serving as molecular track. Imines thus behave as simple prototypes of systems displaying relative motions of molecular moieties, a subject of high current interest in the investigation of synthetic and biological molecular motors. The motional processes described are of dynamic covalent nature and take place without change in molecular constitution. They thus represent a category of dynamic covalent motions, resulting from reversible covalent bond formation and dissociation. They extend dynamic covalent chemistry into the area of molecular motions. A major further step will be to achieve control of directionality. The results reported here for imines open wide perspectives, together with other chemical groups, for the implementation of such features in multifunctional molecules toward the design of molecular devices presenting a complex combination of

  1. Phosphopeptide Enrichment by Covalent Chromatography after Derivatization of Protein Digests Immobilized on Reversed-Phase Supports

    Science.gov (United States)

    Nika, Heinz; Nieves, Edward; Hawke, David H.; Angeletti, Ruth Hogue

    2013-01-01

    A rugged sample-preparation method for comprehensive affinity enrichment of phosphopeptides from protein digests has been developed. The method uses a series of chemical reactions to incorporate efficiently and specifically a thiol-functionalized affinity tag into the analyte by barium hydroxide catalyzed β-elimination with Michael addition using 2-aminoethanethiol as nucleophile and subsequent thiolation of the resulting amino group with sulfosuccinimidyl-2-(biotinamido) ethyl-1,3-dithiopropionate. Gentle oxidation of cysteine residues, followed by acetylation of α- and ε-amino groups before these reactions, ensured selectivity of reversible capture of the modified phosphopeptides by covalent chromatography on activated thiol sepharose. The use of C18 reversed-phase supports as a miniaturized reaction bed facilitated optimization of the individual modification steps for throughput and completeness of derivatization. Reagents were exchanged directly on the supports, eliminating sample transfer between the reaction steps and thus, allowing the immobilized analyte to be carried through the multistep reaction scheme with minimal sample loss. The use of this sample-preparation method for phosphopeptide enrichment was demonstrated with low-level amounts of in-gel-digested protein. As applied to tryptic digests of α-S1- and β-casein, the method enabled the enrichment and detection of the phosphorylated peptides contained in the mixture, including the tetraphosphorylated species of β-casein, which has escaped chemical procedures reported previously. The isolates proved highly suitable for mapping the sites of phosphorylation by collisionally induced dissociation. β-Elimination, with consecutive Michael addition, expanded the use of the solid-phase-based enrichment strategy to phosphothreonyl peptides and to phosphoseryl/phosphothreonyl peptides derived from proline-directed kinase substrates and to their O-sulfono- and O-linked β-N-acetylglucosamine (O

  2. Reversible and formaldehyde-mediated covalent binding of a bis-amino mitoxantrone analogue to DNA.

    Science.gov (United States)

    Konda, Shyam K; Kelso, Celine; Pumuye, Paul P; Medan, Jelena; Sleebs, Brad E; Cutts, Suzanne M; Phillips, Don R; Collins, J Grant

    2016-05-18

    The ability of a bis-amino mitoxantrone anticancer drug (named WEHI-150) to form covalent adducts with DNA, after activation by formaldehyde, has been studied by electrospray ionisation mass spectrometry and HPLC. Mass spectrometry results showed that WEHI-150 could form covalent adducts with d(ACGCGCGT)2 that contained one, two or three covalent links to the octanucleotide, whereas the control drugs (daunorubicin and the anthracenediones mitoxantrone and pixantrone) only formed adducts with one covalent link to the octanucleotide. HPLC was used to examine the extent of covalent bond formation of WEHI-150 with d(CGCGCG)2 and d(CG(5Me)CGCG)2. Incubation of WEHI-150 with d(CG(5Me)CGCG)2 in the presence of formaldehyde resulted in the formation of significantly greater amounts of covalent adducts than was observed with d(CGCGCG)2. In order to understand the observed increase of covalent adducts with d(CG(5Me)CGCG)2, an NMR study of the reversible interaction of WEHI-150 at both CpG and (5Me)CpG sites was undertaken. Intermolecular NOEs were observed in the NOESY spectra of d(ACGGCCGT)2 with added WEHI-150 that indicated that the drug selectively intercalated at the CpG sites and from the major groove. In particular, NOEs were observed from the WEHI-150 H2,3 protons to the H1' protons of G3 and G7 and from the H6,7 protons to the H5 protons of C2 and C6. By contrast, intermolecular NOEs were observed between the WEHI-150 H2,3 protons to the H2'' proton of the (5Me)C3 in d(CG(5Me)CGCG)2, and between the drug aliphatic protons and the H1' proton of G4. This demonstrated that WEHI-150 preferentially intercalates at (5Me)CpG sites, compared to CpG sequences, and predominantly via the minor groove at the (5Me)CpG site. The results of this study demonstrate that WEHI-150 is likely to form interstrand DNA cross-links, upon activation by formaldehyde, and consequently exhibit greater cytotoxicity than other current anthracenedione drugs.

  3. Reversible covalent binding of neratinib to human serum albumin in vitro.

    Science.gov (United States)

    Chandrasekaran, Appavu; Shen, Li; Lockhead, Susan; Oganesian, Aram; Wang, Jianyao; Scatina, JoAnn

    2010-12-01

    Neratinib (HKI-272), an irreversible inhibitor of Her 2 tyrosine kinase, is currently in development as an alternative for first and second line therapy in metastatic breast cancer patients who overexpress Her 2. Following incubation of [(14)C]neratinib in control human plasma at 37°C for 6 hours, about 60% to 70% of the radioactivity was not extractable, due to covalent binding to albumin. In this study, factors that could potentially affect the covalent binding of neratinib to plasma proteins, specifically to albumin were investigated. When [(14)C]neratinib was incubated at 10 μg/mL in human serum albumin (HSA) or control human plasma, the percent binding increased with time; the highest percentages of binding (46 and 67%, respectively) were observed at 6 hours, the longest duration of incubation examined. Binding increased with increasing temperature; the highest percentages of binding to HSA or human plasma (59 and 78%) were observed at 45°C, the highest temperature tested. The binding also increased with increasing pH of incubation; the highest percentages of binding (56 and 65%) were observed at pH 8.5, the highest pH value tested. The percentages of binding were similar (53% to 57%) when a wide range of concentrations of [(14)C]neratinib (50 ng/mL to 10 μg/mL) were incubated with human plasma at 37°C for 6 hours, indicating that the binding was independent of the substrate concentration, especially in the therapeutic range (50 to 200 ng/mL). When human plasma proteins containing covalently bound [(14)C]neratinb were suspended in a 10 fold volume of phosphate buffer at pH 4.0, 6.0, 7.4, and 8.5, and further incubated at 37°C for ~ 16 hours, about 45%, 44%, 32%, and 12% of the total radioactivity, respectively, was released as unchanged [(14)C]neratinib, indicating that the binding is reversible in nature, with more released at pH 7.4 and below. In conclusion, the covalent binding of neratinib to serum albumin is pH, time and temperature dependent, but

  4. Irreversible inactivation of snake venom l-amino acid oxidase by covalent modification during catalysis of l-propargylglycine☆

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    Mitra, Jyotirmoy; Bhattacharyya, Debasish

    2013-01-01

    Snake venom l-amino acid oxidase (SV-LAAO, a flavor-enzyme) has attracted considerable attention due to its multifunctional nature, which is manifest in diverse clinical and biological effects such as inhibition of platelet aggregation, induction of cell apoptosis and cytotoxicity against various cells. The majority of these effects are mediated by H2O2 generated during the catalytic conversion of l-amino acids. The substrate analog l-propargylglycine (LPG) irreversibly inhibited the enzyme from Crotalus adamanteus and Crotalus atrox in a dose- and time-dependent manner. Inactivation was irreversible which was significantly protected by the substrate l-phenylalanine. A Kitz–Wilson replot of the inhibition kinetics suggested formation of reversible enzyme–LPG complex, which occurred prior to modification and inactivation of the enzyme. UV–visible and fluorescence spectra of the enzyme and the cofactor strongly suggested formation of covalent adduct between LPG and an active site residue of the enzyme. A molecular modeling study revealed that the FAD-binding, substrate-binding and the helical domains are conserved in SV-LAAOs and both His223 and Arg322 are the important active site residues that are likely to get modified by LPG. Chymotrypsin digest of the LPG inactivated enzyme followed by RP-HPLC and MALDI mass analysis identified His223 as the site of modification. The findings reported here contribute towards complete inactivation of SV-LAAO as a part of snake envenomation management. PMID:23772385

  5. Electron Beam Modification and Functionalization of MWNT for Covalent Dispersion into Polymeric Systems

    International Nuclear Information System (INIS)

    Palmese, G. R.

    2006-01-01

    The discovery of multiwalled carbon nanotubes (MWNT) and singlewalled nanotubes (SWNT) has allowed for the development of structural and conductive reinforcement fillers for polymers and electronic systems. Due to their small diameter, high aspect ratio, strength, and conductive and semi-conductive properties, nanotubes are excellent reinforcing fillers for systems requiring enhanced electrical or material properties and may disperse into such systems at low percolation concentrations. However, despite their potential for enhanced composites properties, van der Waals interactions between nanotubes as well as their highly stable graphitic structure render them insoluble in water, organic solvents and most monomers. As a result, nanotubes separate from solution, and their excellent material properties are not realized on a macroscopic scale. Furthermore, in order for nanotube-reinforced systems to be structurally enhanced (allowing for load transfer from the bulk material to the nanotube filler), covalent interactions between nanotubes and the polymer chains are preferred. Therefore, the development of nanotube-based polymer composites with improved mechanical properties and electrical conductivity requires the covalent dispersion of carbon nanotubes. In this work, we have developed a novel method of nanotube surface modification in which dry MWNT are irradiated with a high-energy electron-beam (EB) in ambient air environment. Raman spectroscopy was performed to characterize the influence of EB irradiation on nanotubes, namely, variance of the disorder, or D band (∼1360 cm - 1) with respect to the graphitic, or G, peak (∼1580 cm - 1). Spectra show increased deformation to the graphitic structure, as well as increased strain on the carbon-carbon bonds, weakening the nanotube. Transmission Electron Microscopy (TEM) confirms that nanotubes remain intact despite high EB dose. In addition, minimal surface deformation and length reduction occurred on irradiated MWNT

  6. Dynamic Covalent Chemistry within Biphenyl Scaffolds: Reversible Covalent Bonding, Control of Selectivity, and Chirality Sensing with a Single System.

    Science.gov (United States)

    Ni, Cailing; Zha, Daijun; Ye, Hebo; Hai, Yu; Zhou, Yuntao; Anslyn, Eric V; You, Lei

    2018-01-26

    Axial chirality is a prevalent and important phenomenon in chemistry. Herein we report a combination of dynamic covalent chemistry and axial chirality for the development of a versatile platform for the binding and chirality sensing of multiple classes of mononucleophiles. An equilibrium between an open aldehyde and its cyclic hemiaminal within biphenyl derivatives enabled the dynamic incorporation of a broad range of alcohols, thiols, primary amines, and secondary amines with high efficiency. Selectivity toward different classes of nucleophiles was also achieved by regulating the distinct reactivity of the system with external stimuli. Through induced helicity as a result of central-to-axial chirality transfer, the handedness and ee values of chiral monoalcohol and monoamine analytes were reported by circular dichroism. The strategies introduced herein should find application in many contexts, including assembly, sensing, and labeling. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  7. Covalent Modifications of Histone H3K9 Promote Binding of CHD3

    Directory of Open Access Journals (Sweden)

    Adam H. Tencer

    2017-10-01

    Full Text Available Chromatin remodeling is required for genome function and is facilitated by ATP-dependent complexes, such as nucleosome remodeling and deacetylase (NuRD. Among its core components is the chromodomain helicase DNA binding protein 3 (CHD3 whose functional significance is not well established. Here, we show that CHD3 co-localizes with the other NuRD subunits, including HDAC1, near the H3K9ac-enriched promoters of the NuRD target genes. The tandem PHD fingers of CHD3 bind histone H3 tails and posttranslational modifications that increase hydrophobicity of H3K9—methylation or acetylation (H3K9me3 or H3K9ac—enhance this interaction. Binding of CHD3 PHDs promotes H3K9Cme3-nucleosome unwrapping in vitro and perturbs the pericentric heterochromatin structure in vivo. Methylation or acetylation of H3K9 uniquely alleviates the intra-nucleosomal interaction of histone H3 tails, increasing H3K9 accessibility. Collectively, our data suggest that the targeting of covalently modified H3K9 by CHD3 might be essential in diverse functions of NuRD.

  8. Covalent modification of serum transferrin with phospholipid and incorporation into liposomal membranes

    DEFF Research Database (Denmark)

    Afzelius, P; Demant, E J; Hansen, Gert Helge

    1989-01-01

    A method is described for incorporation of water-soluble proteins into liposomal membranes using covalent protein-phospholipid conjugates in detergent solution. A disulfide derivative of phosphatidylethanolamine containing a reactive N-hydroxysuccinimide ester group is synthesized, and the deriva......A method is described for incorporation of water-soluble proteins into liposomal membranes using covalent protein-phospholipid conjugates in detergent solution. A disulfide derivative of phosphatidylethanolamine containing a reactive N-hydroxysuccinimide ester group is synthesized...

  9. Epigenetic modification and inheritance in sexual reversal of fish.

    Science.gov (United States)

    Shao, Changwei; Li, Qiye; Chen, Songlin; Zhang, Pei; Lian, Jinmin; Hu, Qiaomu; Sun, Bing; Jin, Lijun; Liu, Shanshan; Wang, Zongji; Zhao, Hongmei; Jin, Zonghui; Liang, Zhuo; Li, Yangzhen; Zheng, Qiumei; Zhang, Yong; Wang, Jun; Zhang, Guojie

    2014-04-01

    Environmental sex determination (ESD) occurs in divergent, phylogenetically unrelated taxa, and in some species, co-occurs with genetic sex determination (GSD) mechanisms. Although epigenetic regulation in response to environmental effects has long been proposed to be associated with ESD, a systemic analysis on epigenetic regulation of ESD is still lacking. Using half-smooth tongue sole (Cynoglossus semilaevis) as a model-a marine fish that has both ZW chromosomal GSD and temperature-dependent ESD-we investigated the role of DNA methylation in transition from GSD to ESD. Comparative analysis of the gonadal DNA methylomes of pseudomale, female, and normal male fish revealed that genes in the sex determination pathways are the major targets of substantial methylation modification during sexual reversal. Methylation modification in pseudomales is globally inherited in their ZW offspring, which can naturally develop into pseudomales without temperature incubation. Transcriptome analysis revealed that dosage compensation occurs in a restricted, methylated cytosine enriched Z chromosomal region in pseudomale testes, achieving equal expression level in normal male testes. In contrast, female-specific W chromosomal genes are suppressed in pseudomales by methylation regulation. We conclude that epigenetic regulation plays multiple crucial roles in sexual reversal of tongue sole fish. We also offer the first clues on the mechanisms behind gene dosage balancing in an organism that undergoes sexual reversal. Finally, we suggest a causal link between the bias sex chromosome assortment in the offspring of a pseudomale family and the transgenerational epigenetic inheritance of sexual reversal in tongue sole fish.

  10. System in biology leading to cell pathology: stable protein-protein interactions after covalent modifications by small molecules or in transgenic cells.

    Science.gov (United States)

    Malina, Halina Z

    2011-01-19

    The physiological processes in the cell are regulated by reversible, electrostatic protein-protein interactions. Apoptosis is such a regulated process, which is critically important in tissue homeostasis and development and leads to complete disintegration of the cell. Pathological apoptosis, a process similar to apoptosis, is associated with aging and infection. The current study shows that pathological apoptosis is a process caused by the covalent interactions between the signaling proteins, and a characteristic of this pathological network is the covalent binding of calmodulin to regulatory sequences. Small molecules able to bind covalently to the amino group of lysine, histidine, arginine, or glutamine modify the regulatory sequences of the proteins. The present study analyzed the interaction of calmodulin with the BH3 sequence of Bax, and the calmodulin-binding sequence of myristoylated alanine-rich C-kinase substrate in the presence of xanthurenic acid in primary retinal epithelium cell cultures and murine epithelial fibroblast cell lines transformed with SV40 (wild type [WT], Bid knockout [Bid-/-], and Bax-/-/Bak-/- double knockout [DKO]). Cell death was observed to be associated with the covalent binding of calmodulin, in parallel, to the regulatory sequences of proteins. Xanthurenic acid is known to activate caspase-3 in primary cell cultures, and the results showed that this activation is also observed in WT and Bid-/- cells, but not in DKO cells. However, DKO cells were not protected against death, but high rates of cell death occurred by detachment. The results showed that small molecules modify the basic amino acids in the regulatory sequences of proteins leading to covalent interactions between the modified sequences (e.g., calmodulin to calmodulin-binding sites). The formation of these polymers (aggregates) leads to an unregulated and, consequently, pathological protein network. The results suggest a mechanism for the involvement of small molecules

  11. Covalent Bonding of Chlorogenic Acid Induces Structural Modifications on Sunflower Proteins

    NARCIS (Netherlands)

    Karefyllakis, D.; Salakou, Stavroula; Bitter, J.H.; Goot, van der A.J.; Nikiforidis, K.

    2018-01-01

    Proteins and phenols coexist in the confined space of plant cells leading to reactions between them, which result in new covalently bonded complex molecules. This kind of reactions has been widely observed during storage and processing of plant materials. However, the nature of the new complex

  12. Achieving enhanced hydrophobicity of graphene membranes by covalent modification with polydimethylsiloxane

    Energy Technology Data Exchange (ETDEWEB)

    Lei, Wei-Wei; Li, Hang [College of Polymer Science and Engineering, State Key Laboratory of Polymer Materials Engineering, Sichuan University, Chengdu 610065 (China); Shi, Ling-Ying, E-mail: shilingying@scu.edu.cn [College of Polymer Science and Engineering, State Key Laboratory of Polymer Materials Engineering, Sichuan University, Chengdu 610065 (China); Diao, Yong-Fu; Zhang, Yu-Lin; Ran, Rong [College of Polymer Science and Engineering, State Key Laboratory of Polymer Materials Engineering, Sichuan University, Chengdu 610065 (China); Ni, Wei, E-mail: niwei@iccas.ac.cn [Institute of Chemical Materials, China Academy of Engineering Physics, Chengdu 610200 (China)

    2017-05-15

    Highlights: • The graphene oxide (GO) was covalently modified by amino terminated polydimethylsiloxane (PDMS) through amidation reaction. • Through the vacuum filtration method, the GO, RGO and PDMS-modified graphene membranes were successfully prepared respectively. • The morphology of membranes had smooth surface and well-stacked structure indicated by SEM and EDS mapping results. • The contact angle of GO-g-PDMS membrane was high to be 129.5° indicating a great enhancement of hydrophobicity. - Abstract: In this study, the graphene oxide was covalently modified by amino terminated polydimethylsiloxane (PDMS) through amidation reaction. And the membranes of the graphene oxide (GO), reduced graphene oxide (RGO) and PDMS-covalently modified graphene were prepared respectively by a vacuum filtration method, and the wettability of these membranes were investigated. Infrared spectroscopy, Raman, X-ray diffraction, X-ray photoelectron spectroscopy, and thermogravimetry analysis combined with dispersion ability indicated that PDMS chains were successfully grafted on the surface of graphene oxide sheets. The morphology of the prepared membranes had smooth surface and well-stacked structure in the cross-section indicated by the scanning electron microscope and EDS-mapping. The contact angle measurements indicated that the PDMS-modified graphene membrane with water contact angle 129.5° showed increased hydrophobicity compared with GO and RGO membranes.

  13. Covalent modification of calcium hydroxyapatite surface by grafting phenyl phosphonate moieties

    International Nuclear Information System (INIS)

    Aissa, Abdallah; Debbabi, Mongi; Gruselle, Michel; Thouvenot, Rene; Gredin, Patrick; Traksmaa, Rainer; Tonsuaadu, Kaia

    2007-01-01

    The reaction between phenyl phosphonic dichloride (C 6 H 5 P(O)Cl 2 ) and synthetic calcium hydroxy- and fluorapatite has been investigated. The presence of mono- or polymeric (C 6 H 5 PO) fragment bound to hydroxyapatite was evidenced by IR, and solid-state 31 P NMR spectroscopy. X-ray powder analysis has shown that the apatitic structure remains unchanged during the reaction. In contrast, no reaction was found using fluorapatite. According to the results found for these two different apatites a mechanism was proposed for the formation of covalent P-O-P bonds as the result of a reaction between the C 6 H 5 P(O)Cl 2 organic reagent and (HPO 4 ) - and/or OH - ions of the hydroxyapatite. - Graphical abstract: Representation of the first step of the reaction between the phenyl phosphonic dichloride and the hydroxyl groups on the surface of the apatite, leading to covalent P-O-P bond with elimination of HCl

  14. Covalent modification of boron-doped diamond electrodes with an imidazolium-based ionic liquid

    Energy Technology Data Exchange (ETDEWEB)

    Wang Mei [Institut de Recherche Interdisciplinaire (IRI, USR 3078), Parc de la Haute Borne, 50 Avenue de Halley, BP 70478, 59658 Villeneuve d' Ascq (France); Institut d' Electronique, de Microelectronique et de Nanotechnologie (IEMN, UMR 8520), Cite Scientifique, Avenue Poincare, BP 60069, 59652 Villeneuve d' Ascq (France); School of Materials Science and Engineering, Shandong University, 19723 Jingshi Road, Jinan, Shandong Province (China); Schneider, Amene [Austrian Centre of Competence for Tribology, Viktor Kaplan Strasse 2, 2700, Wiener Neustadt (Austria); Niedziolka-Joensson, Joanna; Marcon, Lionel [Institut de Recherche Interdisciplinaire (IRI, USR 3078), Parc de la Haute Borne, 50 Avenue de Halley, BP 70478, 59658 Villeneuve d' Ascq (France); Institut d' Electronique, de Microelectronique et de Nanotechnologie (IEMN, UMR 8520), Cite Scientifique, Avenue Poincare, BP 60069, 59652 Villeneuve d' Ascq (France); Ghodbane, Slimane; Steinmueller-Nethl, Doris [Rho-BeSt Coating GmbH, Exlgasse 20a, 6020 Innsbruck (Austria); Li Musen [School of Materials Science and Engineering, Shandong University, 19723 Jingshi Road, Jinan, Shandong Province (China); Boukherroub, Rabah [Institut de Recherche Interdisciplinaire (IRI, USR 3078), Parc de la Haute Borne, 50 Avenue de Halley, BP 70478, 59658 Villeneuve d' Ascq (France); Institut d' Electronique, de Microelectronique et de Nanotechnologie (IEMN, UMR 8520), Cite Scientifique, Avenue Poincare, BP 60069, 59652 Villeneuve d' Ascq (France); Szunerits, Sabine, E-mail: sabine.szunerits@iri.univ-lille1.f [Institut de Recherche Interdisciplinaire (IRI, USR 3078), Parc de la Haute Borne, 50 Avenue de Halley, BP 70478, 59658 Villeneuve d' Ascq (France); Institut d' Electronique, de Microelectronique et de Nanotechnologie (IEMN, UMR 8520), Cite Scientifique, Avenue Poincare, BP 60069, 59652 Villeneuve d' Ascq (France)

    2010-02-01

    An ionic liquid (IL, 1-(methylcarboxylic acid)-3-octylimidazolium-bis (trifluoromethylsulfonyl)imide) was covalently coupled onto a boron-doped diamond (BDD) surface through an esterification reaction. The resulting surface was characterized by X-ray photoelectron spectroscopy, water contact angle and electrochemical measurements. Selective electron transfer towards positively and negatively charged redox species was recorded. While the presence of Fe(CN){sub 6}{sup 4-} could be detected on the IL-modified BDD interface, no surface-immobilized Ru(NH{sub 3}){sub 6}{sup 3+} was recorded. The IL-modified BDD electrode showed in addition changes in surface wettability when immersed into aqueous solution containing different anions.

  15. Covalent adduct formation between the plasmalogen-derived modification product 2-chlorohexadecanal and phloretin

    Science.gov (United States)

    Üllen, Andreas; Nusshold, Christoph; Glasnov, Toma; Saf, Robert; Cantillo, David; Eibinger, Gerald; Reicher, Helga; Fauler, Günter; Bernhart, Eva; Hallstrom, Seth; Kogelnik, Nora; Zangger, Klaus; Oliver Kappe, C.; Malle, Ernst; Sattler, Wolfgang

    2015-01-01

    Hypochlorous acid added as reagent or generated by the myeloperoxidase (MPO)-H2O2-Cl− system oxidatively modifies brain ether-phospholipids (plasmalogens). This reaction generates a sn2-acyl-lysophospholipid and chlorinated fatty aldehydes. 2-Chlorohexadecanal (2-ClHDA), a prototypic member of chlorinated long-chain fatty aldehydes, has potent neurotoxic potential by inflicting blood–brain barrier (BBB) damage. During earlier studies we could show that the dihydrochalcone-type polyphenol phloretin attenuated 2-ClHDA-induced BBB dysfunction. To clarify the underlying mechanism(s) we now investigated the possibility of covalent adduct formation between 2-ClHDA and phloretin. Coincubation of 2-ClHDA and phloretin in phosphatidylcholine liposomes revealed a half-life of 2-ClHDA of approx. 120 min, decaying at a rate of 5.9 × 10−3 min−1. NMR studies and enthalpy calculations suggested that 2-ClHDA-phloretin adduct formation occurs via electrophilic aromatic substitution followed by hemiacetal formation on the A-ring of phloretin. Adduct characterization by high-resolution mass spectroscopy confirmed these results. In contrast to 2-ClHDA, the covalent 2-ClHDA-phloretin adduct was without adverse effects on MTT reduction (an indicator for metabolic activity), cellular adenine nucleotide content, and barrier function of brain microvascular endothelial cells (BMVEC). Of note, 2-ClHDA-phloretin adduct formation was also observed in BMVEC cultures. Intraperitoneal application and subsequent GC–MS analysis of brain lipid extracts revealed that phloretin is able to penetrate the BBB of C57BL/6J mice. Data of the present study indicate that phloretin scavenges 2-ClHDA, thereby attenuating 2-ClHDA-mediated brain endothelial cell dysfunction. We here identify a detoxification pathway for a prototypic chlorinated fatty aldehyde (generated via the MPO axis) that compromises BBB function in vitro and in vivo. PMID:25576489

  16. Atom-scale covalent electrochemical modification of single-layer graphene on SiC substrates by diaryliodonium salts

    International Nuclear Information System (INIS)

    Gearba, Raluca I.; Mueller, Kory M.; Veneman, Peter A.; Holliday, Bradley J.; Chan, Calvin K.; Stevenson, Keith J.

    2015-01-01

    Owing to its high conductivity, graphene holds promise as an electrode for energy devices such as batteries and photovoltaics. However, to this end, the work function and doping levels in graphene need to be precisely tuned. One promising route for modifying graphene's electronic properties is via controlled covalent electrochemical grafting of molecules. We show that by employing diaryliodonium salts instead of the commonly used diazonium salts, spontaneous functionalization is avoided. This then allows for precise tuning of the grafting density. Moreover, by employing bis(4-nitrophenyl)iodonium(III) tetrafluoroborate (DNP) salt calibration curves, the surface functionalization density (coverage) of glassy carbon was controlled using cyclic voltammetry in varying salt concentrations. These electro-grafting conditions and calibration curves translated directly over to modifying single layer epitaxial graphene substrates (grown on insulating 6H-SiC (0 0 0 1)). In addition to quantifying the functionalization densities using electrochemical methods, samples with low grafting densities were characterized by low-temperature scanning tunneling microscopy (LT-STM). We show that the use of buffer-layer free graphene substrates is required for clear observation of the nitrophenyl modifications. Furthermore, atomically-resolved STM images of single site modifications were obtained, showing no preferential grafting at defect sites or SiC step edges as supposed previously in the literature. Most of the grafts exhibit threefold symmetry, but occasional extended modifications (larger than 4 nm) were observed as well

  17. Dimethyl Fumarate Inhibits the Nuclear Factor κB Pathway in Breast Cancer Cells by Covalent Modification of p65 Protein.

    Science.gov (United States)

    Kastrati, Irida; Siklos, Marton I; Calderon-Gierszal, Esther L; El-Shennawy, Lamiaa; Georgieva, Gergana; Thayer, Emily N; Thatcher, Gregory R J; Frasor, Jonna

    2016-02-12

    In breast tumors, activation of the nuclear factor κB (NFκB) pathway promotes survival, migration, invasion, angiogenesis, stem cell-like properties, and resistance to therapy--all phenotypes of aggressive disease where therapy options remain limited. Adding an anti-inflammatory/anti-NFκB agent to breast cancer treatment would be beneficial, but no such drug is approved as either a monotherapy or adjuvant therapy. To address this need, we examined whether dimethyl fumarate (DMF), an anti-inflammatory drug already in clinical use for multiple sclerosis, can inhibit the NFκB pathway. We found that DMF effectively blocks NFκB activity in multiple breast cancer cell lines and abrogates NFκB-dependent mammosphere formation, indicating that DMF has anti-cancer stem cell properties. In addition, DMF inhibits cell proliferation and significantly impairs xenograft tumor growth. Mechanistically, DMF prevents p65 nuclear translocation and attenuates its DNA binding activity but has no effect on upstream proteins in the NFκB pathway. Dimethyl succinate, the inactive analog of DMF that lacks the electrophilic double bond of fumarate, is unable to inhibit NFκB activity. Also, the cell-permeable thiol N-acetyl l-cysteine, reverses DMF inhibition of the NFκB pathway, supporting the notion that the electrophile, DMF, acts via covalent modification. To determine whether DMF interacts directly with p65, we synthesized and used a novel chemical probe of DMF by incorporating an alkyne functionality and found that DMF covalently modifies p65, with cysteine 38 being essential for the activity of DMF. These results establish DMF as an NFκB inhibitor with anti-tumor activity that may add therapeutic value in the treatment of aggressive breast cancers. © 2016 by The American Society for Biochemistry and Molecular Biology, Inc.

  18. Covalent and stable CuAAC modification of silicon surfaces for control of cell adhesion

    DEFF Research Database (Denmark)

    Vutti, Surendra; Buch-Månson, Nina; Schoffelen, Sanne

    2015-01-01

    in the vapor or liquid phase. In this work, we compared these two methods for oxidized silicon surfaces and thoroughly characterized the functionalization steps by tagging and fluorescence imaging. We demonstrate that the vapor-phase functionalization only provided transient surface modification that was lost...... on extensive washing. For stable surface modification, a liquid-phase method was developed. In this method, silicon wafers were decorated with azides, either by silanization with (3-azidopropyl)triethoxysilane or by conversion of the amine groups of an aminopropylated surface by means of the azido...

  19. Temperature Scanning Stress Relaxation of an Autonomous Self-Healing Elastomer Containing Non-Covalent Reversible Network Junctions

    Directory of Open Access Journals (Sweden)

    Amit Das

    2018-01-01

    Full Text Available In this work, we report about the mechanical relaxation characteristics of an intrinsically self-healable imidazole modified commercial rubber. This kind of self-healing rubber was prepared by melt mixing of 1-butyl imidazole with bromo-butyl rubber (bromine modified isoprene-isobutylene copolymer, BIIR. By this melt mixing process, the reactive allylic bromine of bromo-butyl rubber was converted into imidazole bromide salt. The resulting development of an ionic character to the polymer backbone leads to an ionic association of the groups which ultimately results to the formation of a network structure of the rubber chains. The modified BIIR thus behaves like a robust crosslinked rubber and shows unusual self-healing properties. The non-covalent reversible network has been studied in detail with respect to stress relaxation experiments, scanning electron microscopic and X-ray scattering.

  20. Covalent immobilization of glucose oxidase on amino MOFs via post-synthetic modification

    NARCIS (Netherlands)

    Tudisco, C.G.; Zolubas, G.; Seoane de la Cuesta, B.; Zafarani, H.; Kazemzad Asiabi, M.; Gascon Sabate, J.; Hagedoorn, P.L.; Rassaei, L.

    2016-01-01

    The post-synthetic modification (PSM) of two amino-MOFs with glucose oxidase is reported in this study. The multi-step approach preserved the MOFs' structure and allowed the production of enzyme-functionalized MOFs (MOFs@GOx), which retained the enzymatic activity and showed selective properties

  1. Covalent Surface Modification of Silicon Oxides with Alcohols in Polar Aprotic Solvents.

    Science.gov (United States)

    Lee, Austin W H; Gates, Byron D

    2017-09-05

    Alcohol-based monolayers were successfully formed on the surfaces of silicon oxides through reactions performed in polar aprotic solvents. Monolayers prepared from alcohol-based reagents have been previously introduced as an alternative approach to covalently modify the surfaces of silicon oxides. These reagents are readily available, widely distributed, and are minimally susceptible to side reactions with ambient moisture. A limitation of using alcohol-based compounds is that previous reactions required relatively high temperatures in neat solutions, which can degrade some alcohol compounds or could lead to other unwanted side reactions during the formation of the monolayers. To overcome these challenges, we investigate the condensation reaction of alcohols on silicon oxides carried out in polar aprotic solvents. In particular, propylene carbonate has been identified as a polar aprotic solvent that is relatively nontoxic, readily accessible, and can facilitate the formation of alcohol-based monolayers. We have successfully demonstrated this approach for tuning the surface chemistry of silicon oxide surfaces with a variety of alcohol containing compounds. The strategy introduced in this research can be utilized to create silicon oxide surfaces with hydrophobic, oleophobic, or charged functionalities.

  2. N-terminal pro-atrial natriuretic peptide measurement in plasma suggests covalent modification

    DEFF Research Database (Denmark)

    Hunter, Ingrid; Alehagen, Urban; Dahlström, Ulf

    2011-01-01

    different proANP assays on clinical outcome. METHODS: We examined 474 elderly patients with symptoms of heart failure presenting in a primary healthcare setting. Samples were analyzed with an automated immunoluminometric midregion proANP (MR-proANP) assay and a new processing-independent assay (PIA.......74 (95% CI, 0.66–0.81); P = 0.32]. The prognostic ability to report cardiovascular mortality during a 10-year follow-up revealed AUC values of 0.66 (95% CI, 0.60–0.71) for the proANP PIA and 0.69 (95% CI, 0.63–0.74) for the MR-proANP assay (P = 0.08, for comparing the 2 assays). CONCLUSIONS: Our data......BACKGROUND: The N-terminal fragment of cardiac-derived pro–B-type natriuretic peptide is a glycosylated polypeptide. It is unknown whether N-terminal pro–atrial natriuretic peptide (proANP) fragments are also covalently modified. We therefore evaluated the clinical performance of 2 distinctly...

  3. Covalent protein modification with ISG15 via a conserved cysteine in the hinge region.

    Directory of Open Access Journals (Sweden)

    Veronika N Bade

    Full Text Available The ubiquitin-like protein ISG15 (interferon-stimulated gene of 15 kDa is strongly induced by type I interferons and displays antiviral activity. As other ubiquitin-like proteins (Ubls, ISG15 is post-translationally conjugated to substrate proteins by an isopeptide bond between the C-terminal glycine of ISG15 and the side chains of lysine residues in the substrates (ISGylation. ISG15 consists of two ubiquitin-like domains that are separated by a hinge region. In many orthologs, this region contains a single highly reactive cysteine residue. Several hundred potential substrates for ISGylation have been identified but only a few of them have been rigorously verified. In order to investigate the modification of several ISG15 substrates, we have purified ISG15 conjugates from cell extracts by metal-chelate affinity purification and immunoprecipitations. We found that the levels of proteins modified by human ISG15 can be decreased by the addition of reducing agents. With the help of thiol blocking reagents, a mutational analysis and miRNA mediated knock-down of ISG15 expression, we revealed that this modification occurs in living cells via a disulphide bridge between the substrates and Cys78 in the hinge region of ISG15. While the ISG15 activating enzyme UBE1L is conjugated by ISG15 in the classical way, we show that the ubiquitin conjugating enzyme Ubc13 can either be classically conjugated by ISG15 or can form a disulphide bridge with ISG15 at the active site cysteine 87. The latter modification would interfere with its function as ubiquitin conjugating enzyme. However, we found no evidence for an ISG15 modification of the dynamin-like GTPases MxA and hGBP1. These findings indicate that the analysis of potential substrates for ISG15 conjugation must be performed with great care to distinguish between the two types of modification since many assays such as immunoprecipitation or metal-chelate affinity purification are performed with little or no

  4. Covalent versus Charge Transfer Modification of Graphene/Carbon-Nanotubes with Vitamin B1: Co/N/S-C Catalyst toward Excellent Oxygen Reduction.

    Science.gov (United States)

    Vij, Varun; Tiwari, Jitendra N; Kim, Kwang S

    2016-06-29

    High-performance nonprecious cathodic catalysts for oxygen reduction are highly demanded for low-temperature polymer electrolyte membrane fuel cells (PEMFCs). Here, we report a noble-meta- free, nitrogen and sulfur codoped graphene(G)/carbon-nanotube(CNT) material decorated with Co nanoparticles (NPs), which serve as catalytic sites for excellent oxygen reduction reaction (ORR) in basic and acidic media. Out of the cathodic catalysts synthesized by either covalent (cov) or charge transfer (CT) modification of graphen oxide (GO) with thiamine (Th: Vitamin B1), ThG/CNT/Co-cov shows more promising ORR properties than ThG/CNT/Co-CT. Catalyst ThG/CNT/Co-cov exhibits onset/halfwave potentials of 0.95/0.86 V in 0.1 M KOH and 0.92/0.83 V in 0.1 M HClO4, which are comparable to those of commercial catalyst Pt/C (0.95/0.86 V). As compared to Pt/C, our catalyst shows higher current densities of 6.72 mA cm(-2) in basic medium and 7.08 mA cm(-2) in acidic medium at 0.55 V (vs reversible hydrogen electrode (RHE)). It also exhibits better catalytic stability and methanol tolerance. High catalytic efficiency and stability of ThG/CNT/Co-cov show a promising prospect of materialization of PEMFCs for clean energy production.

  5. Covalent modification of hepatic microsomal lipids of rats by carbon tetrachloride

    International Nuclear Information System (INIS)

    Kaphalia, B.S.; Ansari, G.A.

    1989-01-01

    The present study was undertaken to isolate and identify various lipids bound to 14C label during hepatic microsomal metabolism of 14CCl4 in vitro under anaerobic conditions and in vivo in rats. The two major radioactive fractions identified by thin-layer chromatography each for neutral lipids and phospholipids from in vitro and in vivo experiments corresponded to fatty acids and triglycerides and to phosphatidylcholine (PC) and phosphatidylethanolamine (PE), respectively. Approximately 89% of the radioactivity associated with phospholipids was found in PC and PE fractions. Hydrolysis of PC and PE with phospholipase A2 released about 50% of the total radioactivity as lipid moieties corresponding to fatty acids. The radioactive neutral lipids and the lipid moieties hydrolyzed from PC and PE were methylated with boron trifluoride in methanol. These methylated lipids were separated by reversed-phase high-performance liquid chromatography (HPLC), and the elution profiles of 14C label found for the lipids obtained from in vitro experiments were similar to those from in vivo. The major radioactive fractions eluted immediately after methyl oleate were identified as trichloromethyloctadecenoic and trichloromethyleicosatrienoic acid methyl esters by chemical ionization mass spectrometry. The mass spectral analysis of these fractions also indicated the formation of dichlorocarbene adduct of oleic acid. However, similar mass spectrometric detection of trichloromethylated lipids was not evident in neutral lipids and phospholipids isolated from in vivo studies. The 14C-labeled lipids eluted as a nonpolar fraction exhibited a high molecular weight containing more than three chlorines. Dimerization and cross-linking of trichloromethylated lipids based on HPLC and mass spectral analysis are also discussed in this paper

  6. Multifunctional Pt(II) Reagents: Covalent Modifications of Pt Complexes Enable Diverse Structural Variation and In-Cell Detection.

    Science.gov (United States)

    White, Jonathan D; Haley, Michael M; DeRose, Victoria J

    2016-01-19

    To enhance the functionality of Pt-based reagents, several strategies have been developed that utilize Pt compounds modified with small, reactive handles. This Account encapsulates work done by us and other groups regarding the use of Pt(II) compounds with reactive handles for subsequent elaboration with fluorophores or other functional moieties. Described strategies include the incorporation of substituents for well-known condensation or nucleophilic displacement-type reactions and their use, for example, to tether spectroscopic handles to Pt reagents for in vivo investigation. Other chief uses of displacement-type reactions have included tethering various small molecules exhibiting pharmacological activity directly to Pt, thus adding synergistic effects. Click chemistry-based ligation techniques have also been applied, primarily with azide- and alkyne-appended Pt complexes. Orthogonally reactive click chemistry reactions have proven invaluable when more traditional nucleophilic displacement reactions induce side-reactivity with the Pt center or when systematic functionalization of a larger number of Pt complexes is desired. Additionally, a diverse assortment of Pt-fluorophore conjugates have been tethered via click chemistry conjugation. In addition to providing a convenient synthetic path for diversifying Pt compounds, the use of click-capable Pt complexes has proved a powerful strategy for postbinding covalent modification and detection with fluorescent probes. This strategy bypasses undesirable influences of the fluorophore camouflaged as reactivity due to Pt that may be present when detecting preattached Pt-fluorophore conjugates. Using postbinding strategies, Pt reagent distributions in HeLa and lung carcinoma (NCI-H460) cell cultures were observed with two different azide-modified Pt compounds, a monofunctional Pt(II)-acridine type and a difunctional Pt(II)-neutral complex. In addition, cellular distribution was observed with an alkyne-appended difunctional

  7. Modification of encapsulation pressure of reverse micelles in liquid ethane.

    Science.gov (United States)

    Peterson, Ronald W; Nucci, Nathaniel V; Wand, A Joshua

    2011-09-01

    Encapsulation within reverse micelles dissolved in low viscosity fluids offers a potential solution to the slow tumbling problem presented by large soluble macromolecules to solution NMR spectroscopy. The reduction in effective macromolecular tumbling is directly dependent upon the viscosity of the solvent. Liquid ethane is of sufficiently low viscosity at pressures below 5000 psi to offer a significant advantage. Unfortunately, the viscosity of liquid ethane shows appreciable pressure dependence. Reverse micelle encapsulation in liquid ethane often requires significantly higher pressures, which obviates the potential advantages offered by liquid ethane over liquid propane. Addition of co-surfactants or co-solvents can be used to manipulate the minimum pressure required to obtain stable, well-behaved solutions of reverse micelles prepared in liquid ethane. A library of potential additives is examined and several candidates suitable for use with encapsulated proteins are described. Copyright © 2011 Elsevier Inc. All rights reserved.

  8. Covalent Modification of Highly Ordered Pyrolytic Graphite with a Stable Organic Free Radical by Using Diazonium Chemistry.

    Science.gov (United States)

    Seber, Gonca; Rudnev, Alexander V; Droghetti, Andrea; Rungger, Ivan; Veciana, Jaume; Mas-Torrent, Marta; Rovira, Concepció; Crivillers, Núria

    2017-01-26

    A novel, persistent, electrochemically active perchlorinated triphenylmethyl (PTM) radical with a diazonium functionality has been covalently attached to highly ordered pyrolytic graphite (HOPG) by electrografting in a single-step process. Electrochemical scanning tunneling microscopy (EC-STM) and Raman spectroscopy measurements revealed that PTM molecules had a higher tendency to covalently react at the HOPG step edges. The cross-section profiles from EC-STM images showed that there was current enhancement at the functionalized areas, which could be explained by redox-mediated electron tunneling through surface-confined redox-active molecules. Cyclic voltammetry clearly demonstrated that the intrinsic properties of the organic radical were preserved upon grafting and DFT calculations also revealed that the magnetic character of the PTM radical was preserved. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  9. Reversibility of hepatocyte nuclear modifications in mice fed on genetically modified soybean

    Directory of Open Access Journals (Sweden)

    M Malatesta

    2009-06-01

    Full Text Available In the literature, the reports on the effects of a genetically modified (GM diet are scanty and heterogeneous; in particular, no direct evidence has so far been reported that GM food may affect human or animal health. Hepatocytes represent a suitable model for monitoring the effects of a GM diet, the liver potentially being a primary target. In a previous study, we demonstrated that some modifications occur in hepatocyte nuclei of mice fed on GM soybean. In order to elucidate whether such modifications can be reversed, in the present study, 3 months old mice fed on GM soybean since their weaning were submitted to a diet containing wild type soybean only, for one month. In parallel, to investigate the influence of GM soybean on adult individuals, mice fed on wild type soybean were changed to a GM diet, for the same time. Using immunoelectron microscopy, we demonstrated that a one-month diet reversion can influence some nuclear features in adult mice, restoring typical characteristics of controls in GM-fed animals, and inducing in control mice modifications similar to those observed in animals fed on GM soybean from weaning. This suggests that the modifications related to GM soybean are potentially reversible, but also that some modifications are inducible in adult organisms in a short time.

  10. Pharmacokinetics and pharmacodynamics of orally administered acetylenic tricyclic bis(cyanoenone), a highly potent Nrf2 activator with a reversible covalent mode of action

    Energy Technology Data Exchange (ETDEWEB)

    Kostov, Rumen V.; Knatko, Elena V.; McLaughlin, Lesley A.; Henderson, Colin J. [Jacqui Wood Cancer Centre, Division of Cancer Research, Medical Research Institute, University of Dundee, Dundee, DD1 9SY, Scotland (United Kingdom); Zheng, Suqing [Department of Chemistry and Institute of Chemical Biology & Drug Discovery, Stony Brook University, Stony Brook, NY, 11794 (United States); Huang, Jeffrey T.-J. [Jacqui Wood Cancer Centre, Division of Cancer Research, Medical Research Institute, University of Dundee, Dundee, DD1 9SY, Scotland (United Kingdom); Honda, Tadashi [Department of Chemistry and Institute of Chemical Biology & Drug Discovery, Stony Brook University, Stony Brook, NY, 11794 (United States); Dinkova-Kostova, Albena T., E-mail: a.dinkovakostova@dundee.ac.uk [Jacqui Wood Cancer Centre, Division of Cancer Research, Medical Research Institute, University of Dundee, Dundee, DD1 9SY, Scotland (United Kingdom); Department of Medicine, Johns Hopkins University School of Medicine, Baltimore, MD, 21205 (United States); Department of Pharmacology and Molecular Sciences, Johns Hopkins University School of Medicine, Baltimore, MD, 21205 (United States)

    2015-09-25

    The acetylenic tricyclic bis(cyanoenone) TBE-31 is a highly potent cysteine targeting compound with a reversible covalent mode of action; its best-characterized target being Kelch-like ECH-associated protein-1 (Keap1), the cellular sensor for oxidants and electrophiles. TBE-31 reacts with cysteines of Keap1, impairing its ability to target nuclear factor-erythroid 2 p45-related factor 2 (Nrf2) for degradation. Consequently, Nrf2 accumulates and orchestrates cytoprotective gene expression. In this study we investigated the pharmacokinetic and pharmacodynamic properties of TBE-31 in C57BL/6 mice. After a single oral dose of 10 μmol/kg (∼200 nmol/animal), the concentration of TBE-31 in blood exhibited two peaks, at 22.3 nM and at 15.5 nM, 40 min and 4 h after dosing, respectively, as determined by a quantitative stable isotope dilution LC-MS/MS method. The AUC{sub 0–24h} was 195.5 h/nmol/l, the terminal elimination half-life was 10.2 h, and the k{sub el} was 0.068 h{sup −1}. To assess the pharmacodynamics of Nrf2 activation by TBE-31, we determined the enzyme activity of its prototypic target, NAD(P)H:quinone oxidoreductase 1 (NQO1) and found it elevated by 2.4- and 1.5-fold in liver and heart, respectively. Continuous feeding for 18 days with diet delivering the same daily doses of TBE-31 under conditions of concurrent treatment with the immunosuppressive agent azathioprine had a similar effect on Nrf2 activation without any indications of toxicity. Together with previous reports showing the cytoprotective effects of TBE-31 in animal models of carcinogenesis, our results demonstrate the high potency, efficacy and suitability for chronic administration of cysteine targeting reversible covalent drugs. - Highlights: • TBE-31 is a cysteine targeting compound with a reversible covalent mode of action. • After a single oral dose, the blood concentration of TBE-31 exhibits two peaks. • Oral TBE-31 is a potent activator of Nrf2-dependent enzymes in

  11. Covalent modifications of the amyloid beta peptide by hydroxynonenal: Effects on metal ion binding by monomers and insights into the fibril topology.

    Science.gov (United States)

    Grasso, G; Komatsu, H; Axelsen, P H

    2017-09-01

    Amyloid β peptides (Aβ) and metal ions are associated with oxidative stress in Alzheimer's disease (AD). Oxidative stress, acting on ω-6 polyunsaturated fatty acyl chains, produces diverse products, including 4-hydroxy-2-nonenal (HNE), which can covalently modify the Aβ that helped to produce it. To examine possible feedback mechanisms involving Aβ, metal ions and HNE production, the effects of HNE modification and fibril formation on metal ion binding was investigated. Results indicate that copper(II) generally inhibits the modification of His side chains in Aβ by HNE, but that once modified, copper(II) still binds to Aβ with high affinity. Fibril formation protects only one of the three His residues in Aβ from HNE modification, and this protection is consistent with proposed models of fibril structure. These results provide insight into a network of biochemical reactions that may be operating as a consequence of oxidative stress in AD, or as part of the pathogenic process. Copyright © 2016. Published by Elsevier Inc.

  12. Fabrication and non-covalent modification of highly oriented thin films of a zeolite-like metal-organic framework (ZMOF) with rho topology

    KAUST Repository

    Shekhah, Osama

    2015-01-01

    Here we report the fabrication of the first thin film of a zeolite-like metal-organic framework (ZMOF) with rho topology (rho-ZMOF-1, ([In48(HImDC)96]48-)n) in a highly oriented fashion on a gold-functionalized substrate. The oriented rho-ZMOF-1 film was functionalized by non-covalent modification via post-synthetic exchange of different probe molecules, such as acridine yellow, methylene blue, and Nile red. In addition, encapsulation of a porphyrin moiety was achieved via in situ synthesis and construction of the rho-ZMOF. Adsorption kinetics of volatile organic compounds on rho-ZMOF-1 thin films was also investigated. This study suggests that rho-ZMOF-1 thin films can be regarded as a promising platform for various applications such as sensing and catalysis. This journal is

  13. Reversible electrochemical modification of the surface of a semiconductor by an atomic-force microscope probe

    Energy Technology Data Exchange (ETDEWEB)

    Kozhukhov, A. S., E-mail: antonkozhukhov@yandex.ru; Sheglov, D. V.; Latyshev, A. V. [Russian Academy of Sciences, Rzhanov Institute of Semiconductor Physics, Siberian Branch (Russian Federation)

    2017-04-15

    A technique for reversible surface modification with an atomic-force-microscope (AFM) probe is suggested. In this method, no significant mechanical or topographic changes occur upon a local variation in the surface potential of a sample under the AFM probe. The method allows a controlled relative change in the ohmic resistance of a channel in a Hall bridge within the range 20–25%.

  14. Covalent modification of multiwalled carbon nanotubes with neutral red for the fabrication of an amperometric hydrogen peroxide sensor

    International Nuclear Information System (INIS)

    Jeykumari, D R Shobha; Narayanan, S Sriman

    2007-01-01

    The nanoscale dimensions, graphitic surface chemistry and electronic properties of multiwalled carbon nanotubes (MWNTs) make them an ideal candidate for chemical and biochemical sensing. In this paper we explore a covalent chemical strategy for functionalization of MWNTs with neutral red through carbodiimide coupling between the primary amine of neutral red and carboxyl groups of the carbon nanotubes. The construction of an amperometric sensor was achieved by abrasive immobilization of the functionalized MWNTs on a paraffin impregnated graphite electrode followed by a coating of a thin film of nafion. The neutral red functionalized MWNTs were characterized by spectroscopic and electroanalytical methods. From the voltammetric studies, MWNTs were found to exhibit a higher accessible surface area in electrochemical reactions. The modified electrode exhibited stable electrocatalytic activity toward hydrogen peroxide reduction in a wide potential range. A significant decrease in overvoltage for the reduction of hydrogen peroxide, as well as a dramatic increase in the peak currents in comparison with a bare graphite electrode were observed. Such an ability of neutral red functionalized carbon nanotubes to promote the hydrogen peroxide electron transfer reaction with a short response time (<4 s) and long-term stability, a low detection limit, an extended linear concentration range and a high sensitivity suggest great promise for dehydrogenase and oxidase based amperometric biosensors

  15. Covalent modification of multiwalled carbon nanotubes with neutral red for the fabrication of an amperometric hydrogen peroxide sensor

    Energy Technology Data Exchange (ETDEWEB)

    Jeykumari, D R Shobha; Narayanan, S Sriman [Department of Analytical Chemistry, School of Chemical Sciences, University of Madras, Guindy Campus, Chennai-600 025 (India)

    2007-03-28

    The nanoscale dimensions, graphitic surface chemistry and electronic properties of multiwalled carbon nanotubes (MWNTs) make them an ideal candidate for chemical and biochemical sensing. In this paper we explore a covalent chemical strategy for functionalization of MWNTs with neutral red through carbodiimide coupling between the primary amine of neutral red and carboxyl groups of the carbon nanotubes. The construction of an amperometric sensor was achieved by abrasive immobilization of the functionalized MWNTs on a paraffin impregnated graphite electrode followed by a coating of a thin film of nafion. The neutral red functionalized MWNTs were characterized by spectroscopic and electroanalytical methods. From the voltammetric studies, MWNTs were found to exhibit a higher accessible surface area in electrochemical reactions. The modified electrode exhibited stable electrocatalytic activity toward hydrogen peroxide reduction in a wide potential range. A significant decrease in overvoltage for the reduction of hydrogen peroxide, as well as a dramatic increase in the peak currents in comparison with a bare graphite electrode were observed. Such an ability of neutral red functionalized carbon nanotubes to promote the hydrogen peroxide electron transfer reaction with a short response time (<4 s) and long-term stability, a low detection limit, an extended linear concentration range and a high sensitivity suggest great promise for dehydrogenase and oxidase based amperometric biosensors.

  16. Covalent modification of reduced graphene oxide by means of diazonium chemistry and use as a drug-delivery system.

    Science.gov (United States)

    Wei, Guangcheng; Yan, Miaomiao; Dong, Renhao; Wang, Dong; Zhou, Xiangzhu; Chen, Jingfei; Hao, Jingcheng

    2012-11-12

    Under acidic conditions, reduced graphene oxide (rGO) was functionalized with p-aminobenzoic acid, which formed the diazonium ions through the diazotization with a wet-chemical method. Surfactants or stabilizers were not applied during the diazotization. After the functionalized rGO was treated through mild sonication in aqueous solution, these functionalized rGO sheets were less than two layers, which was determined by atomic force microscopy (AFM) imaging. The water solubility of functionalized rGO after the introduction of polyethyleneimine (PEI) was improved significantly; it was followed by covalent binding of folic acid (FA) molecules to the functionalized rGO to allow us to specifically target CBRH7919 cancer cells by using FA as a receptor. The loading and release behaviors of elsinochrome A (EA) and doxorubicin (DOX) on the functionalized rGO sheets were investigated. The EA loading ratio onto rGO-C(6)H(4)-CO-NH-PEI-NH-CO-FA (abbreviated rGO-PEI-FA, the weight ratio of drug loaded onto rGO-PEI-FA) was approximately 45.56 %, and that of DOX was approximately 28.62 %. It was interesting that the drug release from rGO-PEI-FA was pH- and salt-dependent. The results of cytotoxicity (3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide (MTT) and flow cytometry (FCM) assays, as well as cell morphology observations) clearly showed that the concentration of rGO-PEI-FA as the drug-delivery composite should be less than 12.5 mg L(-1). The conjugation of DOX and rGO-PEI-FA can enhance the cancer-cell apoptosis effectively and can also push the cancer cells to the vulnerable G2 phase of the cell cycle, which is most sensitive and susceptible to damage by drugs or radiation. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  17. Monolayer covalent modification of 5-hydroxytryptophan on glassy carbon electrodes for simultaneous determination of uric acid and ascorbic acid

    International Nuclear Information System (INIS)

    Lin Xiangqin; Li Yongxin

    2006-01-01

    5-Hydroxytryptophan (5-HTP) was covalently grafted on the surface of glassy carbon electrodes (GCEs) using cyclic voltammetric method in a phosphate buffer solution. The prepared electrode, denoded as 5-HTP/GCE, was characterized by X-ray photoelectron spectroscopy, cyclic voltammetry and differential pulse voltammetry (DPV). Tryptophan grafted GCE (TRP/GCE) and 5-hydroxytryptamine grafted GCE (5-HTP/GCE) were also prepared by the same method for comparison. It was found that the electrocatalytic activities toward the oxidation of uric acid (UA) and ascorbic acid (AA) was in the order of 5-HT/GCE > 5-HTP/GCE > TRP/GCE for UA oxidation and 5-HT/GCE 5-HTP/GCE > TRP/GCE for AA oxidation. However, the CV current sensitivity was estimated as 4:2:1 for 5-HTP/GCE:5-HT/GCE:TRP/GCE. The DPV peaks for UA and AA oxidation appeared at 0.07 V and 0.34 V versus SCE, respectively, allowing simultaneous determination in mixtures. A linearly response in the range of: 5.0 x 10 -7 to 1.1 x 10 -5 M with the detection limit (s/n = 3) of 2.8 x 10 -7 M for UA determination, and a linear response in the range of: 5.0 x 10 -6 to 1.0 x 10 -4 M with the detection limit of 4.2 x 10 -6 M for AA determination were obtained. This electrode was used for UA and AA determinations in human urine samples satisfactorily

  18. Collaborative action of Brca1 and CtIP in elimination of covalent modifications from double-strand breaks to facilitate subsequent break repair.

    Directory of Open Access Journals (Sweden)

    Kyoko Nakamura

    2010-01-01

    Full Text Available Topoisomerase inhibitors such as camptothecin and etoposide are used as anti-cancer drugs and induce double-strand breaks (DSBs in genomic DNA in cycling cells. These DSBs are often covalently bound with polypeptides at the 3' and 5' ends. Such modifications must be eliminated before DSB repair can take place, but it remains elusive which nucleases are involved in this process. Previous studies show that CtIP plays a critical role in the generation of 3' single-strand overhang at "clean" DSBs, thus initiating homologous recombination (HR-dependent DSB repair. To analyze the function of CtIP in detail, we conditionally disrupted the CtIP gene in the chicken DT40 cell line. We found that CtIP is essential for cellular proliferation as well as for the formation of 3' single-strand overhang, similar to what is observed in DT40 cells deficient in the Mre11/Rad50/Nbs1 complex. We also generated DT40 cell line harboring CtIP with an alanine substitution at residue Ser332, which is required for interaction with BRCA1. Although the resulting CtIP(S332A/-/- cells exhibited accumulation of RPA and Rad51 upon DNA damage, and were proficient in HR, they showed a marked hypersensitivity to camptothecin and etoposide in comparison with CtIP(+/-/- cells. Finally, CtIP(S332A/-/-BRCA1(-/- and CtIP(+/-/-BRCA1(-/- showed similar sensitivities to these reagents. Taken together, our data indicate that, in addition to its function in HR, CtIP plays a role in cellular tolerance to topoisomerase inhibitors. We propose that the BRCA1-CtIP complex plays a role in the nuclease-mediated elimination of oligonucleotides covalently bound to polypeptides from DSBs, thereby facilitating subsequent DSB repair.

  19. Inhibition of mitochondrial division through covalent modification of Drp1 protein by 15 deoxy-Δ12,14-prostaglandin J2

    International Nuclear Information System (INIS)

    Mishra, Nandita; Kar, Rekha; Singha, Prajjal K.; Venkatachalam, Manjeri A.; McEwen, Donald G.; Saikumar, Pothana

    2010-01-01

    Arachidonic acid derived endogenous electrophile 15d-PGJ2 has gained much attention in recent years due to its potent anti-proliferative and anti-inflammatory actions mediated through thiol modification of cysteine residues in its target proteins. Here, we show that 15d-PGJ2 at 1 μM concentration converts normal mitochondria into large elongated and interconnected mitochondria through direct binding to mitochondrial fission protein Drp1 and partial inhibition of its GTPase activity. Mitochondrial elongation induced by 15d-PGJ2 is accompanied by increased assembly of Drp1 into large oligomeric complexes through plausible intermolecular interactions. The role of decreased GTPase activity of Drp1 in the formation of large oligomeric complexes is evident when Drp1 is incubated with a non-cleavable GTP analog, GTPγS or by a mutation that inactivated GTPase activity of Drp1 (K38A). The mutation of cysteine residue (Cys644) in the GTPase effector domain, a reported target for modification by reactive electrophiles, to alanine mimicked K38A mutation induced Drp1 oligomerization and mitochondrial elongation, suggesting the importance of cysteine in GED to regulate the GTPase activity and mitochondrial morphology. Interestingly, treatment of K38A and C644A mutants with 15d-PGJ2 resulted in super oligomerization of both mutant Drp1s indicating that 15d-PGJ2 may further stabilize Drp1 oligomers formed by loss of GTPase activity through covalent modification of middle domain cysteine residues. The present study documents for the first time the regulation of a mitochondrial fission activity by a prostaglandin, which will provide clues for understanding the pathological and physiological consequences of accumulation of reactive electrophiles during oxidative stress, inflammation and degeneration.

  20. Linear Discriminant Analysis for the in Silico Discovery of Mechanism-Based Reversible Covalent Inhibitors of a Serine Protease: Application of Hydration Thermodynamics Analysis and Semi-empirical Molecular Orbital Calculation.

    Science.gov (United States)

    Masuda, Yosuke; Yoshida, Tomoki; Yamaotsu, Noriyuki; Hirono, Shuichi

    2018-01-01

    We recently reported that the Gibbs free energy of hydrolytic water molecules (ΔG wat ) in acyl-trypsin intermediates calculated by hydration thermodynamics analysis could be a useful metric for estimating the catalytic rate constants (k cat ) of mechanism-based reversible covalent inhibitors. For thorough evaluation, the proposed method was tested with an increased number of covalent ligands that have no corresponding crystal structures. After modeling acyl-trypsin intermediate structures using flexible molecular superposition, ΔG wat values were calculated according to the proposed method. The orbital energies of antibonding π* molecular orbitals (MOs) of carbonyl C=O in covalently modified catalytic serine (E orb ) were also calculated by semi-empirical MO calculations. Then, linear discriminant analysis (LDA) was performed to build a model that can discriminate covalent inhibitor candidates from substrate-like ligands using ΔG wat and E orb . The model was built using a training set (10 compounds) and then validated by a test set (4 compounds). As a result, the training set and test set ligands were perfectly discriminated by the model. Hydrolysis was slower when (1) the hydrolytic water molecule has lower ΔG wat ; (2) the covalent ligand presents higher E orb (higher reaction barrier). Results also showed that the entropic term of hydrolytic water molecule (-TΔS wat ) could be used for estimating k cat and for covalent inhibitor optimization; when the rotational freedom of the hydrolytic water molecule is limited, the chance for favorable interaction with the electrophilic acyl group would also be limited. The method proposed in this study would be useful for screening and optimizing the mechanism-based reversible covalent inhibitors.

  1. Surface modification of seawater desalination reverse osmosis membranes: Characterization studies & performance evaluation

    KAUST Repository

    Matin, Asif

    2014-06-01

    In this work we report surface modification of commercial reverse osmosis membranes by depositing ultrathin copolymer coatings, which could potentially enhance the biofouling resistance of RO membranes. Hydrophilic monomer hydroxyethyl methacrylate (HEMA) and a hydrophobic monomer, perfluorodecyl acrylate (PFDA) were copolymerized directly on the active layer of commercial aromatic polyamide reverse osmosis (RO) membranes using an initiated Chemical Vapor Deposition (iCVD) technique. Attenuated total reflective Fourier transform infrared spectra (ATR-FTIR) verified the successful modification of the membrane surfaces as a new FTIR adsorption band around 1730cm-1 corresponding to carbonyl groups in the copolymer film appeared after the deposition. X-ray Photoelectron spectroscopy (XPS) analysis also confirmed the presence of the copolymer film on the membrane surface by showing strong fluorine peaks emanating from the fluorinated alkyl side chains of the PFA molecules. Contact angle measurements with deionized water showed the modified membrane surfaces to be initially very hydrophobic but quickly assumed a hydrophilic character within few minutes. Atomic Force Microscopy (AFM) revealed that the deposited films were smooth and conformal as the surface topology of the underlying membrane surface remained virtually unchanged after the deposition. FESEM images of the top surface also showed that the typical ridge-and-valley structure associated with polyamide remained intact after the deposition. Short-term permeation tests using DI water and 2000ppm NaCl water showed that the deposited copolymer coatings had negligible effect on permeate water flux and salt rejection. © 2013 Elsevier B.V.

  2. Gibbs Free Energy of Hydrolytic Water Molecule in Acyl-Enzyme Intermediates of a Serine Protease: A Potential Application for Computer-Aided Discovery of Mechanism-Based Reversible Covalent Inhibitors.

    Science.gov (United States)

    Masuda, Yosuke; Yamaotsu, Noriyuki; Hirono, Shuichi

    2017-01-01

    In order to predict the potencies of mechanism-based reversible covalent inhibitors, the relationships between calculated Gibbs free energy of hydrolytic water molecule in acyl-trypsin intermediates and experimentally measured catalytic rate constants (k cat ) were investigated. After obtaining representative solution structures by molecular dynamics (MD) simulations, hydration thermodynamics analyses using WaterMap™ were conducted. Consequently, we found for the first time that when Gibbs free energy of the hydrolytic water molecule was lower, logarithms of k cat were also lower. The hydrolytic water molecule with favorable Gibbs free energy may hydrolyze acylated serine slowly. Gibbs free energy of hydrolytic water molecule might be a useful descriptor for computer-aided discovery of mechanism-based reversible covalent inhibitors of hydrolytic enzymes.

  3. Influence of non-covalent modification of multiwalled carbon nanotubes on the crystallization behaviour of binary blends of polypropylene and polyamide 6.

    Science.gov (United States)

    Mukhopadhyay, Nabaneeta; Panwar, Ajay S; Kumar, Gulshan; Samajdar, I; Bhattacharyya, Arup R

    2015-02-14

    Blends of polypropylene (PP) and polyamide 6 (PA6) with multiwalled carbon nanotubes (MWNTs) were prepared using different processing strategies in a twin-screw micro-compounder. The effect of MWNTs on the crystallization behaviour of the PP phase and the PA6 phase of the blend has been investigated through non-isothermal crystallization studies by differential scanning calorimetric analysis. Furthermore, the effect of the addition of the compatibilizer (PP-g-MA) and the modification of MWNTs (m-MWNTs) with a non-covalent organic modifier (Li-salt of 6 amino hexanoic acid, Li-AHA) has also been studied in context to the crystallization behaviour of the PP and PA6 phase in the blend. The crystallization studies have indicated a significant increase in bulk crystallization temperature of the PP phase in the blend in the presence of MWNTs. Moreover, the formation of 'trans-lamellar crystalline' structure consisting of PA6 'trans-crystalline lamellae' on MWNTs surface was facilitated in the case of blends prepared via 'protocol 2' as compared to the corresponding blends prepared via 'protocol 1'. Wide angle X-ray diffraction analysis has showed the existence of a β-polymorph of the PP phase due to incorporation of the PA6 phase in the blend. Addition of MWNTs in the blends has facilitated further β-crystalline structure formation of the PP phase. In the presence of m-MWNTs, a higher β-fraction was observed in the PP phase as compared to the blend with pristine MWNTs. Addition of PP-g-MA has suppressed the β-phase formation in the PP phase in the blend. X-ray bulk texture analysis revealed that incorporation of PA6 as well as pristine/modified MWNTs has influenced the extent of orientation of the PP chains towards specific crystalline planes in various blend compositions of PP and PA6.

  4. Chemical Modification of a Dehydratase Enzyme Involved in Bacterial Virulence by an Ammonium Derivative: Evidence of its Active Site Covalent Adduct.

    Science.gov (United States)

    González-Bello, Concepción; Tizón, Lorena; Lence, Emilio; Otero, José M; van Raaij, Mark J; Martinez-Guitian, Marta; Beceiro, Alejandro; Thompson, Paul; Hawkins, Alastair R

    2015-07-29

    The first example of an ammonium derivative that causes a specific modification of the active site of type I dehydroquinase (DHQ1), a dehydratase enzyme that is a promising target for antivirulence drug discovery, is described. The resolution at 1.35 Å of the crystal structure of DHQ1 from Salmonella typhi chemically modified by this ammonium derivative revealed that the ligand is covalently attached to the essential Lys170 through the formation of an amine. The detection by mass spectroscopy of the reaction intermediates, in conjunction with the results of molecular dynamics simulations, allowed us to explain the inhibition mechanism and the experimentally observed differences between S. typhi and Staphylococcus aureus enzymes. The results presented here reveal that the replacement of Phe225 in St-DHQ1 by Tyr214 in Sa-DHQ1 and its hydrogen bonding interaction with the conserved water molecule observed in several crystal structures protects the amino adduct against further dehydration/aromatization reactions. In contrast, for the St-DHQ1 enzyme, the carboxylate group of Asp114, with the assistance of this water molecule, would trigger the formation of a Schiff base that can undergo further dehydration reactions until full aromatization of the cyclohexane ring is achieved. Moreover, in vitro antivirulence studies showed that the reported compound is able to reduce the ability of Salmonella Enteritidis to kill A459 respiratory cells. These studies have identified a good scaffold for the design of irreversible inhibitors that can be used as drugs and has opened up new opportunities for the development of novel antivirulence agents by targeting the DHQ1 enzyme.

  5. Novel covalent modification of human anaplastic lymphoma kinase (ALK and potentiation of crizotinib-mediated inhibition of ALK activity by BNP7787

    Directory of Open Access Journals (Sweden)

    Parker AR

    2015-02-01

    Full Text Available Aulma R Parker,1 Pavankumar N Petluru,1 Vicki L Nienaber,2 Min Zhao,1 Philippe Y Ayala,1 John Badger,2 Barbara Chie-Leon,2 Vandana Sridhar,2 Cheyenne Logan,2 Harry Kochat,1 Frederick H Hausheer1 1BioNumerik Pharmaceuticals, Inc., San Antonio, TX, USA; 2Zenobia Therapeutics, Inc., La Jolla, CA, USA Abstract: BNP7787 (Tavocept, disodium 2,2’-dithio-bis-ethanesulfonate is a novel, investigational, water-soluble disulfide that is well-tolerated and nontoxic. In separate randomized multicenter Phase II and Phase III clinical trials in non-small-cell lung cancer (NSCLC patients, treatment with BNP7787 in combination with standard chemotherapy resulted in substantial increases in the overall survival of patients with advanced adenocarcinoma of the lung in the first-line treatment setting. We hypothesized that BNP7787 might interact with and modify human anaplastic lymphoma kinase (ALK. At least seven different variants of ALK fusions with the gene encoding the echinoderm microtubule-associated protein-like 4 (EML4 are known to occur in NSCLC. EML4–ALK fusions are thought to account for approximately 3% of NSCLC cases. Herein, we report the covalent modification of the kinase domain of human ALK by a BNP7787-derived mesna moiety and the functional consequences of this modification in ALK assays evaluating kinase activity. The kinase domain of the ALK protein crystallizes as a monomer, and BNP7787-derived mesna-cysteine adducts were observed at Cys 1235 and Cys 1156. The BNP7787-derived mesna adduct at Cys 1156 is located in close proximity to the active site and results in substantial disorder of the P-loop and activation loop (A-loop. Comparison with the P-loop of apo-ALK suggests that the BNP7787-derived mesna adduct at Cys 1156 interferes with the positioning of Phe 1127 into a small pocket now occupied by mesna, resulting in a destabilization of the loop's binding orientation. Additionally, in vitro kinase activity assays indicate that BNP7787

  6. Modification of Polyamide-Urethane (PAUt Thin Film Composite Membrane for Improving the Reverse Osmosis Performance

    Directory of Open Access Journals (Sweden)

    Li-Fen Liu

    2018-03-01

    Full Text Available In the current study, the poly (amide-urethane (PAUt membranes were successfully fabricated by interfacial polymerization of m-phenylenediamine (MPD and 5-choroformyloxyisophaloyl chloride (CFIC on the polysulfone substrates. Two modification methods based on layer-by-layer assembly were applied to modify the PAUt membrane surface to achieve antifouling property: 1. Chitosan (CS was directly self-assembled on the PAUt membrane (i.e., PAUt-CS; and 2. polydimethyl diallyl ammonium chloride (PDDA, polystyrene sulfonate (PSS, and CS were successively self-assembled on the membrane surface (i.e., PAUt-PDDA/PSS/CS. The resultant membranes were symmetrically characterized by Attenuated Total Reflection Fourier Transform Infrared Spectroscopy (ATR-FTIR, X-ray Photoelectron Spectroscopy (XPS, Scanning Electron Microscopy (SEM, Atomic Force Microscopy (AFM and Contact Angle Meter (CAM, respectively. The results indicated that the modified membranes had much smoother and more hydrophilic surfaces as compared to the nascent PAUt membrane. Meanwhile, the modified membranes exhibited better reverse osmosis performance in terms of water permeability and salt rejection. After the modified membranes were fouled by lake water, the PAUt-PDDA/PSS/CS membrane presented the best antifouling performance among the three types of membranes. Combining the reverse osmosis performance with the anti-fouling property obviously, the PAUt-PDDA/PSS/CS membrane behaved as a promising candidate to be used in real applications.

  7. FTO, m6 Am , and the hypothesis of reversible epitranscriptomic mRNA modifications.

    Science.gov (United States)

    Mauer, Jan; Jaffrey, Samie R

    2018-05-12

    The fate of mRNA is regulated by epitranscriptomic nucleotide modifications, the most abundant of which is N 6 -methyladenosine (m 6 A). Although the pattern and distribution of m 6 A in mRNA is mediated by specific methyltransferases, a recent hypothesis is that specific demethylases or 'erasers' allow m 6 A to be dynamically reversed by signaling pathways. In this Review, we discuss the data in support and against this model. New insights into the function of fat mass and obesity-associated protein (FTO), the original enzyme thought to be an m 6 A eraser, reveal that its physiologic target is not m 6 A, but instead is N 6 ,2'-O-dimethyladenosine (m 6 A m ). Another m 6 A demethylase, ALKBH5, appears to have functions limited to sperm development in normal mice. Overall, the majority of the data suggest that m 6 A is generally not reversible, although m 6 A may be susceptible to demethylation in pathophysiological states such as cancer. © 2018 Federation of European Biochemical Societies.

  8. Covalent Organic

    DEFF Research Database (Denmark)

    Vutti, Surendra

    chemistry of silicon, InAs and GaAs materials, covalentsurface functionalization using organosilanes, liquid-phase, and vapor-phasefunctionalizations, diazo-transfer reaction, CuAAC click chemistry, different types ofbiorthogonal chemistries, SPAAC chemistry, and cellular interactions of chemically...... immobilization of D-amino acid adhesion peptideson azide functionalized silicon, GaAs and InAs materials by using CuAAC-click chemistry.The covalent immobilization of penetration peptide (TAT) on gold nanotips of InAs NWs isalso demonstrated.In chapter four, the covalent immobilization of GFP on silicon wafers......, GaAs wafers andGaAs NWs is demonstrated. Series of Fmoc-Pra-OH, NHS-PEG5-NHS and BCN-NHSfunctionalized silicon surfaces has been prepared, whereby GFP-N3 and GFP-bicyclononyneare immobilized by using CuAAC and SPAAC chemistry. The specific and covalentimmobilization of GFP-N3 on bicyclononyne...

  9. Surface modification of polyamide reverse osmosis membrane with organic-inorganic hybrid material for antifouling

    Science.gov (United States)

    Zhang, Yang; Wan, Ying; Pan, Guoyuan; Yan, Hao; Yao, Xuerong; Shi, Hongwei; Tang, Yujing; Wei, Xiangrong; Liu, Yiqun

    2018-03-01

    A series of thin-film composite reverse osmosis membranes based on polyamide have been modified by coating the polyvinyl alcohol and 3-mercaptopropyltriethoxysilane aqueous solution prepared by a sol-gel process on the membrane surface, followed by thermal crosslinking treatment. In order to improve the hydrophilicity of the modified TFC membranes, the membranes were then immersed into H2O2 aqueous solution to convert -SH into -SO3H. The resulting TFC membranes were characterized by SEM, AFM, ATR-FTIR, streaming potential, XPS as well as static contact angle. After surface modification with the organic-inorganic hybrid material, the TFC membranes show increased NaCl rejection and decreased water flux with increasing 3-mercaptopropyltrimethoxysilane content in coating solution. The optimal modification membrane (PA-SMPTES-0.8) exhibits a NaCl rejection of 99.29%, higher than that (97.20%) of the virgin PA membrane, and a comparable water flux to virgin PA membrane (41.7 L/m2 h vs 47.9 L/m2 h). More importantly, PA-SMPTES-0.8 membrane shows much more improved fouling resistance to BSA than virgin PA and PVA modified PA (PA-PVA-1.0) membranes. PA-SMPTES-0.8 membrane loses about 13% of the initial flux after BSA fouling for 12 h, which is lower than that of virgin PA and PA-PVA-1.0 membranes (42% and 18%). Furthermore, the flux recovery of PA-SMPTES-0.8 membrane reaches 94% after cleaning. Thus the TFC membranes modified by this organic-inorganic hybrid technology show potential applications as antifouling RO membrane for desalination and purification.

  10. Reversible oxidative modification: a key mechanism of Na+-K+ pump regulation.

    Science.gov (United States)

    Figtree, Gemma A; Liu, Chia-Chi; Bibert, Stephanie; Hamilton, Elisha J; Garcia, Alvaro; White, Caroline N; Chia, Karin K M; Cornelius, Flemming; Geering, Kaethi; Rasmussen, Helge H

    2009-07-17

    Angiotensin II (Ang II) inhibits the cardiac sarcolemmal Na(+)-K(+) pump via protein kinase (PK)C-dependent activation of NADPH oxidase. We examined whether this is mediated by oxidative modification of the pump subunits. We detected glutathionylation of beta(1), but not alpha(1), subunits in rabbit ventricular myocytes at baseline. beta(1) Subunit glutathionylation was increased by peroxynitrite (ONOO(-)), paraquat, or activation of NADPH oxidase by Ang II. Increased glutathionylation was associated with decreased alpha(1)/beta(1) subunit coimmunoprecipitation. Glutathionylation was reversed after addition of superoxide dismutase. Glutaredoxin 1, which catalyzes deglutathionylation, coimmunoprecipitated with beta(1) subunit and, when included in patch pipette solutions, abolished paraquat-induced inhibition of myocyte Na(+)-K(+) pump current (I(p)). Cysteine (Cys46) of the beta(1) subunit was the likely candidate for glutathionylation. We expressed Na(+)-K(+) pump alpha(1) subunits with wild-type or Cys46-mutated beta(1) subunits in Xenopus oocytes. ONOO(-) induced glutathionylation of beta(1) subunit and a decrease in Na(+)-K(+) pump turnover number. This was eliminated by mutation of Cys46. ONOO(-) also induced glutathionylation of the Na(+)-K(+) ATPase beta(1) subunit from pig kidney. This was associated with a approximately 2-fold decrease in the rate-limiting E(2)-->E(1) conformational change of the pump, as determined by RH421 fluorescence. We propose that kinase-dependent regulation of the Na(+)-K(+) pump occurs via glutathionylation of its beta(1) subunit at Cys46. These findings have implications for pathophysiological conditions characterized by neurohormonal dysregulation, myocardial oxidative stress and raised myocyte Na(+) levels.

  11. Reversible data hiding for image based on histogram modification of wavelet coefficients

    NARCIS (Netherlands)

    Liang, Xiaoping; Wu, Xiaoyun; Huang, Jiwu; Hao, Y.; Liu, J.; Wang, Y.; Cheung, Y.; Yin, H.; Jiao, L.; Ma, J.; Jiao, Y.C.

    2005-01-01

    Reversible data hiding has drawn intensive attention recently. Reversibility means to embed data into digital media and restore the original media from marked media losslessly. Reversible data hiding technique is desired in sensitive applications that require no permanent loss of signal fidelity. In

  12. Post-Translational Modifications of TRP Channels

    Directory of Open Access Journals (Sweden)

    Olaf Voolstra

    2014-04-01

    Full Text Available Transient receptor potential (TRP channels constitute an ancient family of cation channels that have been found in many eukaryotic organisms from yeast to human. TRP channels exert a multitude of physiological functions ranging from Ca2+ homeostasis in the kidney to pain reception and vision. These channels are activated by a wide range of stimuli and undergo covalent post-translational modifications that affect and modulate their subcellular targeting, their biophysical properties, or channel gating. These modifications include N-linked glycosylation, protein phosphorylation, and covalent attachment of chemicals that reversibly bind to specific cysteine residues. The latter modification represents an unusual activation mechanism of ligand-gated ion channels that is in contrast to the lock-and-key paradigm of receptor activation by its agonists. In this review, we summarize the post-translational modifications identified on TRP channels and, when available, explain their physiological role.

  13. Sulfone-stabilized carbanions for the reversible covalent capture of a posttranslationally-generated cysteine oxoform found in protein tyrosine phosphatase 1B (PTP1B).

    Science.gov (United States)

    Parsons, Zachary D; Ruddraraju, Kasi Viswanatharaju; Santo, Nicholas; Gates, Kent S

    2016-06-15

    Redox regulation of protein tyrosine phosphatase 1B (PTP1B) involves oxidative conversion of the active site cysteine thiolate into an electrophilic sulfenyl amide residue. Reduction of the sulfenyl amide by biological thiols regenerates the native cysteine residue. Here we explored fundamental chemical reactions that may enable covalent capture of the sulfenyl amide residue in oxidized PTP1B. Various sulfone-containing carbon acids were found to react readily with a model peptide sulfenyl amide via attack of the sulfonyl carbanion on the electrophilic sulfur center in the sulfenyl amide. Both the products and the rates of these reactions were characterized. The results suggest that capture of a peptide sulfenyl amide residue by sulfone-stabilized carbanions can slow, but not completely prevent, thiol-mediated generation of the corresponding cysteine-containing peptide. Sulfone-containing carbon acids may be useful components in the construction of agents that knock down PTP1B activity in cells via transient covalent capture of the sulfenyl amide oxoform generated during insulin signaling processes. Copyright © 2016 Elsevier Ltd. All rights reserved.

  14. The measurement of reversible redox dependent post-translational modifications and their regulation of mitochondrial and skeletal muscle function

    Directory of Open Access Journals (Sweden)

    Philip A Kramer

    2015-11-01

    Full Text Available Mitochondrial oxidative stress is a common feature of skeletal myopathies across multiple conditions; however, the mechanism by which it contributes to skeletal muscle dysfunction remains controversial. Oxidative damage to proteins, lipids, and DNA has received the most attention, yet an important role for reversible redox post-translational modifications (PTMs in pathophysiology is emerging. The possibility that these PTMs can exert dynamic control of muscle function implicates them as a mechanism contributing to skeletal muscle dysfunction in chronic disease. Herein, we discuss the significance of thiol-based redox dependent modifications to mitochondrial, myofibrillar and excitation-contraction (EC coupling proteins with an emphasis on how these changes could alter skeletal muscle performance under chronically stressed conditions. A major barrier to a better mechanistic understanding of the role of reversible redox PTMs in muscle function is the technical challenges associated with accurately measuring the changes of site-specific redox PTMs. Here we will critically review current approaches with an emphasis on sample preparation artifacts, quantitation, and specificity. Despite these challenges, the ability to accurately quantify reversible redox PTMs is critical to understanding the mechanisms by which mitochondrial oxidative stress contributes to skeletal muscle dysfunction in chronic diseases.

  15. The Measurement of Reversible Redox Dependent Post-translational Modifications and Their Regulation of Mitochondrial and Skeletal Muscle Function

    Energy Technology Data Exchange (ETDEWEB)

    Kramer, Philip A.; Duan, Jicheng; Qian, Wei-Jun; Marcinek, David J.

    2015-11-25

    Mitochondrial oxidative stress is a common feature of skeletal myopathies across multiple conditions; however, the mechanism by which it contributes to skeletal muscle dysfunction remains controversial. Oxidative damage to proteins, lipids, and DNA has received the most attention, yet an important role for reversible redox post-translational modifications (PTMs) in pathophysiology is emerging. The possibility that these PTMs can exert dynamic control of muscle function implicates them as a mechanism contributing to skeletal muscle dysfunction in chronic disease. Herein, we discuss the significance of thiol-based redox dependent modifications to mitochondrial, myofibrillar and excitation-contraction (EC) coupling proteins with an emphasis on how these changes could alter skeletal muscle performance under chronically stressed conditions. A major barrier to a better mechanistic understanding of the role of reversible redox PTMs in muscle function is the technical challenges associated with accurately measuring the changes of site-specific redox PTMs. Here we will critically review current approaches with an emphasis on sample preparation artifacts, quantitation, and specificity. Despite these challenges, the ability to accurately quantify reversible redox PTMs is critical to understanding the mechanisms by which mitochondrial oxidative stress contributes to skeletal muscle dysfunction in chronic diseases.

  16. Diazonium modification of porous graphitic carbon with catechol and amide groups for hydrophilic interaction and attenuated reversed phase liquid chromatography.

    Science.gov (United States)

    Iverson, Chad D; Zhang, Ya; Lucy, Charles A

    2015-11-27

    Porous graphitic carbon (PGC) is an increasingly popular and attractive phase for HPLC on account of its chemical and thermal stability, and its unique separation mechanism. However, native PGC is strongly hydrophobic and in some instances excessively retentive. As part of our effort to build a library of hydrophilic covalently modified PGC phases, we functionalized PGC with catechol and amide groups by means of aryl diazonium chemistry to produce two new phases. Successful grafting was confirmed by X-ray photoelectron spectroscopy (XPS). Under HILIC conditions, the Catechol-PGC showed up to 5-fold increased retention relative to unmodified PGC and selectivity that differed from four other HILIC phases. Under reversed phase conditions, the Amide-PGC reduced the retentivity of PGC by almost 90%. The chromatographic performance of Catechol-PGC and Amide-PGC is demonstrated by separations of nucleobases, nucleosides, phenols, alkaline pharmaceuticals, and performance enhancing stimulants. These compounds had retention factors (k) ranging from 0.5 to 13. Copyright © 2015 Elsevier B.V. All rights reserved.

  17. Modification by covalent reaction or oxidation of cysteine residues in the tandem-SH2 domains of ZAP-70 and Syk can block phosphopeptide binding.

    Science.gov (United States)

    Visperas, Patrick R; Winger, Jonathan A; Horton, Timothy M; Shah, Neel H; Aum, Diane J; Tao, Alyssa; Barros, Tiago; Yan, Qingrong; Wilson, Christopher G; Arkin, Michelle R; Weiss, Arthur; Kuriyan, John

    2015-01-01

    Zeta-chain associated protein of 70 kDa (ZAP-70) and spleen tyrosine kinase (Syk) are non-receptor tyrosine kinases that are essential for T-cell and B-cell antigen receptor signalling respectively. They are recruited, via their tandem-SH2 (Src-homology domain 2) domains, to doubly phosphorylated immunoreceptor tyrosine-based activation motifs (ITAMs) on invariant chains of immune antigen receptors. Because of their critical roles in immune signalling, ZAP-70 and Syk are targets for the development of drugs for autoimmune diseases. We show that three thiol-reactive small molecules can prevent the tandem-SH2 domains of ZAP-70 and Syk from binding to phosphorylated ITAMs. We identify a specific cysteine residue in the phosphotyrosine-binding pocket of each protein (Cys39 in ZAP-70, Cys206 in Syk) that is necessary for inhibition by two of these compounds. We also find that ITAM binding to ZAP-70 and Syk is sensitive to the presence of H2O2 and these two cysteine residues are also necessary for inhibition by H2O2. Our findings suggest a mechanism by which the reactive oxygen species generated during responses to antigen could attenuate signalling through these kinases and may also inform the development of ZAP-70 and Syk inhibitors that bind covalently to their SH2 domains.

  18. Directed genetic modification of African horse sickness virus by reverse genetics

    Directory of Open Access Journals (Sweden)

    Elaine Vermaak

    2015-07-01

    Full Text Available African horse sickness virus (AHSV, a member of the Orbivirus genus in the family Reoviridae, is an arthropod-transmitted pathogen that causes a devastating disease in horses with a mortality rate greater than 90%. Fundamental research on AHSV and the development of safe, efficacious vaccines could benefit greatly from an uncomplicated genetic modification method to generate recombinant AHSV. We demonstrate that infectious AHSV can be recovered by transfection of permissive mammalian cells with transcripts derived in vitro from purified AHSV core particles. These findings were expanded to establish a genetic modification system for AHSV that is based on transfection of the cells with a mixture of purified core transcripts and a synthetic T7 transcript. This approach was applied successfully to recover a directed cross-serotype reassortant AHSV and to introduce a marker sequence into the viral genome. The ability to manipulate the AHSV genome and engineer specific mutants will increase understanding of AHSV replication and pathogenicity, as well as provide a tool for generating designer vaccine strains.

  19. Atomic Covalent Functionalization of Graphene

    Science.gov (United States)

    Johns, James E.; Hersam, Mark C.

    2012-01-01

    Conspectus Although graphene’s physical structure is a single atom thick, two-dimensional, hexagonal crystal of sp2 bonded carbon, this simple description belies the myriad interesting and complex physical properties attributed to this fascinating material. Because of its unusual electronic structure and superlative properties, graphene serves as a leading candidate for many next generation technologies including high frequency electronics, broadband photodetectors, biological and gas sensors, and transparent conductive coatings. Despite this promise, researchers could apply graphene more routinely in real-world technologies if they could chemically adjust graphene’s electronic properties. For example, the covalent modification of graphene to create a band gap comparable to silicon (~1 eV) would enable its use in digital electronics, and larger band gaps would provide new opportunities for graphene-based photonics. Towards this end, researchers have focused considerable effort on the chemical functionalization of graphene. Due to its high thermodynamic stability and chemical inertness, new methods and techniques are required to create covalent bonds without promoting undesirable side reactions or irreversible damage to the underlying carbon lattice. In this Account, we review and discuss recent theoretical and experimental work studying covalent modifications to graphene using gas phase atomic radicals. Atomic radicals have sufficient energy to overcome the kinetic and thermodynamic barriers associated with covalent reactions on the basal plane of graphene but lack the energy required to break the C-C sigma bonds that would destroy the carbon lattice. Furthermore, because they are atomic species, radicals substantially reduce the likelihood of unwanted side reactions that confound other covalent chemistries. Overall, these methods based on atomic radicals show promise for the homogeneous functionalization of graphene and the production of new classes of two

  20. Covalent Allosteric Inactivation of Protein Tyrosine Phosphatase 1B (PTP1B) by an Inhibitor-Electrophile Conjugate.

    Science.gov (United States)

    Punthasee, Puminan; Laciak, Adrian R; Cummings, Andrea H; Ruddraraju, Kasi Viswanatharaju; Lewis, Sarah M; Hillebrand, Roman; Singh, Harkewal; Tanner, John J; Gates, Kent S

    2017-04-11

    Protein tyrosine phosphatase 1B (PTP1B) is a validated drug target, but it has proven difficult to develop medicinally useful, reversible inhibitors of this enzyme. Here we explored covalent strategies for the inactivation of PTP1B using a conjugate composed of an active site-directed 5-aryl-1,2,5-thiadiazolidin-3-one 1,1-dioxide inhibitor connected via a short linker to an electrophilic α-bromoacetamide moiety. Inhibitor-electrophile conjugate 5a caused time-dependent loss of PTP1B activity consistent with a covalent inactivation mechanism. The inactivation occurred with a second-order rate constant of (1.7 ± 0.3) × 10 2 M -1 min -1 . Mass spectrometric analysis of the inactivated enzyme indicated that the primary site of modification was C121, a residue distant from the active site. Previous work provided evidence that covalent modification of the allosteric residue C121 can cause inactivation of PTP1B [Hansen, S. K., Cancilla, M. T., Shiau, T. P., Kung, J., Chen, T., and Erlanson, D. A. (2005) Biochemistry 44, 7704-7712]. Overall, our results are consistent with an unusual enzyme inactivation process in which noncovalent binding of the inhibitor-electrophile conjugate to the active site of PTP1B protects the nucleophilic catalytic C215 residue from covalent modification, thus allowing inactivation of the enzyme via selective modification of allosteric residue C121.

  1. Surface modification of thin film composite reverse osmosis membrane by glycerol assisted oxidation with sodium hypochlorite

    Science.gov (United States)

    Raval, Hiren D.; Samnani, Mohit D.; Gauswami, Maulik V.

    2018-01-01

    Need for improvement in water flux of thin film composite (TFC) RO membrane has been appreciated by researchers world over and surface modification approach is found promising to achieve higher water flux and solute rejection. Thin film composite RO membrane was exposed to 2000 mg/l sodium hypochlorite solution with varying concentrations of glycerol ranging from 1 to 10%. It was found that there was a drop in concentration of sodium hypochlorite after the addition of glycerol because of a new compound resulted from the oxidation of glycerol with sodium hypochlorite. The water flux of the membrane treated with 1% glycerol with 2000 mg/l sodium hypochlorite for 1 h was about 22% more and salt rejection was 1.36% greater than that of only sodium hypochlorite treated membrane for the same concentration and time. There was an increase in salt rejection of membrane with increase in concentration of glycerol from 1% to 5%, however, increasing glycerol concentration further up to 10%, the salt rejection declined. The water flux was found declining from 1% glycerol solution to 10% glycerol solution. The membrane samples were characterized to understand the change in chemical structure and morphology of the membrane.

  2. Chemistry of Covalent Organic Frameworks.

    Science.gov (United States)

    Waller, Peter J; Gándara, Felipe; Yaghi, Omar M

    2015-12-15

    Linking organic molecules by covalent bonds into extended solids typically generates amorphous, disordered materials. The ability to develop strategies for obtaining crystals of such solids is of interest because it opens the way for precise control of the geometry and functionality of the extended structure, and the stereochemical orientation of its constituents. Covalent organic frameworks (COFs) are a new class of porous covalent organic structures whose backbone is composed entirely of light elements (B, C, N, O, Si) that represent a successful demonstration of how crystalline materials of covalent solids can be achieved. COFs are made by combination of organic building units covalently linked into extended structures to make crystalline materials. The attainment of crystals is done by several techniques in which a balance is struck between the thermodynamic reversibility of the linking reactions and their kinetics. This success has led to the expansion of COF materials to include organic units linked by these strong covalent bonds: B-O, C-N, B-N, and B-O-Si. Since the organic constituents of COFs, when linked, do not undergo significant change in their overall geometry, it has been possible to predict the structures of the resulting COFs, and this advantage has facilitated their characterization using powder X-ray diffraction (PXRD) techniques. It has also allowed for the synthesis of COF structures by design and for their formation with the desired composition, pore size, and aperture. In practice, the modeled PXRD pattern for a given expected COF is compared with the experimental one, and depending on the quality of the match, this is used as a starting point for solving and then refining the crystal structure of the target COF. These characteristics make COFs an attractive class of new porous materials. Accordingly, they have been used as gas storage materials for energy applications, solid supports for catalysis, and optoelectronic devices. A large and

  3. Preparation of an antitumor and antivirus agent: chemical modification of α-MMC and MAP30 from Momordica Charantia L. with covalent conjugation of polyethyelene glycol.

    Science.gov (United States)

    Meng, Yao; Liu, Shuangfeng; Li, Juan; Meng, Yanfa; Zhao, Xiaojun

    2012-01-01

    Alpha-momorcharin (α-MMC) and momordica anti-HIV protein (MAP30) derived from Momordica charantia L. have been confirmed to possess antitumor and antivirus activities due to their RNA-N-glycosidase activity. However, strong immunogenicity and short plasma half-life limit their clinical application. To solve this problem, the two proteins were modified with (mPEG)(2)-Lys-NHS (20 kDa). In this article, a novel purification strategy for the two main type I ribosome-inactivating proteins (RIPs), α-MMC and MAP30, was successfully developed for laboratory-scale preparation. Using this dramatic method, 200 mg of α-MMC and about 120 mg of MAP30 was obtained in only one purification process from 200 g of Momordica charantia seeds. The homogeneity and some other properties of the two proteins were assessed by gradient SDS-PAGE, electrospray ionization quadruple mass spectrometry, and N-terminal sequence analysis as well as Western blot. Two polyethylene glycol (PEG)ylated proteins were synthesized and purified. Homogeneous mono-, di-, or tri-PEGylated proteins were characterized by matrix-assisted laser desorption ionization-time of flight mass spectrometry. The analysis of antitumor and antivirus activities indicated that the serial PEGylated RIPs preserved moderate activities on JAR choriocarcinoma cells and herpes simplex virus-1. Furthermore, both PEGylated proteins showed about 60%-70% antitumor and antivirus activities, and at the same time decreased 50%-70% immunogenicity when compared with their unmodified counterparts. α-MMC and MAP30 obtained from this novel purification strategy can meet the requirement of a large amount of samples for research. Their chemical modification can solve the problem of strong immunogenicity and meanwhile preserve moderate activities. All these findings suggest the potential application of PEGylated α-MMC and PEGylated MAP30 as antitumor and antivirus agents. According to these results, PEGylated RIPs can be constructed with

  4. Preparation of an antitumor and antivirus agent: chemical modification of α-MMC and MAP30 from Momordica Charantia L. with covalent conjugation of polyethyelene glycol

    Directory of Open Access Journals (Sweden)

    Meng Y

    2012-06-01

    virus-1. Furthermore, both PEGylated proteins showed about 60%–70% antitumor and antivirus activities, and at the same time decreased 50%–70% immunogenicity when compared with their unmodified counterparts.Conclusion/significance: α-MMC and MAP30 obtained from this novel purification strategy can meet the requirement of a large amount of samples for research. Their chemical modification can solve the problem of strong immunogenicity and meanwhile preserve moderate activities. All these findings suggest the potential application of PEGylated α-MMC and PEGylated MAP30 as antitumor and antivirus agents. According to these results, PEGylated RIPs can be constructed with nanomaterials to be a targeting drug that can further decrease immunogenicity and side effects. Through nanotechnology we can make them low-release drugs, which can further prolong their half-life period in the human body.Keywords: ribosome-inactivating proteins, alpha-momorcharin, momordica anti-HIV protein, antitumor, antivirus, (mPEG2-Lys-NHS (20 kDa, immunogenicity

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2017-02-28

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

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

    International Nuclear Information System (INIS)

    Vatanpour, Vahid; Zoqi, Naser

    2017-01-01

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

  7. Covalent biofunctionalization of silicon nitride surfaces

    NARCIS (Netherlands)

    Arafat, A.; Giesbers, M.; Rosso, M.; Sudhölter, E.J.R.; Schroën, C.G.P.H.; White, R.G.; Li Yang,; Linford, M.R.; Zuilhof, H.

    2007-01-01

    Covalently attached organic monolayers on etched silicon nitride (SixN4; x 3) surfaces were prepared by reaction of SixN4-coated wafers with neat or solutions of 1-alkenes and 1-alkynes in refluxing mesitylene. The surface modification was monitored by measurement of the static water contact angle,

  8. Reversible targeting of noncatalytic cysteines with chemically tuned electrophiles

    DEFF Research Database (Denmark)

    Serafimova, Iana M; Pufall, Miles A; Krishnan, Shyam

    2012-01-01

    Targeting noncatalytic cysteine residues with irreversible acrylamide-based inhibitors is a powerful approach for enhancing pharmacological potency and selectivity. Nevertheless, concerns about off-target modification motivate the development of reversible cysteine-targeting strategies. Here we...... of these electrophiles into a noncovalent kinase-recognition scaffold produced slowly dissociating, covalent inhibitors of the p90 ribosomal protein S6 kinase RSK2. A cocrystal structure revealed specific noncovalent interactions that stabilize the complex by positioning the electrophilic carbon near the targeted...

  9. Reversible networks in supramolecular polymers

    NARCIS (Netherlands)

    Havermans - van Beek, D.J.M.

    2007-01-01

    Non–covalent interactions between low molecular weight polymers form the basis of supramolecular polymers. The material properties of such polymers are determined by the strength and lifetime of the non–covalent reversible interactions. Due to the reversibility of the interactions between the low

  10. Asymmetric Modification of Hepatitis B Virus (HBV) Genomes by an Endogenous Cytidine Deaminase inside HBV Cores Informs a Model of Reverse Transcription.

    Science.gov (United States)

    Nair, Smita; Zlotnick, Adam

    2018-05-15

    Cytidine deaminases inhibit replication of a broad range of DNA viruses by deaminating cytidines on single-stranded DNA (ssDNA) to generate uracil. While several lines of evidence have revealed hepatitis B virus (HBV) genome editing by deamination, it is still unclear which nucleic acid intermediate of HBV is modified. Hepatitis B virus has a relaxed circular double-stranded DNA (rcDNA) genome that is reverse transcribed within virus cores from a RNA template. The HBV genome also persists as covalently closed circular DNA (cccDNA) in the nucleus of an infected cell. In the present study, we found that in HBV-producing HepAD38 and HepG2.2.15 cell lines, endogenous cytidine deaminases edited 10 to 25% of HBV rcDNA genomes, asymmetrically with almost all mutations on the 5' half of the minus strand. This region corresponds to the last half of the minus strand to be protected by plus-strand synthesis. Within this half of the genome, the number of mutations peaks in the middle. Overexpressed APOBEC3A and APOBEC3G could be packaged in HBV capsids but did not change the amount or distribution of mutations. We found no deamination on pregenomic RNA (pgRNA), indicating that an intact genome is encapsidated and deaminated during or after reverse transcription. The deamination pattern suggests a model of rcDNA synthesis in which pgRNA and then newly synthesized minus-sense single-stranded DNA are protected from deaminase by interaction with the virus capsid; during plus-strand synthesis, when enough dsDNA has been synthesized to displace the remaining minus strand from the capsid surface, the single-stranded DNA becomes deaminase sensitive. IMPORTANCE Host-induced mutation of the HBV genome by APOBEC proteins may be a path to clearing the virus. We examined cytidine-to-thymidine mutations in the genomes of HBV particles grown in the presence or absence of overexpressed APOBEC proteins. We found that genomes were subjected to deamination activity during reverse transcription

  11. Modification of PSf/SPSf Blended Porous Support for Improving the Reverse Osmosis Performance of Aromatic Polyamide Thin Film Composite Membranes

    Directory of Open Access Journals (Sweden)

    Li-Fen Liu

    2018-06-01

    Full Text Available In this study, modification of polysulfone (PSf/sulfonated polysulfone (SPSf blended porous ultrafiltration (UF support membranes was proposed to improve the reverse osmosis (RO performance of aromatic polyamide thin film composite (TFC membranes. The synergistic effects of solvent, polymer concentration, and SPSf doping content in the casting solution were investigated systematically on the properties of both porous supports and RO membranes. SEM and AFM were combined to characterize the physical properties of the membranes, including surface pore natures (porosity, mean pore radius, surface morphology, and section structure. A contact angle meter was used to analyze the membrane surface hydrophilicity. Permeate experiments were carried out to evaluate the separation performances of the membranes. The results showed that the PSf/SPSf blended porous support modified with 6 wt % SPSf in the presence of DMF and 14 wt % PSf had higher porosity, bigger pore diameter, and a rougher and more hydrophilic surface, which was more beneficial for fabrication of a polyamide TFC membrane with favorable reverse osmosis performance. This modified PSf/SPSf support endowed the RO membrane with a more hydrophilic surface, higher water flux (about 1.2 times, as well as a slight increase in salt rejection than the nascent PSf support. In a word, this work provides a new facile method to improve the separation performance of polyamide TFC RO membranes via the modification of conventional PSf porous support with SPSf.

  12. Modification of a Volume-Overload Heart Failure Model to Track Myocardial Remodeling and Device-Related Reverse Remodeling

    Science.gov (United States)

    Tuzun, Egemen; Bick, Roger; Kadipasaoglu, Cihan; Conger, Jeffrey L.; Poindexter, Brian J.; Gregoric, Igor D.; Frazier, O. H.; Towbin, Jeffrey A.; Radovancevic, Branislav

    2011-01-01

    Purpose. To provide an ovine model of ventricular remodeling and reverse remodeling by creating congestive heart failure (CHF) and then treating it by implanting a left ventricular assist device (LVAD). Methods. We induced volume-overload heart failure in 2 sheep; 20 weeks later, we implanted an LVAD and assessed recovery 11 weeks thereafter. We examined changes in histologic and hemodynamic data and levels of cellular markers of CHF. Results. After CHF induction, we found increases in LV end-diastolic pressure, LV systolic and diastolic dimensions, wall thickness, left atrial diameter, and atrial natriuretic protein (ANP) and endothelin-1 (ET-1) levels; β-adrenergic receptor (BAR) and dystrophin expression decreased markedly. Biopsies confirmed LV remodeling. After LVAD support, LV systolic and diastolic dimensions, wall thickness, and mass, and ANP and ET-1 levels decreased. Histopathologic and hemodynamic markers improved, and BAR and dystrophin expression normalized. Conclusions. We describe a successful sheep model for ventricular and reverse remodeling. PMID:22347659

  13. Reversible Thermoset Adhesives

    Science.gov (United States)

    Mac Murray, Benjamin C. (Inventor); Tong, Tat H. (Inventor); Hreha, Richard D. (Inventor)

    2016-01-01

    Embodiments of a reversible thermoset adhesive formed by incorporating thermally-reversible cross-linking units and a method for making the reversible thermoset adhesive are provided. One approach to formulating reversible thermoset adhesives includes incorporating dienes, such as furans, and dienophiles, such as maleimides, into a polymer network as reversible covalent cross-links using Diels Alder cross-link formation between the diene and dienophile. The chemical components may be selected based on their compatibility with adhesive chemistry as well as their ability to undergo controlled, reversible cross-linking chemistry.

  14. Surface modification of reverse osmosis desalination membranes by thin-film coatings deposited by initiated chemical vapor deposition

    Energy Technology Data Exchange (ETDEWEB)

    Ozaydin-Ince, Gozde, E-mail: gozdeince@sabanciuniv.edu [Department of Chemical Engineering, Massachusetts Institute of Technology, Cambridge, MA 02139 (United States); Matin, Asif, E-mail: amatin@mit.edu [Department of Mechanical Engineering, King Fahd University of Petroleum and Minerals, Dhahran 31261 (Saudi Arabia); Khan, Zafarullah, E-mail: zukhan@mit.edu [Department of Mechanical Engineering, King Fahd University of Petroleum and Minerals, Dhahran 31261 (Saudi Arabia); Zaidi, S.M. Javaid, E-mail: zaidismj@kfupm.edu.sa [Department of Mechanical Engineering, King Fahd University of Petroleum and Minerals, Dhahran 31261 (Saudi Arabia); Gleason, Karen K., E-mail: kkgleasn@mit.edu [Department of Chemical Engineering, Massachusetts Institute of Technology, Cambridge, MA 02139 (United States)

    2013-07-31

    Thin-film polymeric reverse osmosis membranes, due to their high permeation rates and good salt rejection capabilities, are widely used for seawater desalination. However, these membranes are prone to biofouling, which affects their performance and efficiency. In this work, we report a method to modify the membrane surface without damaging the active layer or significantly affecting the performance of the membrane. Amphiphilic copolymer films of hydrophilic hydroxyethylmethacrylate and hydrophobic perfluorodecylacrylate (PFA) were synthesized and deposited on commercial RO membranes using an initiated chemical vapor deposition technique which is a polymer deposition technique that involves free-radical polymerization initiated by gas-phase radicals. Relevant surface characteristics such as hydrophilicity and roughness could be systematically controlled by varying the polymer chemistry. Increasing the hydrophobic PFA content in the films leads to an increase in the surface roughness and hydrophobicity. Furthermore, the surface morphology studies performed using the atomic force microscopy show that as the thickness of the coating increases average surface roughness increases. Using this knowledge, the coating thickness and chemistry were optimized to achieve high permeate flux and to reduce cell attachment. Results of the static bacterial adhesion tests show that the attachment of bacterial cells is significantly reduced on the coated membranes. - Highlights: • Thin films are deposited on reverse osmosis membranes. • Amphiphilic thin films are resistant to protein attachment. • The permeation performance of the membranes is not affected by the coating. • The thin film coatings delayed the biofouling.

  15. Hydrogels Based on Dynamic Covalent and Non Covalent Bonds: A Chemistry Perspective

    Directory of Open Access Journals (Sweden)

    Francesco Picchioni

    2018-03-01

    Full Text Available Hydrogels based on reversible covalent bonds represent an attractive topic for research at both academic and industrial level. While the concept of reversible covalent bonds dates back a few decades, novel developments continue to appear in the general research area of gels and especially hydrogels. The reversible character of the bonds, when translated at the general level of the polymeric network, allows reversible interaction with substrates as well as responsiveness to variety of external stimuli (e.g., self-healing. These represent crucial characteristics in applications such as drug delivery and, more generally, in the biomedical world. Furthermore, the several possible choices that can be made in terms of reversible interactions generate an almost endless number of possibilities in terms of final product structure and properties. In the present work, we aim at reviewing the latest developments in this field (i.e., the last five years by focusing on the chemistry of the systems at hand. As such, this should allow molecular designers to develop a toolbox for the synthesis of new systems with tailored properties for a given application.

  16. Reverse osmosis membrane composition, structure and performance modification by bisulphite, iron(III), bromide and chlorite exposure.

    Science.gov (United States)

    Ferrer, O; Gibert, O; Cortina, J L

    2016-10-15

    Reverse osmosis (RO) membrane exposure to bisulphite, chlorite, bromide and iron(III) was assessed in terms of membrane composition, structure and performance. Membrane composition was determined by Rutherford backscattering spectrometry (RBS) and membrane performance was assessed by water and chloride permeation, using a modified version of the solution-diffusion model. Iron(III) dosage in presence of bisulphite led to an autooxidation of the latter, probably generating free radicals which damaged the membrane. It comprised a significant raise in chloride passage (chloride permeation coefficient increased 5.3-5.1 fold compared to the virgin membrane under the conditions studied) rapidly. No major differences in terms of water permeability and membrane composition were observed. Nevertheless, an increase in the size of the network pores, and a raise in the fraction of aggregate pores of the polyamide (PA) layer were identified, but no amide bond cleavage was observed. These structural changes were therefore, in accordance with the transport properties observed. Copyright © 2016 Elsevier Ltd. All rights reserved.

  17. β(3) adrenergic stimulation of the cardiac Na+-K+ pump by reversal of an inhibitory oxidative modification.

    Science.gov (United States)

    Bundgaard, Henning; Liu, Chia-Chi; Garcia, Alvaro; Hamilton, Elisha J; Huang, Yifei; Chia, Karin K M; Hunyor, Stephen N; Figtree, Gemma A; Rasmussen, Helge H

    2010-12-21

    inhibition of L-type Ca(2+) current contributes to negative inotropy of β(3) adrenergic receptor (β(3) AR) activation, but effects on other determinants of excitation-contraction coupling are not known. Of these, the Na(+)-K(+) pump is of particular interest because of adverse effects attributed to high cardiac myocyte Na(+) levels and upregulation of the β(3) AR in heart failure. we voltage clamped rabbit ventricular myocytes and identified electrogenic Na(+)-K(+) pump current (I(p)) as the shift in holding current induced by ouabain. The synthetic β(3) AR agonists BRL37344 and CL316,243 and the natural agonist norepinephrine increased I(p). Pump stimulation was insensitive to the β(1)/β(2) AR antagonist nadolol and the protein kinase A inhibitor H-89 but sensitive to the β(3) AR antagonist L-748,337. Blockade of nitric oxide synthase abolished pump stimulation and an increase in fluorescence of myocytes loaded with a nitric oxide-sensitive dye. Exposure of myocytes to β(3) AR agonists decreased β(1) Na(+)-K(+) pump subunit glutathionylation, an oxidative modification that causes pump inhibition. The in vivo relevance of this was indicated by an increase in myocardial β(1) pump subunit glutathionylation with elimination of β(3) AR-mediated signaling in β(3) AR(-/-) mice. The in vivo effect of BRL37344 on contractility of the nonfailing and failing heart in sheep was consistent with a beneficial effect of Na(+)-K(+) pump stimulation in heart failure. the β(3) AR mediates decreased β(1) subunit glutathionylation and Na(+)-K(+) pump stimulation in the heart. Upregulation of the receptor in heart failure may be a beneficial mechanism that facilitates the export of excess Na(+).

  18. Covalent organic polymer functionalization of activated carbon surfaces through acyl chloride for environmental clean-up

    DEFF Research Database (Denmark)

    Mines, Paul D.; Thirion, Damien; Uthuppu, Basil

    2017-01-01

    Nanoporous networks of covalent organic polymers (COPs) are successfully grafted on the surfaces of activated carbons, through a series of surface modification techniques, including acyl chloride formation by thionyl chloride. Hybrid composites of activated carbon functionalized with COPs exhibit...

  19. Posttranslational Modification Biology of Glutamate Receptors and Drug Addiction

    Directory of Open Access Journals (Sweden)

    Li-Min eMao

    2011-03-01

    Full Text Available Posttranslational covalent modifications of glutamate receptors remain a hot topic. Early studies have established that this family of receptors, including almost all ionotropic and metabotropic glutamate receptor subtypes, undergoes active phosphorylation at serine, threonine, or tyrosine residues on their intracellular domains. Recent evidence identifies several glutamate receptor subtypes to be direct substrates for palmitoylation at cysteine residues. Other modifications such as ubiquitination and sumoylation at lysine residues also occur to certain glutamate receptors. These modifications are dynamic and reversible in nature and are regulatable by changing synaptic inputs. The regulated modifications significantly impact the receptor in many ways, including interrelated changes in biochemistry (synthesis, subunit assembling and protein-protein interactions, subcellular redistribution (trafficking, endocytosis, synaptic delivery and clustering, and physiology, usually associated with changes in synaptic plasticity. Glutamate receptors are enriched in the striatum and cooperate closely with dopamine to regulate striatal signaling. Emerging evidence shows that modification processes of striatal glutamate receptors are sensitive to addictive drugs, such as psychostimulants (cocaine and amphetamines. Altered modifications are believed to be directly linked to enduring receptor/synaptic plasticity and drug-seeking. This review summarizes several major types of modifications of glutamate receptors and analyzes the role of these modifications in striatal signaling and in the pathogenesis of psychostimulant addiction.

  20. Antiparallel Dynamic Covalent Chemistries.

    Science.gov (United States)

    Matysiak, Bartosz M; Nowak, Piotr; Cvrtila, Ivica; Pappas, Charalampos G; Liu, Bin; Komáromy, Dávid; Otto, Sijbren

    2017-05-17

    The ability to design reaction networks with high, but addressable complexity is a necessary prerequisite to make advanced functional chemical systems. Dynamic combinatorial chemistry has proven to be a useful tool in achieving complexity, however with some limitations in controlling it. Herein we introduce the concept of antiparallel chemistries, in which the same functional group can be channeled into one of two reversible chemistries depending on a controllable parameter. Such systems allow both for achieving complexity, by combinatorial chemistry, and addressing it, by switching from one chemistry to another by controlling an external parameter. In our design the two antiparallel chemistries are thiol-disulfide exchange and thio-Michael addition, sharing the thiol as the common building block. By means of oxidation and reduction the system can be reversibly switched from predominantly thio-Michael chemistry to predominantly disulfide chemistry, as well as to any intermediate state. Both chemistries operate in water, at room temperature, and at mildly basic pH, which makes them a suitable platform for further development of systems chemistry.

  1. Facile fabrication of highly controllable gating systems based on the combination of inverse opal structure and dynamic covalent chemistry.

    Science.gov (United States)

    Wang, Chen; Yang, Haowei; Tian, Li; Wang, Shiqiang; Gao, Ning; Zhang, Wanlin; Wang, Peng; Yin, Xianpeng; Li, Guangtao

    2017-06-01

    A three-dimensional (3D) inverse opal with periodic and porous structures has shown great potential for applications not only in optics and optoelectronics, but also in functional membranes. In this work, the benzaldehyde group was initially introduced into a 3D nanoporous inverse opal, serving as a platform for fabricating functional membranes. By employing the dynamic covalent approach, a highly controllable gating system was facilely fabricated to achieve modulable and reversible transport features. It was found that the physical/chemical properties and pore size of the gating system could easily be regulated through post-modification with amines. As a demonstration, the gated nanopores were modified with three kinds of amines to control the wettability, surface charge and nanopore size which in turn was exploited to achieve selective mass transport, including hydrophobic molecules, cations and anions, and the transport with respect to the physical steric hindrance. In particular, the gating system showed extraordinary reversibility and could recover to its pristine state by simply changing pH values. Due to the unlimited variety provided by the Schiff base reaction, the inverse opal described here exhibits a significant extendibility and could be easily post-modified with stimuli-responsive molecules for special purposes. Furthermore, this work can be extended to employ other dynamic covalent routes, for example Diels-Alder, ester exchange and disulfide exchange-based routes.

  2. Covalent and non-covalent functionalization and solubilization of ...

    Indian Academy of Sciences (India)

    Wintec

    photographs of the dispersions of amide-functio- nalized DWNTs in dichloromethane and tetrahydro- furan. In figure 3b, we show a TEM image of DWNTs after covalent functionalization. The images are not as sharp after functionalization as in the case of pris- tine nanotubes (figure 3a), and the bundles seem to be intact.

  3. Posttranslational modification of Klebsiella pneumoniae flavodoxin by covalent attachment of coenzyme A, shown by sup 31 P NMR and electrospray mass spectrometry, prevents electron transfer from the nifJ protein to nitrogenase. A possible new regulatory mechanism for biological nitrogen fixation

    Energy Technology Data Exchange (ETDEWEB)

    Thorneley, R.N.F.; Ashby, G.A.; Drummond, M.H.; Eady, R.R.; Huff, S.; Macdonald, C.J. (Univ. of Sussex, Brighton (United Kingdom)); Abell, C.; Schneier, A. (Univ. Chemical Lab., Cambridge (United Kingdom))

    1992-02-04

    A strain of Escherichia coli (71-18) that produces ca. 15% of its soluble cytoplasmic protein as a flavodoxin, the Klebsiella pneumoniae nifF gene product, has been constructed. The flavodoxin was purified using FPLC and resolved into two forms, designated KpFldI and KpFldII, which were shown to have identical N-terminal amino acid sequences (30 residues) in agreement with that predicted by the K. pneumoniae nifF DNA sequence. {sup 31}P NMR, electrospray mass spectrometry, UV-visible spectra, and thiol group estimations showed that the single cysteine residue (position 68) of KpFldI is posttranslationally modified in KpFldII by the covalent, mixed disulfide, attachment of coenzyme A. KpFldII was inactive as an electron carrier between the K. pneumoniae nifJ product (a pyruvate-flavodoxin oxidoreductase) and K. pneumoniae nifH product (the Fe-protein of nitrogenase). This novel posttranslational modification of a flavodoxin is discussed in terms of the regulation of nitrogenase activity in vivo in response to the level of dissolved O{sub 2} and the carbon status of diazotrophic cultures.

  4. Modificações vocais acústicas produzidas pela fonação reversa Acoustic vocal modifications produced by reverse phonation

    Directory of Open Access Journals (Sweden)

    Leila Susana Finger

    2009-01-01

    Full Text Available OBJETIVO: Descrever as modificações vocais acústicas e as sensações ocorridas após a técnica vocal de fonação reversa em mulheres adultas jovens, sem queixas vocais e com laringe normal. MÉTODOS: Trinta e duas mulheres adultas jovens submeteram-se à avaliação otorrinolaringológica e triagem fonoaudiológica para descartar possíveis alterações que pudessem interferir nos resultados da pesquisa; tiveram amostras vocais coletadas antes e após realizarem três séries de 15 repetições de fonação reversa, em tempo máximo de fonação com tom e intensidade habituais, e 30 segundos de repouso passivo entre cada série. Após, responderam a um questionário referente às sensações percebidas. A análise vocal acústica foi realizada através do software Praat (versão 4.6.10 e os dados analisados por meio da estatística descritiva e pelo teste de Wilcoxon, com nível de significância de 5%. RESULTADOS: Aumento estatisticamente significativo da frequência fundamental e da frequência máxima; diminuição da frequência mínima; aumento das medidas de Jitter, exceto da medida de Jitter local-absoluto que diminuiu; diminuição das medidas de Shimmer, relação ruído/harmônico (NHR e relação harmônico/ruído (HNR; e predomínio das sensações positivas. CONCLUSÃO: A fonação reversa pareceu promover efeito positivo sobre a vibração da mucosa das pregas vocais e sobre o seu alongamento. Sugere efeito sobre a musculatura, favorecendo mudanças de frequência fundamental; e sobre sua homogeneização e modificação da camada de muco. Além disso, promoveu melhora global do sinal vocal e das sensações durante sua produção.PURPOSE: To describe the acoustic vocal modifications and the sensations occurred after the reverse phonation technique in young adult women without vocal complaints and with normal larynx. METHODS: Thirty-two young adult women were submitted to otorhinolaryngologic and speech-language pathology

  5. Cell signaling, post-translational protein modifications and NMR spectroscopy

    International Nuclear Information System (INIS)

    Theillet, Francois-Xavier; Smet-Nocca, Caroline; Liokatis, Stamatios; Thongwichian, Rossukon; Kosten, Jonas; Yoon, Mi-Kyung; Kriwacki, Richard W.; Landrieu, Isabelle; Lippens, Guy; Selenko, Philipp

    2012-01-01

    Post-translationally modified proteins make up the majority of the proteome and establish, to a large part, the impressive level of functional diversity in higher, multi-cellular organisms. Most eukaryotic post-translational protein modifications (PTMs) denote reversible, covalent additions of small chemical entities such as phosphate-, acyl-, alkyl- and glycosyl-groups onto selected subsets of modifiable amino acids. In turn, these modifications induce highly specific changes in the chemical environments of individual protein residues, which are readily detected by high-resolution NMR spectroscopy. In the following, we provide a concise compendium of NMR characteristics of the main types of eukaryotic PTMs: serine, threonine, tyrosine and histidine phosphorylation, lysine acetylation, lysine and arginine methylation, and serine, threonine O-glycosylation. We further delineate the previously uncharacterized NMR properties of lysine propionylation, butyrylation, succinylation, malonylation and crotonylation, which, altogether, define an initial reference frame for comprehensive PTM studies by high-resolution NMR spectroscopy.

  6. Covalent and non-covalent chemical engineering of actin for biotechnological applications.

    Science.gov (United States)

    Kumar, Saroj; Mansson, Alf

    2017-11-15

    The cytoskeletal filaments are self-assembled protein polymers with 8-25nm diameters and up to several tens of micrometres length. They have a range of pivotal roles in eukaryotic cells, including transportation of intracellular cargoes (primarily microtubules with dynein and kinesin motors) and cell motility (primarily actin and myosin) where muscle contraction is one example. For two decades, the cytoskeletal filaments and their associated motor systems have been explored for nanotechnological applications including miniaturized sensor systems and lab-on-a-chip devices. Several developments have also revolved around possible exploitation of the filaments alone without their motor partners. Efforts to use the cytoskeletal filaments for applications often require chemical or genetic engineering of the filaments such as specific conjugation with fluorophores, antibodies, oligonucleotides or various macromolecular complexes e.g. nanoparticles. Similar conjugation methods are also instrumental for a range of fundamental biophysical studies. Here we review methods for non-covalent and covalent chemical modifications of actin filaments with focus on critical advantages and challenges of different methods as well as critical steps in the conjugation procedures. We also review potential uses of the engineered actin filaments in nanotechnological applications and in some key fundamental studies of actin and myosin function. Finally, we consider possible future lines of investigation that may be addressed by applying chemical conjugation of actin in new ways. Copyright © 2017 The Authors. Published by Elsevier Inc. All rights reserved.

  7. Covalent modification of cytochrome c by reactive metabolites of furan.

    Science.gov (United States)

    Phillips, Martin B; Sullivan, Mathilde M; Villalta, Peter W; Peterson, Lisa A

    2014-01-21

    Metabolism of the hepatotoxicant furan leads to protein adduct formation in the target organ. The initial bioactivation step involves cytochrome P450-catalyzed oxidation of furan, generating cis-2-butene-1,4-dial (BDA). BDA reacts with lysine to form pyrrolin-2-one adducts. Metabolic studies indicate that BDA also reacts with glutathione (GSH) to generate 2-(S-glutathionyl)butanedial (GSH-BDA), which then reacts with lysine to form GSH-BDA-lysine cross-links. To explore the relative reactivity of these two reactive intermediates, cytochrome c was reacted with BDA in the presence and absence of GSH. As judged by MALDI-TOF mass spectrometry, BDA reacts extensively with cytochrome c to form adducts that add 66 Da to the protein, consistent with the formation of pyrrolinone adducts. Addition of GSH to the reaction mixture reduced the overall extent of adduct formation. The mass of the adducted protein was shifted by 355 Da as expected for GSH-BDA-protein cross-link formation. LC-MS/MS analysis of the tryptic digests of the alkylated protein indicated that the majority of adducts occurred on lysine residues, with BDA reacting less selectively than GSH-BDA. Both types of adducts may contribute to the toxic effects of furan.

  8. Covalent Modification of Cytochrome C by Reactive Metabolites of Furan

    OpenAIRE

    Phillips, Martin B.; Sullivan, Mathilde M.; Villalta, Peter W.; Peterson, Lisa A.

    2013-01-01

    Metabolism of the hepatotoxicant furan leads to protein adduct formation in the target organ. The initial bioactivation step involves cytochrome P450-catalyzed oxidation of furan, generating cis-2-butene-1,4-dial (BDA). BDA reacts with lysine to form pyrrolin-2-one adducts. Metabolic studies indicate that BDA also reacts with glutathione (GSH) to generate 2-(S-glutathionyl)butanedial (GSH-BDA), which then reacts with lysine to form GSH-BDA-lysine cross-links. To explore the relative reactivit...

  9. Dimeric DNA Aptamer Complexes for High-capacity–targeted Drug Delivery Using pH-sensitive Covalent Linkages

    Directory of Open Access Journals (Sweden)

    Olcay Boyacioglu

    2013-01-01

    Full Text Available Treatment with doxorubicin (Dox results in serious systemic toxicities that limit effectiveness for cancer treatment and cause long-term health issues for cancer patients. We identified a new DNA aptamer to prostate-specific membrane antigen (PSMA using fixed sequences to promote Dox binding and developed dimeric aptamer complexes (DACs for specific delivery of Dox to PSMA+ cancer cells. DACs are stable under physiological conditions and are internalized specifically into PSMA+ C4-2 cells with minimal uptake into PSMA-null PC3 cells. Cellular internalization of DAC was demonstrated by confocal microscopy and flow cytometry. Covalent modification of DAC with Dox (DAC-D resulted in a complex with stoichiometry ~4:1. Dox was covalently bound in DAC-D using a reversible linker that promotes covalent attachment of Dox to genomic DNA following cell internalization. Dox was released from the DAC-D under physiological conditions with a half-life of 8 hours, sufficient for in vivo targeting. DAC-D was used to selectively deliver Dox to C4-2 cells with endosomal release and nuclear localization of Dox. DAC-D was selectively cytotoxic to C4-2 cells with similar cytotoxicity as the molar equivalent of free-Dox. In contrast, DAC-D displayed minimal cytotoxicity to PC3 cells, demonstrating the complex displays a high degree of selectivity for PSMA+ cells. DAC-D displays specificity and stability features that may be useful for improved delivery of Dox selectively to malignant tissue in vivo.

  10. Electron population uncertainty and atomic covalency

    International Nuclear Information System (INIS)

    Chesnut, D.B.

    2006-01-01

    The atoms-in-molecules (AIM) index of atomic covalency is directly related to the AIM atomic population uncertainty. The covalent bond order, delocalization index, and, therefore, the atomic covalency are maximal when electron pairs are equally shared by the atoms involved. When polarization effects are present, these measures of covalent bond character decrease. We present atomic covalences for the single- and double-heavy atom hydrides of elements of the first and second low rows of the periodic table to illustrate these effects. Some usual behavior is seen in hydrogen-bridged species due in some cases to stronger than expected multicenter bonds and in other cases to many atoms contributing to the covalency index

  11. Dynamic covalent gels assembled from small molecules:from discrete gelators to dynamic covalent polymers

    Institute of Scientific and Technical Information of China (English)

    Jian-Yong Zhang; Li-Hua Zeng; Juan Feng

    2017-01-01

    Dynamic covalent chemistry has emerged recently to be a powerful tool to construct functional materials.This article reviews the progress in the research and development of dynamic covalent chemistry in gels assembled from small molecules.First dynamic covalent reactions used in gels are reviewed to understand the dynamic covalent bonding.Afterwards the catalogues of dynamic covalent gels are reviewed according to the nature of gelators and the interactions between gelators.Dynamic covalent bonding can be involved to form low molecular weight gelators.Low molecular weight molecules with multiple functional groups react to form dynamic covalent cross-linked polymers and act as gelators.Two catalogues of gels show different properties arising from their different structures.This review aims to illustrate the structure-property relationships of these dynamic covalent gels.

  12. Dynamic covalent chemistry of bisimines at the solid/liquid interface monitored by scanning tunnelling microscopy.

    Science.gov (United States)

    Ciesielski, Artur; El Garah, Mohamed; Haar, Sébastien; Kovaříček, Petr; Lehn, Jean-Marie; Samorì, Paolo

    2014-11-01

    Dynamic covalent chemistry relies on the formation of reversible covalent bonds under thermodynamic control to generate dynamic combinatorial libraries. It provides access to numerous types of complex functional architectures, and thereby targets several technologically relevant applications, such as in drug discovery, (bio)sensing and dynamic materials. In liquid media it was proved that by taking advantage of the reversible nature of the bond formation it is possible to combine the error-correction capacity of supramolecular chemistry with the robustness of covalent bonding to generate adaptive systems. Here we show that double imine formation between 4-(hexadecyloxy)benzaldehyde and different α,ω-diamines as well as reversible bistransimination reactions can be achieved at the solid/liquid interface, as monitored on the submolecular scale by in situ scanning tunnelling microscopy imaging. Our modular approach enables the structurally controlled reversible incorporation of various molecular components to form sophisticated covalent architectures, which opens up perspectives towards responsive multicomponent two-dimensional materials and devices.

  13. Reversible Modification of Adenomatous Polyposis Coli (APC) with K63-linked Polyubiquitin Regulates the Assembly and Activity of the β-Catenin Destruction Complex

    Science.gov (United States)

    Tran, Hoanh; Polakis, Paul

    2012-01-01

    The adenomatous polyposis coli (APC) tumor suppressor forms a complex with Axin and GSK3β to promote the phosphorylation and degradation of β-catenin, a key co-activator of Wnt-induced transcription. Here, we establish that APC is modified predominantly with K63-linked ubiquitin chains when it is bound to Axin in unstimulated HEK293 cells. Wnt3a stimulation induced a time-dependent loss of K63-polyubiquitin adducts from APC, an effect synchronous with the dissociation of Axin from APC and the stabilization of cytosolic β-catenin. RNAi-mediated depletion of Axin or β-catenin, which negated the association between APC and Axin, resulted in the absence of K63-adducts on APC. Overexpression of wild-type and phosphodegron-mutant β-catenin, combined with analysis of thirteen human cancer cell lines that harbor oncogenic mutations in APC, Axin, or β-catenin, support the hypothesis that a fully assembled APC-Axin-GSK3β-phospho-β-catenin complex is necessary for the K63-polyubiquitylation of APC. Intriguingly, the degree of this modification on APC appears to correlate inversely with the levels of β-catenin in cells. Together, our results indicate that K63-linked polyubiquitin adducts on APC regulate the assembly and/or efficiency of the β-catenin destruction complex. PMID:22761442

  14. Disorder phenomena in covalent semiconductors

    International Nuclear Information System (INIS)

    Popescu, M.A.

    1975-01-01

    The structure of the amorphous semiconductors has been investigated by means of X-ray diffraction and by computer simulation of random network models. Amorphous germanium contains mainly five and six-membered rings of atoms. In glassy state, the ternary compounds A 2 B 4 C 2 5 , such as CdGeAs 2 contain only even rings of atoms (six-membered and eight-membered rings). In the memory glasses of the type A 2 B 4 C 2 5 , such as GeAs 2 Te 7 , the valency state of every element is that from the crystal and important van der Waals forces are effective in the network. No Ge-Ge, Ge-As and As-As bonds are formed. The high pressure forms of the germanium have been simulated by computer. The force constants of the covalent bonds in Ge III and Ge IV differ from those in Ge I. The bond bending force constant decreases rapidly when the density of the crystal increases, a fact which has been imparted to a reduction of the sp 3 hybridization. The compressibility curve of the Ge I has been explained. The effect of the radial and uniaxial deformation on the non-crystalline networks has been studied. The compressibility of the amorphous germanium is by 1.5 per cent greater than that of crystalline germanium. The Poisson coefficient for a-Ge network is 0.233. The structure of the As 2 S 3 glass doped with different amounts of germanium (up to 40 at. per cent) and silver (up to 12 at. per cent) has been investigated. The As 2 S 3 Gesub(x) compositions are constituted from a disordered packing of structural units whose chemical composition and relative proportion in the glass essentially depends on the germanium content. (author)

  15. Covalent bonding in heavy metal oxides

    Energy Technology Data Exchange (ETDEWEB)

    Bagus, Paul S.; Nelin, Connie J.; Hrovat, Dave A.; Ilton, Eugene S.

    2017-04-07

    Novel theoretical methods were used to quantify the magnitude and the energetic contributions of 4f/5f-O2p and 5d/6d-O2p interactions to covalent bonding in lanthanide and actinide oxides. Although many analyses have neglected the involvement of the frontier d orbitals, the present study shows that f and d covalency are of comparable importance. Two trends are identified. As is expected, the covalent mixing is larger when the nominal oxidation state is higher. More subtly, the importance of the nf covalent mixing decreases sharply relative to (n+1)d as the nf occupation increases. Atomic properties of the metal cations that drive these trends are identified.

  16. Covalently linked bisporphyrins bearing tetraphenylporphyrin and ...

    Indian Academy of Sciences (India)

    Covalently linked bisporphyrins bearing tetraphenylporphyrin and perbromoporphyrin units: Synthesis and their properties. Puttaiah Bhyrappa V Krishnan ... yields of the TPP moiety. Electrochemical redox and fluorescence data seem to suggest the possible existence of intramolecular interactions in these bisporphyrins.

  17. Photoreversible Covalent Hydrogels for Soft-Matter Additive Manufacturing.

    Science.gov (United States)

    Kabb, Christopher P; O'Bryan, Christopher S; Deng, Christopher C; Angelini, Thomas E; Sumerlin, Brent S

    2018-05-16

    Reversible covalent chemistry provides access to robust materials with the ability to be degraded and reformed upon exposure to an appropriate stimulus. Photoresponsive units are attractive for this purpose, as the spatial and temporal application of light is easily controlled. Coumarin derivatives undergo a [2 + 2] cycloaddition upon exposure to long-wave UV irradiation (365 nm), and this process can be reversed using short-wave UV light (254 nm). Therefore, polymers cross-linked by coumarin groups are excellent candidates as reversible covalent gels. In this work, copolymerization of coumarin-containing monomers with the hydrophilic comonomer N, N-dimethylacrylamide yielded water-soluble, linear polymers that could be cured with long-wave UV light into free-standing hydrogels, even in the absence of a photoinitiator. Importantly, the gels were reverted back to soluble copolymers upon short-wave UV irradiation. This process could be cycled, allowing for recycling and remolding of the hydrogel into additional shapes. Further, this hydrogel can be imprinted with patterns through a mask-based, post-gelation photoetching method. Traditional limitations of this technique, such as the requirement for uniform etching in one direction, have been overcome by combining these materials with a soft-matter additive manufacturing methodology. In a representative application of this approach, we printed solid structures in which the interior coumarin-cross-linked gel is surrounded by a nondegradable gel. Upon exposure to short-wave UV irradiation, the coumarin-cross-linked gel was reverted to soluble prepolymers that were washed away to yield hollow hydrogel objects.

  18. From covalent bonding to coalescence of metallic nanorods

    Directory of Open Access Journals (Sweden)

    Lee Soohwan

    2011-01-01

    Full Text Available Abstract Growth of metallic nanorods by physical vapor deposition is a common practice, and the origin of their dimensions is a characteristic length scale that depends on the three-dimensional Ehrlich-Schwoebel (3D ES barrier. For most metals, the 3D ES barrier is large so the characteristic length scale is on the order of 200 nm. Using density functional theory-based ab initio calculations, this paper reports that the 3D ES barrier of Al is small, making it infeasible to grow Al nanorods. By analyzing electron density distributions, this paper shows that the small barrier is the result of covalent bonding in Al. Beyond the infeasibility of growing Al nanorods by physical vapor deposition, the results of this paper suggest a new mechanism of controlling the 3D ES barrier and thereby nanorod growth. The modification of local degree of covalent bonding, for example, via the introduction of surfactants, can increase the 3D ES barrier and promote nanorod growth, or decrease the 3D ES barrier and promote thin film growth.

  19. CovalentDock Cloud: a web server for automated covalent docking.

    Science.gov (United States)

    Ouyang, Xuchang; Zhou, Shuo; Ge, Zemei; Li, Runtao; Kwoh, Chee Keong

    2013-07-01

    Covalent binding is an important mechanism for many drugs to gain its function. We developed a computational algorithm to model this chemical event and extended it to a web server, the CovalentDock Cloud, to make it accessible directly online without any local installation and configuration. It provides a simple yet user-friendly web interface to perform covalent docking experiments and analysis online. The web server accepts the structures of both the ligand and the receptor uploaded by the user or retrieved from online databases with valid access id. It identifies the potential covalent binding patterns, carries out the covalent docking experiments and provides visualization of the result for user analysis. This web server is free and open to all users at http://docking.sce.ntu.edu.sg/.

  20. Modification of the magnetic field structure in the vicinity of the x-points by the strong mirror field for a field-reversed configuration (FRC) with the Thick Edge-Layer plasma

    International Nuclear Information System (INIS)

    Suzuki, Yukihisa; Okada, Shigefumi; Goto, Seiichi

    2003-01-01

    Modification of the magnetic field structure in the vicinity of the x-points and changes of the separatrix shape are investigated under the pressure effects due to an edge-layer plasma together with a mirror field by the two-dimensional (2-D) MHD equilibrium solutions of field-reversed configuration (FRC) obtained from the Grad-Shafranov equation. To explore the coupling pressure effects caused by edge-layer plasma and mirror field, the equilibrium calculations are performed by the combinations of several values of mirror ratio (R m ) and of edge-layer width (δ), respectively. A summary of results for present study is as follows. In the condition of weak mirror field (1.0 m m > 1.6, ψ=0 surface never opens up for any δ. These original results make it clear that large magnetic curvature produced by the strong mirror field enhances the magnetic stress around the x-point, so that the ends of FRC are effectively sustained by this enhanced magnetic stress, which counteracts the edge-layer plasma pressure effect. (author)

  1. Effect of photocurrent enhancement in porphyrin–graphene covalent hybrids

    International Nuclear Information System (INIS)

    Tang, Jianguo; Niu, Lin; Liu, Jixian; Wang, Yao; Huang, Zhen; Xie, Shiqiang; Huang, Linjun; Xu, Qingsong; Wang, Yuan; Belfiore, Laurence A.

    2014-01-01

    Graphene oxide (GO) sheets were covalently functionalized with 5-p-aminophenyl-10,15,20-triphenylporphyrin (NH 2 TPP) by an amidation reaction between the amino group in NH 2 TPP and carboxyl groups in GO. The Fourier transform infrared spectroscopy, nuclear magnetic resonance, scanning and transmission electron microscopies reveal that NH 2 TPP covalent bonds form on the double surface of graphene oxide sheets, generating a unique nano-framework, i.e., NH 2 TPP-graphene-NH 2 TPP. Its UV–visible spectroscopy reveals that the absorption spectrum is not a linear superposition of the spectra of NH 2 TPP and graphene oxide, because a 59 nm red shift of the strong graphene oxide absorption is observed from 238 to 297 nm, with significant spectral broadening between 300 and 700 nm. Fluorescence emission spectroscopy indicates efficient quenching of NH 2 TPP photoluminescence in this hybrid material, suggesting that photo-induced electron transfer occurs at the interface between NH 2 TPP and GO. A reversible on/off photo-current density of 47 mA/cm 2 is observed when NH 2 TPP-graphene-NH 2 TPP hybrid sandwiches are subjected to pulsed white-light illumination. Covalently-bound porphyrins decrease the optical HOMO/LUMO band gap of graphene oxide by ≈ 1 eV, according to UV–visible spectroscopy. Cyclic voltammetry predicts a small HOMO/LUMO band gap of 0.84 eV for NH 2 TPP-graphene-NH 2 TPP hybrid sandwiches, which is consistent with efficient electron transfer and fluorescence quenching. - Highlights: • Porphyrins are covalently bound to sheets of graphene oxide via an amidation reaction. • The formed hetero-junction interface decreases the optical band gap of graphene oxide. • Cyclic voltammetry predicts a graphene oxide band gap of 0.84 eV, which is easily photo-excited. • Its on/off photo-current density of 46 μA/cm 2 is 5-fold larger than that for physically stacked hybrid

  2. A method for synthesis and functionalization of ultrasmall superparamagnetic covalent carriers based on maghemite and dextran

    International Nuclear Information System (INIS)

    Mornet, Stephane; Portier, Josik; Duguet, Etienne

    2005-01-01

    A new generation of susceptibility contrast agents for MRI and based on maghemite cores covalently bonded to dextran stabilizing macromolecules was investigated. The multistep preparation of these versatile ultrasmall superparamagnetic iron oxides (VUSPIO) consisted of colloidal maghemite synthesis, surface modification by aminopropylsilane groups, and coupling of partially oxidized dextran via Schiff's bases and secondary amine bonds. The dextran corona might be easily derivatized, e.g. by PEGylation

  3. Reverse Algols

    Science.gov (United States)

    Leung, K. C.

    1989-01-01

    Reverse Algols, binary systems with a semidetached configuration in which the more massive component is in contact with the critical equipotential surface, are examined. Observational evidence for reverse Algols is presented and the parameters of seven reverse Algols are listed. The evolution of Algols and reverse Algols is discussed. It is suggested that, because reverse Algols represent the premass-reversal semidetached phase of close binary evolution, the evolutionary time scale between regular and reverse Algols is the ratio of the number of confirmed systems of these two Algol types.

  4. Reverse Logistics

    OpenAIRE

    Kulikova, Olga

    2016-01-01

    This thesis was focused on the analysis of the concept of reverse logistics and actual reverse processes which are implemented in mining industry and finding solutions for the optimization of reverse logistics in this sphere. The objective of this paper was the assessment of the development of reverse logistics in mining industry on the example of potash production. The theoretical part was based on reverse logistics and mining waste related literature and provided foundations for further...

  5. A QUANTUM MECHANICAL STUDY OF THE PROTONATION AND COVALENT HYDRATION OF QUINAZOLINE IN THE PRESENCE OF METAL CATIONS

    Science.gov (United States)

    We have investigated the protonation and reversible covalent hydration of quinazoline in the presence of Li+, Na+, and Ca2+ ions using ab initio quantum mechanical calculations at the MP2/6-31G**//HF/6-31G*level of theory. Proton affinities, enthalpies of hydration at 298.15K (DH...

  6. Covalent functionalization of graphene with reactive intermediates.

    Science.gov (United States)

    Park, Jaehyeung; Yan, Mingdi

    2013-01-15

    Graphene, a material made exclusively of sp(2) carbon atoms with its π electrons delocalized over the entire 2D network, is somewhat chemically inert. Covalent functionalization can enhance graphene's properties including opening its band gap, tuning conductivity, and improving solubility and stability. Covalent functionalization of pristine graphene typically requires reactive species that can form covalent adducts with the sp(2) carbon structures in graphene. In this Account, we describe graphene functionalization reactions using reactive intermediates of radicals, nitrenes, carbenes, and arynes. These reactive species covalently modify graphene through free radical addition, CH insertion, or cycloaddition reactions. Free radical additions are among the most common reaction, and these radicals can be generated from diazonium salts and benzoyl peroxide. Electron transfer from graphene to aryl diazonium ion or photoactivation of benzoyl peroxide yields aryl radicals that subsequently add to graphene to form covalent adducts. Nitrenes, electron-deficient species generated by thermal or photochemical activation of organic azides, can functionalize graphene very efficiently. Because perfluorophenyl nitrenes show enhanced bimolecular reactions compared with alkyl or phenyl nitrenes, perfluorophenyl azides are especially effective. Carbenes are used less frequently than nitrenes, but they undergo CH insertion and C═C cycloaddition reactions with graphene. In addition, arynes can serve as a dienophile in a Diels-Alder type reaction with graphene. Further study is needed to understand and exploit the chemistry of graphene. The generation of highly reactive intermediates in these reactions leads to side products that complicate the product composition and analysis. Fundamental questions remain about the reactivity and regioselectivity of graphene. The differences in the basal plane and the undercoordinated edges of graphene and the zigzag versus arm-chair configurations

  7. Covalently Bonded Chitosan on Graphene Oxide via Redox Reaction

    Directory of Open Access Journals (Sweden)

    Víctor M. Castaño

    2013-03-01

    Full Text Available Carbon nanostructures have played an important role in creating a new field of materials based on carbon. Chemical modification of carbon nanostructures through grafting has been a successful step to improve dispersion and compatibility in solvents, with biomolecules and polymers to form nanocomposites. In this sense carbohydrates such as chitosan are extremely valuable because their functional groups play an important role in diversifying the applications of carbon nanomaterials. This paper reports the covalent attachment of chitosan onto graphene oxide, taking advantage of this carbohydrate at the nanometric level. Grafting is an innovative route to modify properties of graphene, a two-dimensional nanometric arrangement, which is one of the most novel and promising nanostructures. Chitosan grafting was achieved by redox reaction using different temperature conditions that impact on the morphology and features of graphene oxide sheets. Transmission Electron Microscopy, Fourier Transform Infrared, Raman and Energy Dispersive spectroscopies were used to study the surface of chitosan-grafted-graphene oxide. Results show a successful modification indicated by the functional groups found in the grafted material. Dispersions of chitosan-grafted-graphene oxide samples in water and hexane revealed different behavior due to the chemical groups attached to the graphene oxide sheet.

  8. Reverse Osmosis

    Indian Academy of Sciences (India)

    many applications, one of which is desalination of seawater. The inaugural Nobel Prize in Chemistry was awarded in 1901 to van 't Hoff for his seminal work in this area. The present article explains the principle of osmosis and reverse osmosis. Osmosis and Reverse Osmosis. As the name suggests, reverse osmosis is the ...

  9. A chiroptical switch based on supramolecular chirality transfer through alkyl chain entanglement and dynamic covalent bonding.

    Science.gov (United States)

    Lv, Kai; Qin, Long; Wang, Xiufeng; Zhang, Li; Liu, Minghua

    2013-12-14

    Chirality transfer is an interesting phenomenon in Nature, which represents an important step to understand the evolution of chiral bias and the amplification of the chirality. In this paper, we report the chirality transfer via the entanglement of the alkyl chains between chiral gelator molecules and achiral amphiphilic Schiff base. We have found that although an achiral Schiff base amphiphile could not form organogels in any kind of organic solvents, it formed co-organogels when mixed with a chiral gelator molecule. Interestingly, the chirality of the gelator molecules was transferred to the Schiff base chromophore in the mixed co-gels and there was a maximum mixing ratio for the chirality transfer. Furthermore, the supramolecular chirality was also produced based on a dynamic covalent chemistry of an imine formed by the reaction between an aldehyde and an amine. Such a covalent bond of imine was formed reversibly depending on the pH variation. When the covalent bond was formed the chirality transfer occurred, when it was destroyed, the transfer stopped. Thus, a supramolecular chiroptical switch is obtained based on supramolecular chirality transfer and dynamic covalent chemistry.

  10. Conditional repair by locally switching the thermal healing capability of dynamic covalent polymers with light

    Science.gov (United States)

    Fuhrmann, Anne; Göstl, Robert; Wendt, Robert; Kötteritzsch, Julia; Hager, Martin D.; Schubert, Ulrich S.; Brademann-Jock, Kerstin; Thünemann, Andreas F.; Nöchel, Ulrich; Behl, Marc; Hecht, Stefan

    2016-12-01

    Healable materials could play an important role in reducing the environmental footprint of our modern technological society through extending the life cycles of consumer products and constructions. However, as most healing processes are carried out by heat alone, the ability to heal damage generally kills the parent material's thermal and mechanical properties. Here we present a dynamic covalent polymer network whose thermal healing ability can be switched `on' and `off' on demand by light, thereby providing local control over repair while retaining the advantageous macroscopic properties of static polymer networks. We employ a photoswitchable furan-based crosslinker, which reacts with short and mobile maleimide-substituted poly(lauryl methacrylate) chains forming strong covalent bonds while simultaneously allowing the reversible, spatiotemporally resolved control over thermally induced de- and re-crosslinking. We reason that our system can be adapted to more complex materials and has the potential to impact applications in responsive coatings, photolithography and microfabrication.

  11. Design of a covalently bonded glycosphingolipid microarray

    DEFF Research Database (Denmark)

    Arigi, Emma; Blixt, Klas Ola; Buschard, Karsten

    2012-01-01

    , the major classes of plant and fungal GSLs. In this work, a prototype "universal" GSL-based covalent microarray has been designed, and preliminary evaluation of its potential utility in assaying protein-GSL binding interactions investigated. An essential step in development involved the enzymatic release...... of the fatty acyl moiety of the ceramide aglycone of selected mammalian GSLs with sphingolipid N-deacylase (SCDase). Derivatization of the free amino group of a typical lyso-GSL, lyso-G(M1), with a prototype linker assembled from succinimidyl-[(N-maleimidopropionamido)-diethyleneglycol] ester and 2...

  12. Protein-RNA linkage and posttranslational modifications of feline calicivirus and murine norovirus VPg proteins

    Directory of Open Access Journals (Sweden)

    Allan Olspert

    2016-06-01

    Full Text Available Members of the Caliciviridae family of positive sense RNA viruses cause a wide range of diseases in both humans and animals. The detailed characterization of the calicivirus life cycle had been hampered due to the lack of robust cell culture systems and experimental tools for many of the members of the family. However, a number of caliciviruses replicate efficiently in cell culture and have robust reverse genetics systems available, most notably feline calicivirus (FCV and murine norovirus (MNV. These are therefore widely used as representative members with which to examine the mechanistic details of calicivirus genome translation and replication. The replication of the calicivirus RNA genome occurs via a double-stranded RNA intermediate that is then used as a template for the production of new positive sense viral RNA, which is covalently linked to the virus-encoded protein VPg. The covalent linkage to VPg occurs during genome replication via the nucleotidylylation activity of the viral RNA-dependent RNA polymerase. Using FCV and MNV, we used mass spectrometry-based approach to identify the specific amino acid linked to the 5′ end of the viral nucleic acid. We observed that both VPg proteins are covalently linked to guanosine diphosphate (GDP moieties via tyrosine positions 24 and 26 for FCV and MNV respectively. These data fit with previous observations indicating that mutations introduced into these specific amino acids are deleterious for viral replication and fail to produce infectious virus. In addition, we also detected serine phosphorylation sites within the FCV VPg protein with positions 80 and 107 found consistently phosphorylated on VPg-linked viral RNA isolated from infected cells. This work provides the first direct experimental characterization of the linkage of infectious calicivirus viral RNA to the VPg protein and highlights that post-translational modifications of VPg may also occur during the viral life cycle.

  13. Covalently functionalized graphene sheets with biocompatible natural amino acids

    International Nuclear Information System (INIS)

    Mallakpour, Shadpour; Abdolmaleki, Amir; Borandeh, Sedigheh

    2014-01-01

    Graphene sheets were covalently functionalized with aromatic–aliphatic amino acids (phenylalanine and tyrosine) and aliphatic amino acids (alanine, isoleucine, leucine, methionine and valine) by simple and green procedure. For this aim, at first natural graphite was converted into graphene oxide (GO) through strong oxidation procedure; then, based on the surface-exposed epoxy and carboxylic acid groups in GO solid, its surface modification with naturally occurring amino acids, occurred easily throughout the corresponding nucleophilic substitution and condensation reactions. Amino acid functionalized graphene demonstrates stable dispersion in water and common organic solvents. Fourier transform infrared, Raman and X-ray photoelectron spectroscopies, X-ray diffraction, field emission scanning electron microscopy and transmission electron microscopy were used to investigate the nanostructures and properties of prepared materials. Each amino acid has different considerable effects on the structure and morphology of the pure graphite, from increasing the layer spacing to layer scrolling, based on their structures, functional groups and chain length. In addition, therogravimetric analysis was used for demonstrating a successful grafting of amino acid molecules to the surface of graphene.

  14. Functionalization of multiwalled carbon nanotubes by microwave irradiation for lysozyme attachment: comparison of covalent and adsorption methods by kinetics of thermal inactivation

    Science.gov (United States)

    Puentes-Camacho, Daniel; Velázquez, Enrique F.; Rodríguez-Félix, Dora E.; Castillo-Ortega, Mónica; Sotelo-Mundo, Rogerio R.; del Castillo-Castro, Teresa

    2017-12-01

    Proteins suffer changes in their tertiary structure when they are immobilized, and enzymatic activity is affected due to the low biocompatibility of some supporting materials. In this work immobilization of lysozyme on carbon nanotubes previously functionalized by microwave irradiation was studied. The effectiveness of the microwave-assisted acid treatment of carbon nanotubes was evaluated by XPS, TEM, Raman and FTIR spectroscopy. The carboxylic modification of nanotube surfaces by this fast, simple and feasible method allowed the physical adsorption and covalent linking of active lysozyme onto the carbonaceous material. Thermal inactivation kinetics, thermodynamic parameters and storage stability were studied for adsorbed and covalent enzyme complexes. A major stability was found for lysozyme immobilized by the covalent method, the activation energy for inactivation of the enzyme was higher for the covalent method and it was stable after 50 d of storage at 4 °C. The current study highlights the effect of protein immobilization method on the biotechnological potential of nanostructured biocatalysts.

  15. MODELS OF PROJECT REVERSE ENGINEERING

    Directory of Open Access Journals (Sweden)

    Віктор Володимирович ІВАНОВ

    2017-03-01

    Full Text Available Reverse engineering decided important scientific and technical problems of increasing the cost of the existing technical product by transforming it into a product with other features or design. Search ideas of the new application of existing products on the base of heuristic analysis were created. The concept of reverse engineering and its division into three types: conceptual, aggregate and complete was expanded. The use of heuristic methods for reverse engineering concept was showed. The modification model of Reverse engineering based on the model of РМВОК was developed. Our model includes two new phases: identification and transformation. At the identification phase, technical control is made. At the transformation phase, search heuristic idea of the new applied existing technical product was made. The model of execution phase that included heuristic methods, metrological equipment, and CAD/CAM/CAE program complex was created. The model that connected economic indicators of reverse engineering project was developed.

  16. Conformational analysis of a covalently cross-linked Watson-Crick base pair model.

    Science.gov (United States)

    Jensen, Erik A; Allen, Benjamin D; Kishi, Yoshito; O'Leary, Daniel J

    2008-11-15

    Low-temperature NMR experiments and molecular modeling have been used to characterize the conformational behavior of a covalently cross-linked DNA base pair model. The data suggest that Watson-Crick or reverse Watson-Crick hydrogen bonding geometries have similar energies and can interconvert at low temperatures. This low-temperature process involves rotation about the crosslink CH(2)C(5') (psi) carbon-carbon bond, which is energetically preferred over the alternate CH(2)N(3) (phi) carbon-nitrogen bond rotation.

  17. Conformational Analysis of a Covalently Cross-Linked Watson-Crick Base Pair Model

    OpenAIRE

    Jensen, Erik A.; Allen, Benjamin D.; Kishi, Yoshito; O'Leary, Daniel J.

    2008-01-01

    Low temperature NMR experiments and molecular modeling have been used to characterize the conformational behavior of a covalently cross-linked DNA base pair model. The data suggest that Watson-Crick or reverse Watson-Crick hydrogen bonding geometries have similar energies and can interconvert at low temperatures. This low-temperature process involves rotation about the crosslink CH2–C(5′) (ψ) carbon-carbon bond, which is energetically preferred over the alternate CH2–N(3) (ϕ) carbon-nitrogen ...

  18. Revisiting nitrogen species in covalent triazine frameworks

    KAUST Repository

    Osadchii, Dmitrii Yu.

    2017-11-28

    Covalent triazine frameworks (CTFs) are porous organic materials promising for applications in catalysis and separation due to their high stability, adjustable porosity and intrinsic nitrogen functionalities. CTFs are prepared by ionothermal trimerization of aromatic nitriles, however, multiple side reactions also occur under synthesis conditions, and their influence on the material properties is still poorly described. Here we report the systematic characterization of nitrogen in CTFs using X-ray photoelectron spectroscopy (XPS). With the use of model compounds, we could distinguish several types of nitrogen species. By combining these data with textural properties, we unravel the influence that the reaction temperature, the catalyst and the monomer structure and composition have on the properties of the resulting CTF materials.

  19. Non-covalent associative structure of coal

    Energy Technology Data Exchange (ETDEWEB)

    Shui, H. [Anhui University of Technology, Maanshan (China). School of Chemistry and Chemical Engineering

    2004-06-01

    The recent progress of non-covalent associative structure of coal and the mechanisms of the carbon disulphide-N-methyl-2-pyrrolidone (CS{sub 2}/NMP) are mixed solvent and the additive addition enhancing the extraction yield of coals are reviewed, and the aggregation behaviour of coal in solid and solution states are presented, and the aggregation behavior of coal in solid and solution states are introduced in this paper. Coal extraction and swelling in organic solvents at room temperature were the most useful methods to understand the associative structure of coal. CS{sub 2}/NMP is a unique solvent to give high extraction yields for some bituminous coals. Some additives such as tetracyanoethylene (TCNE) can dissociate the stronger interactions among coal molecules and enhance the extraction yields of coal in the mixed solvent. 37 refs., 1 fig.

  20. Novel hydroxyapatite biomaterial covalently linked to raloxifene.

    Science.gov (United States)

    Meme, L; Santarelli, A; Marzo, G; Emanuelli, M; Nocini, P F; Bertossi, D; Putignano, A; Dioguardi, M; Lo Muzio, L; Bambini, F

    2014-01-01

    Since raloxifene, a drug used in osteoporosis therapy, inhibits osteoclast, but not osteoblast functions, it has been suggested to improve recovery during implant surgery. The present paper describes an effective method to link raloxifene, through a covalent bond, to a nano-Hydroxyapatite-based biomaterial by interfacing with (3-aminopropyl)-Triethoxysilane as assessed by Infra Red-Fourier Transformed (IR-FT) spectroscopy and Scanning Electron Microscope (SEM). To evaluate the safety of this modified new material, the vitality of osteoblast-like cells cultured with the new biomaterial was then investigated. Raloxifene-conjugated HAbiomaterial has been shown to be a safe material easy to obtain which could be an interesting starting point for the use of a new functional biomaterial suitable in bone regeneration procedures.

  1. Revisiting nitrogen species in covalent triazine frameworks

    KAUST Repository

    Osadchii, Dmitrii Yu.; Olivos Suarez, Alma Itzel; Bavykina, Anastasiya V.; Gascon, Jorge

    2017-01-01

    Covalent triazine frameworks (CTFs) are porous organic materials promising for applications in catalysis and separation due to their high stability, adjustable porosity and intrinsic nitrogen functionalities. CTFs are prepared by ionothermal trimerization of aromatic nitriles, however, multiple side reactions also occur under synthesis conditions, and their influence on the material properties is still poorly described. Here we report the systematic characterization of nitrogen in CTFs using X-ray photoelectron spectroscopy (XPS). With the use of model compounds, we could distinguish several types of nitrogen species. By combining these data with textural properties, we unravel the influence that the reaction temperature, the catalyst and the monomer structure and composition have on the properties of the resulting CTF materials.

  2. Pore surface engineering in covalent organic frameworks.

    Science.gov (United States)

    Nagai, Atsushi; Guo, Zhaoqi; Feng, Xiao; Jin, Shangbin; Chen, Xiong; Ding, Xuesong; Jiang, Donglin

    2011-11-15

    Covalent organic frameworks (COFs) are a class of important porous materials that allow atomically precise integration of building blocks to achieve pre-designable pore size and geometry; however, pore surface engineering in COFs remains challenging. Here we introduce pore surface engineering to COF chemistry, which allows the controlled functionalization of COF pore walls with organic groups. This functionalization is made possible by the use of azide-appended building blocks for the synthesis of COFs with walls to which a designable content of azide units is anchored. The azide units can then undergo a quantitative click reaction with alkynes to produce pore surfaces with desired groups and preferred densities. The diversity of click reactions performed shows that the protocol is compatible with the development of various specific surfaces in COFs. Therefore, this methodology constitutes a step in the pore surface engineering of COFs to realize pre-designed compositions, components and functions.

  3. Covalent versus ionic bonding in alkalimetal fluoride oligomers

    NARCIS (Netherlands)

    Bickelhaupt, F.M.; Sola, M.; Fonseca Guerra, C.

    2007-01-01

    The most polar bond in chemistry is that between a fluorine and an alkalimetal atom. Inspired by our recent finding that other polar bonds (C - M and H - M) have important covalent contributions (i.e., stabilization due to bond overlap), we herein address the question if covalency is also essential

  4. Covalent Grafting of the RGD-Peptide onto Polyetheretherketone Surfaces via Schiff Base Formation

    Directory of Open Access Journals (Sweden)

    Marc Becker

    2013-01-01

    Full Text Available In recent years, the synthetic polymer polyetheretherketone (PEEK has increasingly been used in a number of orthopedic implementations, due to its excellent mechanical properties, bioinertness, and chemical resistance. For in vivo applications, the surface of PEEK, which does not naturally support cell adhesion, has to be modified to improve tissue integration. In the present work we demonstrate a novel wet-chemical modification of PEEK to modify the surface, enabling the covalent grafting of the cell-adhesive RGD-peptide. Modification of the polymer surface was achieved via Schiff base formation using an aliphatic diamine and subsequent crosslinker-mediated immobilization of the peptide. In cell culture experiments with primary osteoblasts it was shown that the RGD-modified PEEK not only significantly promoted cellular adhesion but also strongly enhanced the proliferation of osteoblasts on the modified polymer surface.

  5. Thermally reversible rubber-toughened thermoset networks via Diels-Alder chemistry

    NARCIS (Netherlands)

    Araya-Hermosilla, R.; Fortunato, G.; Pucci, A.; Raffa, P.; Polgar, L.; Broekhuis, A. A.; Pourhossein, P.; Lima, G. M. R.; Beljaars, M.; Picchioni, F.

    In this work we present a reversible and toughened thermoset system based on the covalent incorporation of a furane functionalized ethylene-propylene rubber (EPM-Fu) into a thermoset furane functionalized polyketone (PK-Fu) via Diels-Alder (DA) reversible cross-linking with bismaleimide (b-MA).

  6. Detection of HBV Covalently Closed Circular DNA

    Directory of Open Access Journals (Sweden)

    Xiaoling Li

    2017-06-01

    Full Text Available Chronic hepatitis B virus (HBV infection affects approximately 240 million people worldwide and remains a serious public health concern because its complete cure is impossible with current treatments. Covalently closed circular DNA (cccDNA in the nucleus of infected cells cannot be eliminated by present therapeutics and may result in persistence and relapse. Drug development targeting cccDNA formation and maintenance is hindered by the lack of efficient cccDNA models and reliable cccDNA detection methods. Southern blotting is regarded as the gold standard for quantitative cccDNA detection, but it is complicated and not suitable for high-throughput drug screening, so more sensitive and simple methods, including polymerase chain reaction (PCR-based methods, Invader assays, in situ hybridization and surrogates, have been developed for cccDNA detection. However, most methods are not reliable enough, and there are no unified standards for these approaches. This review will summarize available methods for cccDNA detection. It is hoped that more robust methods for cccDNA monitoring will be developed and that standard operation procedures for routine cccDNA detection in scientific research and clinical monitoring will be established.

  7. Covalently crosslinked diels-alder polymer networks.

    Energy Technology Data Exchange (ETDEWEB)

    Bowman, Christopher (University of Colorado, Boulder, CO); Adzima, Brian J. (University of Colorado, Boulder, CO); 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.

  8. Study on immobilization enzyme using radiation grafting and condensation covalent

    International Nuclear Information System (INIS)

    Cao Jin; Su Zongxian; Gao Jianfeng

    1989-01-01

    The immobilization of gluecose oxidase (GOD) on polyethylene and F 46 is described by radiation grafting and condensation covalent. The GOD on polyethylene film is characterized with IR-spectrum. The results show that the enzyme activity on F 46 film is high when dose rate and covalent yield are low. When covalent yield is 4.3% the enzyme relative activity achieves the greatest value for F 46 film. The experiment also demonstrates that acrylic acid affects the relative activity of enzyme and the method of IR-pectrum character is convenient and efficient for GOD on polyethylene film

  9. Strategies to balance covalent and non-covalent biomolecule attachment within collagen-GAG biomaterials.

    Science.gov (United States)

    Pence, Jacquelyn C; Gonnerman, Emily A; Bailey, Ryan C; Harley, Brendan A C

    2014-09-01

    Strategies to integrate instructive biomolecular signals into a biomaterial are becoming increasingly complex and bioinspired. While a large majority of reports still use repeated treatments with soluble factors, this approach can be prohibitively costly and difficult to translate in vivo for applications where spatial control over signal presentation is necessary. Recent efforts have explored the use of covalent immobilization of biomolecules to the biomaterial, via both bulk (ubiquitous) as well as spatially-selective light-based crosslinking, as a means to both enhance stability and bioactivity. However, little is known about how processing conditions during immobilization impact the degree of unintended non-covalent interactions, or fouling, that takes place between the biomaterial and the biomolecule of interest. Here we demonstrate the impact of processing conditions for bulk carbodiimide (EDC) and photolithography-based benzophenone (BP) crosslinking on specific attachment vs. fouling of a model protein (Concanavalin A, ConA) within collagen-glycosaminoglycan (CG) scaffolds. Collagen source significantly impacts the selectivity of biomolecule immobilization. EDC crosslinking intensity and ligand concentration significantly impacted selective immobilization. For benzophenone photoimmobilization we observed that increased UV exposure time leads to increased ConA immobilization. Immobilization efficiency for both EDC and BP strategies was maximal at physiological pH. Increasing ligand concentration during immobilization process led to enhanced immobilization for EDC chemistry, no impact on BP immobilization, but significant increases in non-specific fouling. Given recent efforts to covalently immobilize biomolecules to a biomaterial surface to enhance bioactivity, improved understanding of the impact of crosslinking conditions on selective attachment versus non-specific fouling will inform the design of instructive biomaterials for applications across tissue

  10. Pharmacological modification of multi-drug resistance (MDR) in vitro detected by a novel fluorometric microculture cytotoxicity assay. Reversal of resistance and selective cytotoxic actions of cyclosporin A and verapamil on MDR leukemia T-cells.

    Science.gov (United States)

    Larsson, R; Nygren, P

    1990-07-15

    A novel fluorometric microculture cytotoxicity assay (FMCA), based on measurements of fluorescein diacetate (FDA) hydrolysis and DNA staining by Hoechst 33342, was used for drug sensitivity testing and detection of resistance reversal in acute lymphoblastic leukemia (ALL) cell lines. The 72-hr assay was found to be sensitive, reproducible and linearly related to the number of viable cells within a broad range of cell concentrations. At clinically achievable drug concentrations, the calcium channel blocker Verapamil (ver) and the immunosuppressant Cyclosporin A (csA) were found to partly reverse acquired Vincristine (vcr) resistance in multi-drug resistant (MDR) T-ALL L100 cells with little or no effect on the drug-sensitive parental L0 cell line. By combining the fluorometric indices, we found that low concentrations of csA were growth-inhibitory, whereas higher concentrations (greater than 10 micrograms/ml) were progressively cytotoxic for drug-sensitive L0 cells. In MDR L100 cells, on the other hand, csA produced significant cell kill even at low drug concentrations. Ver had no effects on sensitive L0 cells but showed considerable cytotoxic action towards MDR L100 cells. There was no apparent relationship between drug reversal of vcr resistance and the cytotoxic actions of the drug per se since the calcium channel blocker diltiazem (dil) significantly potentiated the actions of vcr on MDR L100 cells without being more toxic to these cells (compared to vcr-sensitive L0 cells).

  11. Predominantly ligand guided non-covalently linked assemblies of ...

    Indian Academy of Sciences (India)

    JUBARAJ B BARUAH

    2018-05-12

    May 12, 2018 ... Abstract. Various non-covalently linked inorganic self-assemblies formed by the supramolecular interacting .... metal-organic frameworks.59 Inorganic chemists rou- ...... two-dimensional organic–inorganic layered perovskite.

  12. Molecular electrostatic potential analysis of non-covalent complexes

    Indian Academy of Sciences (India)

    Chemical Sciences and Technology Division and Academy of Scientific & Innovative Research (AcSIR), ... workers proposed the electrostatic-covalent model of hydrogen bonding. ..... tain degree of electron donation and acceptance occurs.

  13. Self-Healing Supramolecular Hydrogels Based on Reversible Physical Interactions

    Directory of Open Access Journals (Sweden)

    Satu Strandman

    2016-04-01

    Full Text Available Dynamic and reversible polymer networks capable of self-healing, i.e., restoring their mechanical properties after deformation and failure, are gaining increasing research interest, as there is a continuous need towards extending the lifetime and improving the safety and performance of materials particularly in biomedical applications. Hydrogels are versatile materials that may allow self-healing through a variety of covalent and non-covalent bonding strategies. The structural recovery of physical gels has long been a topic of interest in soft materials physics and various supramolecular interactions can induce this kind of recovery. This review highlights the non-covalent strategies of building self-repairing hydrogels and the characterization of their mechanical properties. Potential applications and future prospects of these materials are also discussed.

  14. Exploring Covalent Allosteric Inhibition of Antigen 85C from Mycobacterium tuberculosis by Ebselen Derivatives.

    Science.gov (United States)

    Goins, Christopher M; Dajnowicz, Steven; Thanna, Sandeep; Sucheck, Steven J; Parks, Jerry M; Ronning, Donald R

    2017-05-12

    Previous studies identified ebselen as a potent in vitro and in vivo inhibitor of the Mycobacterium tuberculosis (Mtb) antigen 85 (Ag85) complex, comprising three homologous enzymes required for the biosynthesis of the mycobacterial cell wall. In this study, the Mtb Ag85C enzyme was cocrystallized with azido and adamantyl ebselen derivatives, resulting in two crystallographic structures of 2.01 and 1.30 Å resolution, respectively. Both structures displayed the anticipated covalent modification of the solvent accessible, noncatalytic Cys209 residue forming a selenenylsulfide bond. Continuous difference density for both thiol modifiers allowed for the assessment of interactions that influence ebselen binding and inhibitor orientation that were unobserved in previous Ag85C ebselen structures. The k inact /K I values for ebselen, adamantyl ebselen, and azido ebselen support the importance of observed constructive chemical interactions with Arg239 for increased in vitro efficacy toward Ag85C. To better understand the in vitro kinetic properties of these ebselen derivatives, the energetics of specific protein-inhibitor interactions and relative reaction free energies were calculated for ebselen and both derivatives using density functional theory. These studies further support the different in vitro properties of ebselen and two select ebselen derivatives from our previously published ebselen library with respect to kinetics and protein-inhibitor interactions. In both structures, the α9 helix was displaced farther from the enzyme active site than the previous Ag85C ebselen structure, resulting in the restructuring of a connecting loop and imparting a conformational change to residues believed to play a role in substrate binding specific to Ag85C. These notable structural changes directly affect protein stability, reducing the overall melting temperature by up to 14.5 °C, resulting in the unfolding of protein at physiological temperatures. Additionally, this structural

  15. Covalent modification of cytoskeletal proteins in neuronal cells by tryptamine-4,5-dione

    Directory of Open Access Journals (Sweden)

    Yoji Kato

    2014-01-01

    Full Text Available Serotonin, 5-hydroxytryptamine, is a systemic bioactive amine that acts in the gut and brain. As a substrate of myeloperoxidase in vitro, serotonin is oxidized to tryptamine-4,5-dione (TD, which is highly reactive with thiols. In this work, we successively prepared a monoclonal antibody to quinone-modified proteins and found that the antibody preferentially recognizes the TD–thiol adduct. Using the antibody, we observed that the chloride ion, the predominant physiological substrate for myeloperoxidase in vivo, is not competitive toward the enzyme catalyzed serotonin oxidation process, suggesting that serotonin is a plausible physiological substrate for the enzyme in vivo. Immunocytochemical analyses revealed that TD staining was observed in the cytosol of SH-SY5Y neuroblastoma cells while blot analyses showed that some cellular proteins were preferentially modified. Pull-down analyses confirmed that the cytoskeletal proteins tubulins, vimentin, and neurofilament-L were modified. When pure tubulins were exposed to micromolar levels of synthetic TD, self-polymerization was initially enhanced and then suppressed. These results suggest that serotonin oxidation by myeloperoxidase or the action of other oxidants could cause functional alteration of cellular proteins, which may be related to neurodegeneration processes or irritable bowel syndrome.

  16. Covalent Modification of Human Serum Albumin by the Natural Sesquiterpene Lactone Parthenolide

    Directory of Open Access Journals (Sweden)

    Michael Plöger

    2015-04-01

    Full Text Available The reactivity of parthenolide (PRT, a natural sesquiterpene lactone from Tanacetum parthenium (Asteraceae, with human serum albumin (HSA was studied by UHPLC/+ESI-QqTOF MS analysis after tryptic digestion of albumin samples after incubation with this compound. It was found that the single free cysteine residue, C34, of HSA (0.6 mM reacted readily with PRT when incubated at approximately 13-fold excess of PRT (8 mM. Time-course studies with PRT and its 11β,13-dihydro derivative at equimolar ratios of the reactants revealed that PRT under the chosen conditions reacts preferably with C34 and does so exclusively via its α-methylene-γ-lactone moiety, while the epoxide structure is not involved in the reaction.

  17. Visible-light sensitization of boron-doped nanocrystalline diamond through non-covalent surface modification

    Czech Academy of Sciences Publication Activity Database

    Krýsová, Hana; Vlčková Živcová, Zuzana; Bartoň, Jan; Petrák, Václav; Nesladek, M.; Cígler, Petr; Kavan, Ladislav

    2015-01-01

    Roč. 17, č. 2 (2015), s. 1165-1172 ISSN 1463-9076 R&D Projects: GA ČR GA13-31783S Institutional support: RVO:61388955 ; RVO:61388963 ; RVO:68378271 Keywords : nanocrystallines * visible-light sensitization * boron-doped diamond Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 4.449, year: 2015

  18. Covalent adduct formation between the plasmalogen-derived modification product 2-chlorohexadecanal and phloretin

    OpenAIRE

    ?llen, Andreas; Nusshold, Christoph; Glasnov, Toma; Saf, Robert; Cantillo, David; Eibinger, Gerald; Reicher, Helga; Fauler, G?nter; Bernhart, Eva; Hallstrom, Seth; Kogelnik, Nora; Zangger, Klaus; Oliver Kappe, C.; Malle, Ernst; Sattler, Wolfgang

    2015-01-01

    Hypochlorous acid added as reagent or generated by the myeloperoxidase (MPO)-H2O2-Cl? system oxidatively modifies brain ether-phospholipids (plasmalogens). This reaction generates a sn2-acyl-lysophospholipid and chlorinated fatty aldehydes. 2-Chlorohexadecanal (2-ClHDA), a prototypic member of chlorinated long-chain fatty aldehydes, has potent neurotoxic potential by inflicting blood?brain barrier (BBB) damage. During earlier studies we could show that the dihydrochalcone-type polyphenol phlo...

  19. Increased Protein Structural Resolution from Diethylpyrocarbonate-based Covalent Labeling and Mass Spectrometric Detection

    Science.gov (United States)

    Zhou, Yuping; Vachet, Richard W.

    2012-04-01

    Covalent labeling and mass spectrometry are seeing increased use together as a way to obtain insight into the 3-dimensional structure of proteins and protein complexes. Several amino acid specific (e.g., diethylpyrocarbonate) and non-specific (e.g., hydroxyl radicals) labeling reagents are available for this purpose. Diethylpyrocarbonate (DEPC) is a promising labeling reagent because it can potentially probe up to 30% of the residues in the average protein and gives only one reaction product, thereby facilitating mass spectrometric analysis. It was recently reported, though, that DEPC modifications are labile for some amino acids. Here, we show that label loss is more significant and widespread than previously thought, especially for Ser, Thr, Tyr, and His residues, when relatively long protein digestion times are used. Such label loss ultimately decreases the amount of protein structural information that is obtainable with this reagent. We find, however, that the number of DEPC modified residues and, thus, protein structural information, can be significantly increased by decreasing the time between the covalent labeling reaction and the mass spectrometric analysis. This is most effectively accomplished using short (e.g., 2 h) proteolytic digestions with enzymes such as immobilized chymotrypsin or Glu-C rather than using methods (e.g., microwave or ultrasonic irradiation) that accelerate proteolysis in other ways. Using short digestion times, we show that the percentage of solvent accessible residues that can be modified by DEPC increases from 44% to 67% for cytochrome c, 35% to 81% for myoglobin, and 76% to 95% for β-2-microglobulin. In effect, these increased numbers of modified residues improve the protein structural resolution available from this covalent labeling method. Compared with typical overnight digestion conditions, the short digestion times decrease the average distance between modified residues from 11 to 7 Å for myoglobin, 13 to 10 Å for

  20. Covalent Stabilization: A Sturdy Molecular Square from Reversible Metal-Ion-Directed Self-Assembly

    Czech Academy of Sciences Publication Activity Database

    Olive, A. G. L.; Parkan, K.; Givelet, C.; Michl, Josef

    2011-01-01

    Roč. 133, č. 50 (2011), s. 20108-20111 ISSN 0002-7863 EU Projects: European Commission(XE) 227756 - DIPOLAR ROTOR ARRAY Grant - others:NSF(US) CHE0848477 Institutional research plan: CEZ:AV0Z40550506 Keywords : prismatic altitudinal rotors * supramolecular coordination chemistry * bond formation * macrocycles * catalysis Subject RIV: CC - Organic Chemistry Impact factor: 9.907, year: 2011

  1. Reversible Statistics

    DEFF Research Database (Denmark)

    Tryggestad, Kjell

    2004-01-01

    The study aims is to describe how the inclusion and exclusion of materials and calculative devices construct the boundaries and distinctions between statistical facts and artifacts in economics. My methodological approach is inspired by John Graunt's (1667) Political arithmetic and more recent work...... within constructivism and the field of Science and Technology Studies (STS). The result of this approach is here termed reversible statistics, reconstructing the findings of a statistical study within economics in three different ways. It is argued that all three accounts are quite normal, albeit...... in different ways. The presence and absence of diverse materials, both natural and political, is what distinguishes them from each other. Arguments are presented for a more symmetric relation between the scientific statistical text and the reader. I will argue that a more symmetric relation can be achieved...

  2. Stereodynamic tetrahydrobiisoindole “NU-BIPHEP(O”s: functionalization, rotational barriers and non-covalent interactions

    Directory of Open Access Journals (Sweden)

    Golo Storch

    2016-07-01

    Full Text Available Stereodynamic ligands offer intriguing possibilities in enantioselective catalysis. “NU-BIPHEPs” are a class of stereodynamic diphosphine ligands which are easily accessible via rhodium-catalyzed double [2 + 2 + 2] cycloadditions. This study explores the preparation of differently functionalized “NU-BIPHEP(O” compounds, the characterization of non-covalent adduct formation and the quantification of enantiomerization barriers. In order to explore the possibilities of functionalization, we studied modifications of the ligand backbone, e.g., with 3,5-dichlorobenzoyl chloride. Diastereomeric adducts with Okamoto-type cellulose derivatives and on-column deracemization were realized on the basis of non-covalent interactions. Enantioselective dynamic HPLC (DHPLC allowed for the determination of rotational barriers of ΔG‡298K = 92.2 ± 0.3 kJ mol−1 and 99.5 ± 0.1 kJ mol−1 underlining the stereodynamic properties of “NU-BIPHEPs” and “NU-BIPHEP(Os”, respectively. These results make the preparation of tailor-made functionalized stereodynamic ligands possible and give an outline for possible applications in enantioselective catalysis.

  3. Surface functionalization of cyclic olefin copolymer with aryldiazonium salts: A covalent grafting method

    International Nuclear Information System (INIS)

    Brisset, Florian; Vieillard, Julien; Berton, Benjamin; Morin-Grognet, Sandrine; Duclairoir-Poc, Cécile; Le Derf, Franck

    2015-01-01

    Graphical abstract: - Highlights: • An effective method to modify cyclic olefin copolymer surface. • The surface of COC was modified by covalent grafting of aryl diazonium salts. • The wettability of COC surface was modulated by diazonium salts. • Photoinitiation and chemical reduction have to be combined to graft diazonium salt on COC surface. - Abstract: Covalent immobilization of biomolecules on the surface of cyclic olefin copolymer (COC) is still a tough challenge. We developed a robust method for COC surface grafting through reaction with aryldiazonium. Chemical diazonium reduction generated an aryl radical and the formation of a grafted film layer on the organic surface. We also demonstrated that the chemical reduction of diazonium salt was not sufficient to form a film on the COC surface. UV illumination had to be combined with chemical reduction to graft an aryl layer onto the COC surface. We optimized organic film deposition by using different chemical reducers, different reaction times and reagent proportions. We characterized surface modifications by fluorescence microscopy and contact angle measurements, infrared spectroscopy, X-ray photoemission spectroscopy and Raman spectroscopy, and assessed the topography of the aryl film by atomic force microscopy. This original strategy allowed us to evidence various organic functions to graft biomolecules onto COC surfaces with a fast and efficient technique

  4. Surface functionalization of cyclic olefin copolymer with aryldiazonium salts: A covalent grafting method

    Energy Technology Data Exchange (ETDEWEB)

    Brisset, Florian, E-mail: florian.brisset@etu.univ-rouen.fr [UMR CNRS 6014 COBRA, FR 3038, Université de Rouen, 55 rue Saint Germain, 27000 Evreux (France); Vieillard, Julien, E-mail: julien.vieillard@univ-rouen.fr [UMR CNRS 6014 COBRA, FR 3038, Université de Rouen, 55 rue Saint Germain, 27000 Evreux (France); Berton, Benjamin, E-mail: benjamin.berton@univ-rouen.fr [EA 3233 SMS, Université de Rouen, 1 rue du 7ème Chasseurs, BP281, 27002 Evreux Cedex (France); Morin-Grognet, Sandrine, E-mail: sandrine.morin@univ-rouen.fr [EA 3829 MERCI, Université de Rouen, 1 rue du 7ème Chasseurs, BP281, 27002 Evreux Cedex (France); Duclairoir-Poc, Cécile, E-mail: cecile.duclairoir@univ-rouen.fr [EA 4312 LMSM, Université de Rouen, 55 rue Saint Germain, 27000 Evreux (France); Le Derf, Franck, E-mail: franck.lederf@univ-rouen.fr [UMR CNRS 6014 COBRA, FR 3038, Université de Rouen, 55 rue Saint Germain, 27000 Evreux (France)

    2015-02-28

    Graphical abstract: - Highlights: • An effective method to modify cyclic olefin copolymer surface. • The surface of COC was modified by covalent grafting of aryl diazonium salts. • The wettability of COC surface was modulated by diazonium salts. • Photoinitiation and chemical reduction have to be combined to graft diazonium salt on COC surface. - Abstract: Covalent immobilization of biomolecules on the surface of cyclic olefin copolymer (COC) is still a tough challenge. We developed a robust method for COC surface grafting through reaction with aryldiazonium. Chemical diazonium reduction generated an aryl radical and the formation of a grafted film layer on the organic surface. We also demonstrated that the chemical reduction of diazonium salt was not sufficient to form a film on the COC surface. UV illumination had to be combined with chemical reduction to graft an aryl layer onto the COC surface. We optimized organic film deposition by using different chemical reducers, different reaction times and reagent proportions. We characterized surface modifications by fluorescence microscopy and contact angle measurements, infrared spectroscopy, X-ray photoemission spectroscopy and Raman spectroscopy, and assessed the topography of the aryl film by atomic force microscopy. This original strategy allowed us to evidence various organic functions to graft biomolecules onto COC surfaces with a fast and efficient technique.

  5. Covalent linkage of nanodiamond-paclitaxel for drug delivery and cancer therapy

    Energy Technology Data Exchange (ETDEWEB)

    Liu, Kuang-Kai; Wang, Chi-Ching; Chao, Jui-I [Department of Biological Science and Technology, National Chiao Tung University, Hsinchu 30013, Taiwan (China); Zheng, Wen-Wei; Lo, Yu-Shiu; Chen, Chinpiao [Department of Chemistry, National Dong Hwa University, Hualien 97401, Taiwan (China); Chiu, Yu-Chung; Cheng, Chia-Liang, E-mail: clcheng@mail.ndhu.edu.tw, E-mail: chinpiao@mail.ndhu.edu.tw, E-mail: jichao@faculty.nctu.edu.tw [Department of Physics, National Dong Hwa University, Hualien 97401, Taiwan (China)

    2010-08-06

    A nanoparticle-conjugated cancer drug provides a novel strategy for cancer therapy. In this study, we manipulated nanodiamond (ND), a carbon nanomaterial, to covalently link paclitaxel for cancer drug delivery and therapy. Paclitaxel was bound to the surface of 3-5 nm sized ND through a succession of chemical modifications. The ND-paclitaxel conjugation was measured by atomic force microscope and nuclear magnetic resonance spectroscopy, and confirmed with infrared spectroscopy by the detection of deuterated paclitaxel. Treatment with 0.1-50 {mu}g ml{sup -1} ND-paclitaxel for 48 h significantly reduced the cell viability in the A549 human lung carcinoma cells. ND-paclitaxel induced both mitotic arrest and apoptosis in A549 cells. However, ND alone or denatured ND-paclitaxel (after treatment with strong alkaline solution, 1 M NaOH) did not induce the damage effects on A549 cells. ND-paclitaxel was taken into lung cancer cells in a concentration-dependent manner using flow cytometer analysis. The ND-paclitaxel particles were located in the microtubules and cytoplasm of A549 cells observed by confocal microscopy. Furthermore, ND-paclitaxel markedly blocked the tumor growth and formation of lung cancer cells in xenograft SCID mice. Together, we provide a functional covalent conjugation of ND-paclitaxel, which can be delivered into lung carcinoma cells and preserves the anticancer activities on the induction of mitotic blockage, apoptosis and anti-tumorigenesis.

  6. Theory and Applications of Covalent Docking in Drug Discovery: Merits and Pitfalls

    Directory of Open Access Journals (Sweden)

    Hezekiel Mathambo Kumalo

    2015-01-01

    Full Text Available he present art of drug discovery and design of new drugs is based on suicidal irreversible inhibitors. Covalent inhibition is the strategy that is used to achieve irreversible inhibition. Irreversible inhibitors interact with their targets in a time-dependent fashion, and the reaction proceeds to completion rather than to equilibrium. Covalent inhibitors possessed some significant advantages over non-covalent inhibitors such as covalent warheads can target rare, non-conserved residue of a particular target protein and thus led to development of highly selective inhibitors, covalent inhibitors can be effective in targeting proteins with shallow binding cleavage which will led to development of novel inhibitors with increased potency than non-covalent inhibitors. Several computational approaches have been developed to simulate covalent interactions; however, this is still a challenging area to explore. Covalent molecular docking has been recently implemented in the computer-aided drug design workflows to describe covalent interactions between inhibitors and biological targets. In this review we highlight: (i covalent interactions in biomolecular systems; (ii the mathematical framework of covalent molecular docking; (iii implementation of covalent docking protocol in drug design workflows; (iv applications covalent docking: case studies and (v shortcomings and future perspectives of covalent docking. To the best of our knowledge; this review is the first account that highlights different aspects of covalent docking with its merits and pitfalls. We believe that the method and applications highlighted in this study will help future efforts towards the design of irreversible inhibitors.

  7. Boosting lithium storage in covalent organic framework via activation of 14-electron redox chemistry.

    Science.gov (United States)

    Lei, Zhendong; Yang, Qinsi; Xu, Yi; Guo, Siyu; Sun, Weiwei; Liu, Hao; Lv, Li-Ping; Zhang, Yong; Wang, Yong

    2018-02-08

    Conjugated polymeric molecules have been heralded as promising electrode materials for the next-generation energy-storage technologies owing to their chemical flexibility at the molecular level, environmental benefit, and cost advantage. However, before any practical implementation takes place, the low capacity, poor structural stability, and sluggish ion/electron diffusion kinetics remain the obstacles that have to be overcome. Here, we report the synthesis of a few-layered two-dimensional covalent organic framework trapped by carbon nanotubes as the anode of lithium-ion batteries. Remarkably, upon activation, this organic electrode delivers a large reversible capacity of 1536 mAh g -1 and can sustain 500 cycles at 100 mA g -1 . Aided by theoretical calculations and electrochemical probing of the electrochemical behavior at different stages of cycling, the storage mechanism is revealed to be governed by 14-electron redox chemistry for a covalent organic framework monomer with one lithium ion per C=N group and six lithium ions per benzene ring. This work may pave the way to the development of high-capacity electrodes for organic rechargeable batteries.

  8. Enzymatic Activity Enhancement of Non-Covalent Modified Superoxide Dismutase and Molecular Docking Analysis

    Directory of Open Access Journals (Sweden)

    Fa-Jun Song

    2012-03-01

    Full Text Available The enzyme activity of superoxide dismutase was improved in the pyrogallol autoxidation system by about 27%, after interaction between hydroxypropyl-β-cyclo- dextrin and superoxide dismutase. Fluorescence spectrometry was used to study the interaction between hydroxypropyl-β-cyclodextrin and superoxide dismutase at different temperatures. By doing this, it can be found that these interactions increase fluorescence sensitivity. In the meantime, the synchronous fluorescence intensity revealed the interaction sites to be close to the tryptophan (Trp and tyrosine (Tyr residues of superoxide dismutase. Furthermore, molecular docking was applied to explore the binding mode between the ligands and the receptor. This suggested that HP-β-CD interacted with the B ring, G ring and the O ring and revealed that the lysine (Lys residues enter the nanocavity. It was concluded that the HP-β-CD caused specific conformational changes in SOD by non-covalent modification.

  9. Covalent functionalization and passivation of exfoliated black phosphorus via aryl diazonium chemistry

    Science.gov (United States)

    Ryder, Christopher R.; Wood, Joshua D.; Wells, Spencer A.; Yang, Yang; Jariwala, Deep; Marks, Tobin J.; Schatz, George C.; Hersam, Mark C.

    2016-06-01

    Functionalization of atomically thin nanomaterials enables the tailoring of their chemical, optical and electronic properties. Exfoliated black phosphorus (BP)—a layered two-dimensional semiconductor—exhibits favourable charge-carrier mobility, tunable bandgap and highly anisotropic properties, but it is chemically reactive and degrades rapidly in ambient conditions. Here we show that covalent aryl diazonium functionalization suppresses the chemical degradation of exfoliated BP even after three weeks of ambient exposure. This chemical modification scheme spontaneously forms phosphorus-carbon bonds, has a reaction rate sensitive to the aryl diazonium substituent and alters the electronic properties of exfoliated BP, ultimately yielding a strong, tunable p-type doping that simultaneously improves the field-effect transistor mobility and on/off current ratio. This chemical functionalization pathway controllably modifies the properties of exfoliated BP, and thus improves its prospects for nanoelectronic applications.

  10. A covalent attraction between two molecular cation TTF·~+

    Institute of Scientific and Technical Information of China (English)

    WANG FangFang; WANG Yi; WANG BingQiang; WANG YinFeng; MA Fang; Li ZhiRu

    2009-01-01

    The optimized structure of the tetrathiafulvalence radical-cation dimer (TTF·~+-TTF·~+) with all-real frequencies is obtained at MP2/6-311G level,which exhibits the attraction between two molecular cation TTF·~+.The new attraction interaction is a 20-center-2-electron intermolecular covalent π/π bonding with a telescope shape.The covalent π/π bonding has the bonding energy of about-21 kcal·mol~(-1) and is concealed by the Coulombic repulsion between two TTF·~+ cations.This intermolecular covalent attraction also influences the structure of the TTF·~+ subunit,I.e.,its molecular plane is bent by an angle θ=5.6°.This work provides new knowledge on intermolecular interaction.

  11. A covalent attraction between two molecular cation TTF·~+

    Institute of Scientific and Technical Information of China (English)

    2009-01-01

    The optimized structure of the tetrathiafulvalence radical-cation dimer(TTF·+-TTF·+) with all-real frequencies is obtained at MP2/6-311G level,which exhibits the attraction between two molecular cation TTF·+.The new attraction interaction is a 20-center-2-electron intermolecular covalent π /π bonding with a telescope shape.The covalent π /π bonding has the bonding energy of about -21 kcal·mol-1 and is concealed by the Coulombic repulsion between two TTF·+ cations.This intermolecular covalent attraction also influences the structure of the TTF·+ subunit,i.e.,its molecular plane is bent by an angle θ=5.6°.This work provides new knowledge on intermolecular interaction.

  12. Dialing in the Ratio of Covalent and Coordination Cross-links in Self-healing Hydrogels

    DEFF Research Database (Denmark)

    Andersen, Amanda; Krogsgaard, Marie; Birkedal, Henrik

    ; it is of great interest to control the degree of which these are present; i.e. controlling the degree of catechol oxidation. Here, we report hydrogels in which the catechols participating in reversible (oxidation resistant catechol-analogue6) and irreversible oxidation cross-links are separated, enabling one...... to predefine the ratio of the two by altering the composition. The oxidation-resistant catechol-analogue was grafted onto polyallylamine,4 while the oxidation cross-links are introduced by addition of tannic acid that has the same useful properties as catechols.5,7,8 This affords hydrogels that retain self......-healing abilities even at high pH but that can be stiffened at will by dialing in the required degree of covalent crosslinking. This dial-in method thus harnesses two aspects of catechol-type chemistries to yield double network hydrogels in a straightforward and highly controllable manner....

  13. Covalent dimers of 1,3-diphenylisobenzofuran for singlet fission: synthesis and electrochemistry.

    Science.gov (United States)

    Akdag, Akin; Wahab, Abdul; Beran, Pavel; Rulíšek, Lubomír; Dron, Paul I; Ludvík, Jiří; Michl, Josef

    2015-01-02

    The synthesis of covalent dimers in which two 1,3-diphenylisobenzofuran units are connected through one phenyl substituent on each is reported. In three of the dimers, the subunits are linked directly, and in three others, they are linked via an alkane chain. A seventh new compound in which two 1,3-diphenylisobenzofuran units share a phenyl substituent is also described. These materials are needed for investigations of the singlet fission process, which promises to increase the efficiency of solar cells. The electrochemical oxidation and reduction of the monomer, two previously known dimers, and the seven new compounds have been examined, and reversible redox potentials have been compared with results obtained from density functional theory. Although the overall agreement is satisfactory, some discrepancies are noted and discussed.

  14. Covalent and non-covalent curcumin loading in acid-responsive polymeric micellar nanocarriers

    Science.gov (United States)

    Gao, Min; Chen, Chao; Fan, Aiping; Zhang, Ju; Kong, Deling; Wang, Zheng; Zhao, Yanjun

    2015-07-01

    Poor aqueous solubility, potential degradation, rapid metabolism and elimination lead to low bioavailability of pleiotropic impotent curcumin. Herein, we report two types of acid-responsive polymeric micelles where curcumin was encapsulated via both covalent and non-covalent modes for enhanced loading capacity and on-demand release. Biodegradable methoxy poly(ethylene glycol)-poly(lactic acid) copolymer (mPEG-PLA) was conjugated with curcumin via a hydrazone linker, generating two conjugates differing in architecture (single-tail versus double-tail) and free curcumin was encapsulated therein. The two micelles exhibited similar hydrodynamic size at 95 ± 3 nm (single-tail) and 96 ± 3 nm (double-tail), but their loading capacities differed significantly at 15.0 ± 0.5% (w/w) (single-tail) and 4.8 ± 0.5% (w/w) (double-tail). Under acidic sink conditions (pH 5.0 and 6.0), curcumin displayed a faster release from the single-tail nanocarrier, which was correlated to a low IC50 of 14.7 ± 1.6 (μg mL-1) compared to the value of double-tail micelle (24.9 ± 1.3 μg mL-1) in HeLa cells. The confocal imaging and flow cytometry analysis demonstrated a superior capability of single-tail micelle for intracellular curcumin delivery, which was a consequence of the higher loading capacity and lower degree of mPEG surface coverage. In conclusion, the dual loading mode is an effective means to increase the drug content in the micellar nanocarriers whose delivery efficiency is highly dependent on its polymer-drug conjugate architecture. This strategy offers an alternative nanoplatform for intracellularly delivering impotent hydrophobic agents (i.e. curcumin) in an efficient stimuli-triggered way, which is valuable for the enhancement of curcumin’s efficacy in managing a diverse range of disorders.

  15. Covalent and non-covalent curcumin loading in acid-responsive polymeric micellar nanocarriers

    International Nuclear Information System (INIS)

    Gao, Min; Chen, Chao; Fan, Aiping; Wang, Zheng; Zhao, Yanjun; Zhang, Ju; Kong, Deling

    2015-01-01

    Poor aqueous solubility, potential degradation, rapid metabolism and elimination lead to low bioavailability of pleiotropic impotent curcumin. Herein, we report two types of acid-responsive polymeric micelles where curcumin was encapsulated via both covalent and non-covalent modes for enhanced loading capacity and on-demand release. Biodegradable methoxy poly(ethylene glycol)-poly(lactic acid) copolymer (mPEG-PLA) was conjugated with curcumin via a hydrazone linker, generating two conjugates differing in architecture (single-tail versus double-tail) and free curcumin was encapsulated therein. The two micelles exhibited similar hydrodynamic size at 95 ± 3 nm (single-tail) and 96 ± 3 nm (double-tail), but their loading capacities differed significantly at 15.0 ± 0.5% (w/w) (single-tail) and 4.8 ± 0.5% (w/w) (double-tail). Under acidic sink conditions (pH 5.0 and 6.0), curcumin displayed a faster release from the single-tail nanocarrier, which was correlated to a low IC_5_0 of 14.7 ± 1.6 (μg mL"−"1) compared to the value of double-tail micelle (24.9 ± 1.3 μg mL"−"1) in HeLa cells. The confocal imaging and flow cytometry analysis demonstrated a superior capability of single-tail micelle for intracellular curcumin delivery, which was a consequence of the higher loading capacity and lower degree of mPEG surface coverage. In conclusion, the dual loading mode is an effective means to increase the drug content in the micellar nanocarriers whose delivery efficiency is highly dependent on its polymer–drug conjugate architecture. This strategy offers an alternative nanoplatform for intracellularly delivering impotent hydrophobic agents (i.e. curcumin) in an efficient stimuli-triggered way, which is valuable for the enhancement of curcumin’s efficacy in managing a diverse range of disorders. (paper)

  16. Chemical modifications and reactions in DNA nanostructures

    DEFF Research Database (Denmark)

    Gothelf, Kurt Vesterager

    2017-01-01

    such as hydrocarbons or steroids have been introduced to change the surface properties of DNA origami structures, either to protect the DNA nanostructure or to dock it into membranes and other hydrophobic surfaces. DNA nanostructures have also been used to control covalent chemical reactions. This article provides......DNA nanotechnology has the power to form self-assembled and well-defined nanostructures, such as DNA origami, where the relative positions of each atom are known with subnanometer precision. Our ability to synthesize oligonucleotides with chemical modifications in almost any desired position...... provides rich opportunity to incorporate molecules, biomolecules, and a variety of nanomaterials in specific positions on DNA nanostructures. Several standard modifications for oligonucleotides are available commercially, such as dyes, biotin, and chemical handles, and such modified oligonucleotides can...

  17. Construction of covalently coupled, concatameric dimers of 7TM receptors

    DEFF Research Database (Denmark)

    Terpager, Marie; Scholl, D Jason; Kubale, Valentina

    2009-01-01

    -Ala repeats flanked by flexible spacers and positively charged residues to ensure correct inside-out orientation plus an extracellular HA-tag to construct covalently coupled dimers of 7TM receptors. Such 15 TM concatameric homo- and heterodimers of the beta(2)-adrenergic and the NK(1) receptors, which...... for either of the protomers, which was not observed upon simple coexpression of the two receptors. It is concluded that covalently joined 7TM receptor dimers with surprisingly normal receptor properties can be constructed with use of an artificial transmembrane connector, which perhaps can be used to fuse...

  18. Protein modification by acrolein: Formation and stability of cysteine adducts

    OpenAIRE

    Cai, Jian; Bhatnagar, Aruni; Pierce, William M.

    2009-01-01

    The toxicity of the ubiquitous pollutant and endogenous metabolite, acrolein, is due in part to covalent protein modifications. Acrolein reacts readily with protein nucleophiles via Michael addition and Schiff base formation. Potential acrolein targets in protein include the nucleophilic side chains of cysteine, histidine, and lysine residues as well as the free amino terminus of proteins. Although cysteine is the most acrolein-reactive residue, cysteine-acrolein adducts are difficult to iden...

  19. The isothiocyanate class of bioactive nutrients covalently inhibit the MEKK1 protein kinase

    Directory of Open Access Journals (Sweden)

    Macdonald Timothy L

    2007-09-01

    Full Text Available Abstract Background Dietary isothiocyanates (ITCs are electrophilic compounds that have diverse biological activities including induction of apoptosis and effects on cell cycle. They protect against experimental carcinogenesis in animals, an activity believed to result from the transcriptional induction of "Phase 2" enzymes. The molecular mechanism of action of ITCs is unknown. Since ITCs are electrophiles capable of reacting with sulfhydryl groups on amino acids, we hypothesized that ITCs induce their biological effects through covalent modification of proteins, leading to changes in cell regulatory events. We previously demonstrated that stress-signaling kinase pathways are inhibited by other electrophilic compounds such as menadione. We therefore tested the effects of nutritional ITCs on MEKK1, an upstream regulator of the SAPK/JNK signal transduction pathway. Methods The activity of MEKK1 expressed in cells was monitored using in vitro kinase assays to measure changes in catalytic activity. The activity of endogenous MEKK1, immunopurified from ITC treated and untreated LnCAP cells was also measured by in vitro kinase assay. A novel labeling and affinity reagent for detection of protein modification by ITCs was synthesized and used in competition assays to monitor direct modification of MEKK1 by ITC. Finally, immunoblots with phospho-specific antibodies were used to measure the activity of MAPK protein kinases. Results ITCs inhibited the MEKK1 protein kinase in a manner dependent on a specific cysteine residue in the ATP binding pocket. Inhibition of MEKK1 catalytic activity was due to direct, covalent and irreversible modification of the MEKK1 protein itself. In addition, ITCs inhibited the catalytic activity of endogenous MEKK1. This correlated with inhibition of the downstream target of MEKK1 activity, i.e. the SAPK/JNK kinase. This inhibition was specific to SAPK, as parallel MAPK pathways were unaffected. Conclusion These results

  20. The isothiocyanate class of bioactive nutrients covalently inhibit the MEKK1 protein kinase

    International Nuclear Information System (INIS)

    Cross, Janet V; Foss, Frank W; Rady, Joshua M; Macdonald, Timothy L; Templeton, Dennis J

    2007-01-01

    Dietary isothiocyanates (ITCs) are electrophilic compounds that have diverse biological activities including induction of apoptosis and effects on cell cycle. They protect against experimental carcinogenesis in animals, an activity believed to result from the transcriptional induction of 'Phase 2' enzymes. The molecular mechanism of action of ITCs is unknown. Since ITCs are electrophiles capable of reacting with sulfhydryl groups on amino acids, we hypothesized that ITCs induce their biological effects through covalent modification of proteins, leading to changes in cell regulatory events. We previously demonstrated that stress-signaling kinase pathways are inhibited by other electrophilic compounds such as menadione. We therefore tested the effects of nutritional ITCs on MEKK1, an upstream regulator of the SAPK/JNK signal transduction pathway. The activity of MEKK1 expressed in cells was monitored using in vitro kinase assays to measure changes in catalytic activity. The activity of endogenous MEKK1, immunopurified from ITC treated and untreated LnCAP cells was also measured by in vitro kinase assay. A novel labeling and affinity reagent for detection of protein modification by ITCs was synthesized and used in competition assays to monitor direct modification of MEKK1 by ITC. Finally, immunoblots with phospho-specific antibodies were used to measure the activity of MAPK protein kinases. ITCs inhibited the MEKK1 protein kinase in a manner dependent on a specific cysteine residue in the ATP binding pocket. Inhibition of MEKK1 catalytic activity was due to direct, covalent and irreversible modification of the MEKK1 protein itself. In addition, ITCs inhibited the catalytic activity of endogenous MEKK1. This correlated with inhibition of the downstream target of MEKK1 activity, i.e. the SAPK/JNK kinase. This inhibition was specific to SAPK, as parallel MAPK pathways were unaffected. These results demonstrate that MEKK1 is directly modified and inhibited by

  1. Covalent attachment of pyridine-type molecules to glassy carbon surfaces by electrochemical reduction of in situ generated diazonium salts. Formation of ruthenium complexes on ligand-modified surfaces

    International Nuclear Information System (INIS)

    Yesildag, Ali; Ekinci, Duygu

    2010-01-01

    In this study, pyridine, quinoline and phenanthroline molecules were covalently bonded to glassy carbon (GC) electrode surfaces for the first time using the diazonium modification method. Then, the complexation ability of the modified films with ruthenium metal cations was investigated. The derivatization of GC surfaces with heteroaromatic molecules was achieved by electrochemical reduction of the corresponding in situ generated diazonium salts. X-ray photoelectron spectroscopy (XPS) was used to confirm the attachment of heteroaromatic molecules to the GC surfaces and to determine the surface concentration of the films. The barrier properties of the modified GC electrodes were studied in the presence of redox probes such as Fe(CN) 6 3- and Ru(NH 3 ) 6 3+ by cyclic voltammetry. Additionally, the presence of the resulting organometallic films on the surfaces was verified by XPS after the chemical transformation of the characterized ligand films to the ruthenium complex films. The electrochemical behavior of these films in acetonitrile solution was investigated using voltammetric methods, and the surface coverage of the organometallic films was determined from the reversible metal-based Ru(II)/Ru(III) oxidation waves.

  2. Covalent attachment of pyridine-type molecules to glassy carbon surfaces by electrochemical reduction of in situ generated diazonium salts. Formation of ruthenium complexes on ligand-modified surfaces

    Energy Technology Data Exchange (ETDEWEB)

    Yesildag, Ali [Department of Chemistry, Faculty of Sciences, Atatuerk University, 25240 Erzurum (Turkey); Ekinci, Duygu, E-mail: dekin@atauni.edu.t [Department of Chemistry, Faculty of Sciences, Atatuerk University, 25240 Erzurum (Turkey)

    2010-09-30

    In this study, pyridine, quinoline and phenanthroline molecules were covalently bonded to glassy carbon (GC) electrode surfaces for the first time using the diazonium modification method. Then, the complexation ability of the modified films with ruthenium metal cations was investigated. The derivatization of GC surfaces with heteroaromatic molecules was achieved by electrochemical reduction of the corresponding in situ generated diazonium salts. X-ray photoelectron spectroscopy (XPS) was used to confirm the attachment of heteroaromatic molecules to the GC surfaces and to determine the surface concentration of the films. The barrier properties of the modified GC electrodes were studied in the presence of redox probes such as Fe(CN){sub 6}{sup 3-} and Ru(NH{sub 3}){sub 6}{sup 3+} by cyclic voltammetry. Additionally, the presence of the resulting organometallic films on the surfaces was verified by XPS after the chemical transformation of the characterized ligand films to the ruthenium complex films. The electrochemical behavior of these films in acetonitrile solution was investigated using voltammetric methods, and the surface coverage of the organometallic films was determined from the reversible metal-based Ru(II)/Ru(III) oxidation waves.

  3. Solid-state mAbs and ADCs subjected to heat-stress stability conditions can be covalently modified with buffer and excipient molecules.

    Science.gov (United States)

    Valliere-Douglass, John F; Lewis, Patsy; Salas-Solano, Oscar; Jiang, Shan

    2015-02-01

    We report that a unique type of chemical modification occurs on lyophilized proteins. Freeze-dried mAbs and antibody-drug conjugates (ADCs) can be covalently modified with buffer and excipient molecules on the side chains of Glu, Asp, Thr, and Ser amino acids when subjected to temperature stress. The reaction occurs primarily via condensation of common buffers and excipients such as histidine, tris, trehalose and sucrose, with Glu and Asp carboxylates in the primary sequence of proteins. The reaction was also found to proceed through condensation of carboxylate containing buffers such as citrate, with Thr and Ser hydroxyls in the primary sequence of proteins. Based on the mass of the covalent adducts observed on mAbs and ADCs, it is apparent that the reaction produces water as a product and is thus favored in a low moisture environments such as a lyophilized protein cake. Herein, we present the evidence for the covalent modification of proteins drawn from case studies of in-depth characterization of heat-stressed mAbs and ADCs in the solid state. We also demonstrate how common charge variant assays such as imaged capillary isoelectric focusing and mass spectrometry can be used to monitor this specific class of protein modification. © 2014 Wiley Periodicals, Inc. and the American Pharmacists Association.

  4. Covalent microcontact printing of proteins fro cell patterning

    NARCIS (Netherlands)

    Rozkiewicz, D.I.; Kraan, Yvonne M.; Werten, Marc W.T.; de Wolf, Frits A.; Subramaniam, Vinod; Ravoo, B.J.; Reinhoudt, David

    2006-01-01

    We describe a straightforward approach to the covalent immobilization of cytophilic proteins by microcontact printing, which can be used to pattern cells on substrates. Cytophilic proteins are printed in micropatterns on reactive self-assembled monolayers by using imine chemistry. An

  5. Capillary electrophoresis of covalently functionalized single-chirality carbon nanotubes.

    Science.gov (United States)

    He, Pingli; Meany, Brendan; Wang, Chunyan; Piao, Yanmei; Kwon, Hyejin; Deng, Shunliu; Wang, YuHuang

    2017-07-01

    We demonstrate the separation of chirality-enriched single-walled carbon nanotubes (SWCNTs) by degree of surface functionalization using high-performance CE. Controlled amounts of negatively charged and positively charged functional groups were attached to the sidewall of chirality-enriched SWCNTs through covalent functionalization using 4-carboxybenzenediazonium tetrafluoroborate or 4-diazo-N,N-diethylaniline tetrafluoroborate, respectively. Surfactant- and pH-dependent studies confirmed that under conditions that minimized ionic screening effects, separation of these functionalized SWCNTs was strongly dependent on the surface charge density introduced through covalent surface chemistry. For both heterogeneous mixtures and single-chirality-enriched samples, covalently functionalized SWCNTs showed substantially increased peak width in electropherogram spectra compared to nonfunctionalized SWCNTs, which can be attributed to a distribution of surface charges along the functionalized nanotubes. Successful separation of functionalized single-chirality SWCNTs by functional density was confirmed with UV-Vis-NIR absorption and Raman scattering spectroscopies of fraction collected samples. These results suggest a high degree of structural heterogeneity in covalently functionalized SWCNTs, even for chirality-enriched samples, and show the feasibility of applying CE for high-performance separation of nanomaterials based on differences in surface functional density. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  6. COVAL, Compound Probability Distribution for Function of Probability Distribution

    International Nuclear Information System (INIS)

    Astolfi, M.; Elbaz, J.

    1979-01-01

    1 - Nature of the physical problem solved: Computation of the probability distribution of a function of variables, given the probability distribution of the variables themselves. 'COVAL' has been applied to reliability analysis of a structure subject to random loads. 2 - Method of solution: Numerical transformation of probability distributions

  7. Covalent Attachment of Bent-Core Mesogens to Silicon Surfaces

    NARCIS (Netherlands)

    Scheres, L.; Achten, R.; Giesbers, M.; Smet, de L.; Arafat, A.; Sudhölter, E.J.R.; Marcelis, A.T.M.; Zuilhof, H.

    2009-01-01

    Two vinyl-terminated bent core-shaped liquid crystalline molecules that exhibit thermotropic antiferroelectric SmCPA phases have been covalently attached onto a hydrogen-terminated silicon(111) surface. The surface attachment was achieved via a mild procedure from a mesitylene solution, using

  8. Multi-step non-covalent pathways to supramolecular systems

    NARCIS (Netherlands)

    Hermans, T.M.

    2010-01-01

    The spontaneous organization of building blocks into ordered structures governed by non-covalent interactions, or self-assembly, is a commonly encountered pathway in nature to obtain functional materials. These materials often consist of many different components ordered into intricate structures.

  9. Covalent Functionalization of Carbon Nanotube by Tetrasubtituted Amino Manganese Phthalocyanine

    Institute of Scientific and Technical Information of China (English)

    Zheng Long YANG; Hong Zheng CHEN; Lei CAO; Han Yin LI; Mang WANG

    2004-01-01

    The multiwall carbon nanotube (MWCNT) bonded to 2, 9, 16, 23-tetraamino manganese phthalocyanine (TAMnPc) was obtained by covalent functionalization, and its chemical structure was characterized by TEM. The photoconductivity of single-layered photoreceptors, where MWCNT bonded by TAMnPc (MWCNT-b-TAMnPc) served as the charge generation material (CGM), was also studied.

  10. Double Dynamic Supramolecular Polymers of Covalent Oligo-Dynamers

    NARCIS (Netherlands)

    Schaeffer, Gaël; Buhler, Eric; Candau, Sauveur Jean; Lehn, Jean-Marie

    2013-01-01

    Double-dynamic polymers, incorporating both molecular and supramolecular dynamic features (“double dynamers”) have been generated, where these functions are present in a nonstoichiometric ratio in the main chain of the polymer. It has been achieved by (1) the formation of covalent oligo-dynamers in

  11. Covalent bindings in proteins following UV-C irradiation

    International Nuclear Information System (INIS)

    Diezel, W.; Meffert, H.; Soennichsen, N.; Reinicke, C.

    1980-01-01

    Following a UV-C irradiation of catalase cross-linked catalase subunits could be detected by sodium dodecylsulfate gel electrophoresis. The subunits of aldolase were not cross-linked. The origin of covalent bindings in the catalase molecule is suggested to be effected by a free radical chain reaction induced by the heme component of catalase after UV-C irradiation. (author)

  12. Milk whey protein modification by coffee-specific phenolics: effect on structural and functional properties.

    Science.gov (United States)

    Ali, Mostafa; Homann, Thomas; Khalil, Mahmoud; Kruse, Hans-Peter; Rawel, Harshadrai

    2013-07-17

    A suitable vehicle for integration of bioactive plant constituents is proposed. It involves modification of proteins using phenolics and applying these for protection of labile constituents. It dissects the noncovalent and covalent interactions of β-lactoglobulin with coffee-specific phenolics. Alkaline and polyphenol oxidase modulated covalent reactions were compared. Tryptic digestion combined with MALDI-TOF-MS provided tentative allocation of the modification type and site in the protein, and an in silico modeling of modified β-lactoglobulin is proposed. The modification delivers proteins with enhanced antioxidative properties. Changed structural properties and differences in solubility, surface hydrophobicity, and emulsification were observed. The polyphenol oxidase modulated reaction provides a modified β-lactoglobulin with a high antioxidative power, is thermally more stable, requires less energy to unfold, and, when emulsified with lutein esters, exhibits their higher stability against UV light. Thus, adaptation of this modification provides an innovative approach for functionalizing proteins and their uses in the food industry.

  13. Trafficking and function of the cystic fibrosis transmembrane conductance regulator: a complex network of posttranslational modifications

    Science.gov (United States)

    McClure, Michelle L.; Barnes, Stephen; Brodsky, Jeffrey L.

    2016-01-01

    Posttranslational modifications add diversity to protein function. Throughout its life cycle, the cystic fibrosis transmembrane conductance regulator (CFTR) undergoes numerous covalent posttranslational modifications (PTMs), including glycosylation, ubiquitination, sumoylation, phosphorylation, and palmitoylation. These modifications regulate key steps during protein biogenesis, such as protein folding, trafficking, stability, function, and association with protein partners and therefore may serve as targets for therapeutic manipulation. More generally, an improved understanding of molecular mechanisms that underlie CFTR PTMs may suggest novel treatment strategies for CF and perhaps other protein conformational diseases. This review provides a comprehensive summary of co- and posttranslational CFTR modifications and their significance with regard to protein biogenesis. PMID:27474090

  14. Mass spectrometric identification of isocyanate-induced modifications of keratins in human skin

    NARCIS (Netherlands)

    Hulst, A.G.; Verstappen, D.R.W.; Riet-van Oeveren, D. van der; Vermeulen, N.P.E.; Noort, D.

    2015-01-01

    In the current paper we show that exposure of human callus to isocyanates leads to covalent modifications within keratin proteins. Mass spectrometric analyses of pronase digests of keratin isolated from exposed callus show that both mono- and di-adducts (for di-isocyanates) are predominantly formed

  15. Radiation modification of glass fiber - reinforced plastics

    International Nuclear Information System (INIS)

    Allayarov, S.R.; Smirnov, Yu.N.; Lesnichaya, V.A.; Ol'khov, Yu.A.; Belov, G.P.; Dixon, D.A.; Kispert, L.D.

    2007-01-01

    Modification of glass fiber - reinforced plastics (GFRPs) by gamma-irradiation has been researched to receipt of polymeric composite materials. They were produced by the film - technology method and the cheapest thermoplastics (polythene, polyamide were used as polymeric matrixes for their manufacture. GFRPs were irradiated with Co 60 gamma-rays from a Gammatok-100 source in air and in vacuum. The strength properties of GFRPs and initial polymeric matrixes were investigated before and after radiolysis. Molecular - topological structure of the polymeric matrixes were tested by the method of thermomechanical spectroscopy. The strength properties of GFRPs depend on a parity of speeds of structural (physical) and chemical modification of the polymeric matrixes. These two processes proceed simultaneously. The structural modification includes physical transformation of polymers at preservation of their chemical structure. Covalent bonds between various macromolecules or between macromolecules and surface of fiberglasses are formed at the chemical modification of polymeric matrixes induced by radiation. Action of ionizing radiation on the used polymeric matrix results to its structurization (polythene) or to destruction (polyamide). Increasing of durability of GFRPs containing polythene is caused by formation of the optimum molecular topological structure of the polymeric matrix. (authors)

  16. Gelation of covalently edge-modified laponites in aqueous media. 1. rheology and nuclear magnetic resonance.

    Science.gov (United States)

    Patil, Suhas P; Mathew, Renny; Ajithkumar, T G; Rajamohanan, P R; Mahesh, T S; Kumaraswamy, Guruswamy

    2008-04-17

    We describe the covalent modification of the edges of laponite with organic groups and the influence of this modification on gelation behavior. We compare three materials: an unmodified laponite, a laponite edge modified with a trimethyl moiety (MLap), and an octyldimethyl moiety (OLap). Gelation is investigated using rheology and NMR T1 relaxation measurements and nuclear Overhauser enhancement spectroscopy (NOESY). MLap and OLap show qualitatively different gelation. Gelation of MLap is very similar to laponite: MLap gels over the same time scale as laponite and has about the same solid modulus, and the MLap gel is almost as transparent as laponite. In contrast, OLap gels rapidly relative to laponite and forms a weak, turbid gel. We believe that gelation in laponite and MLap results from the formation of a network of well-dispersed platelets (or a few platelets), while in OLap, gelation results from a network of stacks of several platelets. NMR relaxation measurements indicate that gelation does not affect the average relaxation of water protons. However, T1 increases marginally for the protons in the organic moieties in MLap and decreases for protons in the organic moieties in OLap. Relaxation measurements, analyses of line width, and NOESY taken together suggest that, in OLap, gelation is a consequence of association of the organic moieties on the laponite edges, and that this association strengthens with time. Thus, the time-dependent changes in NMR suggest a structural origin for the time-dependent changes in the rheological behavior.

  17. ZT-40M system design, modification, and installation

    International Nuclear Information System (INIS)

    Hammer, C.F.

    1981-01-01

    ZT-40 is a reversed field pinch experiment which had been operated as originally designed, with a ceramic discharge tube until November 1980. At that time, the experiment was shut down for major modifications. This paper will describe these modifications in general and discuss in detail the design of the energy system

  18. Three-dimensionally Functionalized Reverse Phase Glycoprotein Array for Cancer Biomarker Discovery and Validation

    OpenAIRE

    Pan, Li; Aguilar, Hillary Andaluz; Wang, Linna; Iliuk, Anton; Tao, W. Andy

    2016-01-01

    Glycoproteins have vast structural diversity which plays an important role in many biological processes and have great potential as disease biomarkers. Here we report a novel functionalized reverse phase protein array (RPPA), termed polymer-based reverse phase GlycoProtein Array (polyGPA), to specifically capture and profile glycoproteomes, and validate glycoproteins. Nitrocellulose membrane functionalized with globular hydroxyaminodendrimers was used to covalently capture pre-oxidized glycan...

  19. Binding matter with antimatter: the covalent positron bond.

    Science.gov (United States)

    Charry, Jorge Alfonso; Varella, Marcio T Do N; Reyes, Andrés

    2018-05-16

    We report sufficient theoretical evidence of the energy stability of the e⁺H₂²⁻ molecule, formed by two H⁻ anions and one positron. Analysis of the electronic and positronic densities of the latter compound undoubtedly points out the formation of a positronic covalent bond between the otherwise repelling hydride anions. The lower limit for the bonding energy of the e⁺H₂²⁻ molecule is 74 kJ/mol (0.77 eV), accounting for the zero-point vibrational correction. The formation of a non electronic covalent bond is fundamentally distinct from positron attachment to stable molecules, as the latter process is characterized by a positron affinity, analogous to the electron affinity. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  20. Two supramolecular complexes based on polyoxometalates and Co-EDTA units via covalent connection or non-covalent interaction

    Energy Technology Data Exchange (ETDEWEB)

    Teng, Chunlin; Xiao, Hanxi [Key Laboratory of Theoretical Organic Chemistry and Functional Molecule for Ministry of Education, Hunan University of Science and Technology, Xiangtan 411201 (China); Cai, Qing [Chemistry Department, City University of New York, New York, NY 10016 (United States); Tang, Jianting; Cai, Tiejun [Key Laboratory of Theoretical Organic Chemistry and Functional Molecule for Ministry of Education, Hunan University of Science and Technology, Xiangtan 411201 (China); Deng, Qian, E-mail: dengqian10502@163.com [Key Laboratory of Theoretical Organic Chemistry and Functional Molecule for Ministry of Education, Hunan University of Science and Technology, Xiangtan 411201 (China)

    2016-11-15

    Two new 3D network organic-inorganic hybrid supramolecular complexes ([Na{sub 6}(CoEDTA){sub 2}(H{sub 2}O){sub 13}]·(H{sub 2}SiW{sub 12}O{sub 40})·xH{sub 2}O)n (1) and [CoH{sub 4}EDTA(H{sub 2}O)]{sub 2}(SiW{sub 12}O{sub 40})·15H{sub 2}O (2) (H{sub 4}EDTA=Ethylenediamine tetraacetic acid) have been successfully synthesized by solution method, and characterized by infrared spectrum (IR), thermogravimetric-differential thermal analysis (TG-DTA), cyclic voltammetry (CV) and single{sup −}crystal X-ray diffraction (XRD). Both of the complexes are the supramolecules, but with different liking mode, they are two representative models of supramolecule. complex (1) is a 3D infinite network supramolecular coordination polymer with a rare multi-metal sturcture of sodium-cobalt-containing, which is mainly linked through coordinate-covalent bonds. While complex (2) is normal supramolecule, which linked by non-covalent interactions, such as H-bonding interaction, electrostatic interaction and van der waals force. Both of complex (1) and (2) exhibit good catalytic activities for catalytic oxidation of methanol, when the initial concentration of methanol is 3.0 g m{sup −3}, flow rate is 10 mL min{sup −1}, and the quality of catalyst is 0.2 g, for complex (1) and complex (2) the maximum elimination rates of methanol are 85% (150 °C) and 92% (120 °C), respectively. - Graphical abstract: Two new organic-inorganic hybrid supramolecular complexes based on Co-EDTA, and Keggin polyanions have been successfully synthesized with different pH value by solution method. They are attributed to two representative models of supramolecule. Complex(1) is an infinite coordination polymer with a rare multi-metal sturcture of sodium-cobalt-containing, which is mainly linked through covalent bonds. Complex (2) is a normal supramolecule, which linked by non-covalent interactions of H-bonding interaction, electrostatic interaction and van der waals force. - Highlights: • Two supramolecules

  1. Building high-coverage monolayers of covalently bound magnetic nanoparticles

    Energy Technology Data Exchange (ETDEWEB)

    Williams, Mackenzie G.; Teplyakov, Andrew V., E-mail: andrewt@udel.edu

    2016-12-01

    Graphical abstract: - Highlights: • A method for forming a layer of covalently bound nanoparticles is offered. • A nearly perfect monolayer of covalently bound magnetic nanoparticles was formed on gold. • Spectroscopic techniques confirmed covalent binding by the “click” reaction. • The influence of the functionalization scheme on surface coverage was investigated. - Abstract: This work presents an approach for producing a high-coverage single monolayer of magnetic nanoparticles using “click chemistry” between complementarily functionalized nanoparticles and a flat substrate. This method highlights essential aspects of the functionalization scheme for substrate surface and nanoparticles to produce exceptionally high surface coverage without sacrificing selectivity or control over the layer produced. The deposition of one single layer of magnetic particles without agglomeration, over a large area, with a nearly 100% coverage is confirmed by electron microscopy. Spectroscopic techniques, supplemented by computational predictions, are used to interrogate the chemistry of the attachment and to confirm covalent binding, rather than attachment through self-assembly or weak van der Waals bonding. Density functional theory calculations for the surface intermediate of this copper-catalyzed process provide mechanistic insight into the effects of the functionalization scheme on surface coverage. Based on this analysis, it appears that steric limitations of the intermediate structure affect nanoparticle coverage on a flat solid substrate; however, this can be overcome by designing a functionalization scheme in such a way that the copper-based intermediate is formed on the spherical nanoparticles instead. This observation can be carried over to other approaches for creating highly controlled single- or multilayered nanostructures of a wide range of materials to result in high coverage and possibly, conformal filling.

  2. Dislocations in materials with mixed covalent and metallic bonding

    International Nuclear Information System (INIS)

    Nguyen-Manh, D.; Cawkwell, M.J.; Groeger, R.; Mrovec, M.; Porizek, R.; Pettifor, D.G.; Vitek, V.

    2005-01-01

    Environment-dependent bond-order potentials have been developed for L1 0 TiAl, bcc Mo and fcc Ir. They comprise both the angular character of bonding and the screening effect of nearly free electrons. These potentials have been employed in atomistic studies of screw dislocations that revealed the non-planar character of their cores. It is argued that both covalent as well as metallic character of bonding govern these structures, which in turn control the mechanical behaviour

  3. Preparation and characterization of two types of covalently immobilized amyloglucosidase

    Directory of Open Access Journals (Sweden)

    ZORAN VUJCIC

    2005-05-01

    Full Text Available Amyloglucosidase from A. niger was covalently immobilized onto poly (GMA-co-EGDMA by the glutaraldehyde and periodate method. The immobilization of amyloglucosidase after periodate oxidation gave a preparate with the highest specific activity reported so far on similar polymers. The obtained immobilized preparates show the same pH optimum, but a higher temperature optimum compared with the soluble enzyme. The kinetic parameters for the hydrolysis of soluble starch by free and both immobilized enzymes were determined.

  4. Covalently coupled hybrid of graphitic carbon nitride with reduced graphene oxide as a superior performance lithium-ion battery anode

    Science.gov (United States)

    Fu, Yongsheng; Zhu, Junwu; Hu, Chong; Wu, Xiaodong; Wang, Xin

    2014-10-01

    An in situ chemical synthetic approach has been designed for the fabrication of a covalently coupled hybrid consisting of graphitic carbon nitride (g-C3N4) with reduced graphene oxide (rGO) with differing g-C3N4/rGO ratio. The epoxy groups of graphene oxide (GO) undergo a nucleophilic substitution reaction with dicyandiamide (C2H4N4) to form the C2H4N4-GO composite via a covalent C-N bond, and then both the in situ polymerization of C2H4N4 and the thermal reduction of GO can be achieved at higher temperatures, forming the covalently coupled g-C3N4-rGO. FT-IR, CP-MAS NMR and XPS analyses, clearly revealed a covalent interaction between the g-C3N4 and rGO sheets. The g-C3N4-rGO exhibits an unprecedented high, stable and reversible capacity of 1525 mA h g-1 at a current density of 100 mA g-1 after 50 cycles. Even at a large current density of 1000 mA g-1, a reversible capacity of 943 mA h g-1 can still be retained. The superior electrochemical performance of g-C3N4-rGO is attributed to the specific characteristics of the unique nanostructure of g-C3N4-rGO and the concerted effects of g-C3N4 and rGO, including covalent interactions between the two moieties, the good conductivity and high special surface area of the nanocomposite, as well as the template effect of the planar amino group of g-C3N4 for the dispersed decoration of Li+ ions.An in situ chemical synthetic approach has been designed for the fabrication of a covalently coupled hybrid consisting of graphitic carbon nitride (g-C3N4) with reduced graphene oxide (rGO) with differing g-C3N4/rGO ratio. The epoxy groups of graphene oxide (GO) undergo a nucleophilic substitution reaction with dicyandiamide (C2H4N4) to form the C2H4N4-GO composite via a covalent C-N bond, and then both the in situ polymerization of C2H4N4 and the thermal reduction of GO can be achieved at higher temperatures, forming the covalently coupled g-C3N4-rGO. FT-IR, CP-MAS NMR and XPS analyses, clearly revealed a covalent interaction between

  5. Evidence of significant covalent bonding in Au(CN)(2)(-).

    Science.gov (United States)

    Wang, Xue-Bin; Wang, Yi-Lei; Yang, Jie; Xing, Xiao-Peng; Li, Jun; Wang, Lai-Sheng

    2009-11-18

    The Au(CN)(2)(-) ion is the most stable Au compound known for centuries, yet a detailed understanding of its chemical bonding is still lacking. Here we report direct experimental evidence of significant covalent bonding character in the Au-C bonds in Au(CN)(2)(-) using photoelectron spectroscopy and comparisons with its lighter congeners, Ag(CN)(2)(-) and Cu(CN)(2)(-). Vibrational progressions in the Au-C stretching mode were observed for all detachment transitions for Au(CN)(2)(-), in contrast to the atomic-like transitions for Cu(CN)(2)(-), revealing the Au-C covalent bonding character. In addition, rich electronic structural information was obtained for Au(CN)(2)(-) by employing 118 nm detachment photons. Density functional theory and high-level ab initio calculations were carried out to understand the photoelectron spectra and obtain insight into the nature of the chemical bonding in the M(CN)(2)(-) complexes. Significant covalent character in the Au-C bonding due to the strong relativistic effects was revealed in Au(CN)(2)(-), consistent with its high stability.

  6. Covalently bound molecular states in beryllium and carbon isotopes

    International Nuclear Information System (INIS)

    Wolfram von, Oertzen; Hans-Gerhard, Bohlen; Wolfram von, Oertzen

    2003-01-01

    Nuclear clustering in N=Z nuclei has been studied since many decades. States close to the decay thresholds, as described by the Ikeda diagram, are of particular interest. Recent studies in loosely bound systems, as observed with neutron-rich nuclei has revived the interest in cluster structures in nuclei, with additional valence neutrons, which give rise to pronounced covalent molecular structures. The Beryllium isotopes represent the first example of such unique states in nuclear physics with extreme deformations. In the deformed shell model these are referred to as super- and hyper-deformation. These states can be described explicitly by molecular concepts, with neutrons in covalent binding orbits. Examples of recent experiments performed at the HMI-Berlin demonstrating the molecular structure of the rotational bands in Beryllium isotopes are presented. Further work on chain states (nuclear polymers) in the carbon isotopes is in progress, these are the first examples of deformed structures in nuclei with an axis ratio of 3:1. A threshold diagram with clusters bound via neutrons in covalent molecular configurations can be established, which can serve as a guideline for future work. (authors)

  7. Managing Reverse Logistics or Reversing Logistics Management?

    OpenAIRE

    Brito, Marisa

    2004-01-01

    textabstractIn the past, supply chains were busy fine-tuning the logistics from raw material to the end customer. Today an increasing flow of products is going back in the chain. Thus, companies have to manage reverse logistics as well.This thesis contributes to a better understanding of reverse logistics. The thesis brings insights on reverse logistics decision-making and it lays down theoretical principles for reverse logistics as a research field.In particular it puts together a framework ...

  8. Reverse micelles as a tool for probing solvent modulation of protein dynamics: Reverse micelle encapsulated hemoglobin

    Science.gov (United States)

    Roche, Camille J.; Dantsker, David; Heller, Elizabeth R.; Sabat, Joseph E.; Friedman, Joel M.

    2013-08-01

    Hydration waters impact protein dynamics. Dissecting the interplay between hydration waters and dynamics requires a protein that manifests a broad range of dynamics. Proteins in reverse micelles (RMs) have promise as tools to achieve this objective because the water content can be manipulated. Hemoglobin is an appropriate tool with which to probe hydration effects. We describe both a protocol for hemoglobin encapsulation in reverse micelles and a facile method using PEG and cosolvents to manipulate water content. Hydration properties are probed using the water-sensitive fluorescence from Hb bound pyranine and covalently attached Badan. Protein dynamics are probed through ligand recombination traces derived from photodissociated carbonmonoxy hemoglobin on a log scale that exposes the potential role of both α and β solvent fluctuations in modulating protein dynamics. The results open the possibility of probing hydration level phenomena in this system using a combination of NMR and optical probes.

  9. Protein covalent immobilization via its scarce thiol versus abundant amine groups: Effect on orientation, cell binding domain exposure and conformational lability.

    Science.gov (United States)

    Ba, O M; Hindie, M; Marmey, P; Gallet, O; Anselme, K; Ponche, A; Duncan, A C

    2015-10-01

    Quantity, orientation, conformation and covalent linkage of naturally cell adhesive proteins adsorbed or covalently linked to a surface, are known to influence the preservation of their subsequent long term cell adhesion properties and bioactivity. In the present work, we explore two different strategies for the covalent linking of plasma fibronectin (pFN) - used as a cell adhesive model protein, onto a polystyrene (PS) surface. One is aimed at tethering the protein to the surface in a semi-oriented fashion (via one of the 4 free thiol reactive groups on the protein) with a heterofunctional coupling agent (SSMPB method). The other aims to immobilize the protein in a more random fashion by reaction between the abundant pendant primary amine bearing amino acids of the pFN and activated carboxylic surface functions obtained after glutaric anhydride surface treatment (GA method). The overall goal will be to verify the hypothesis of a correlation between covalent immobilization of a model cell adhesive protein to a PS surface in a semi-oriented configuration (versus randomly oriented) with promotion of enhanced exposure of the protein's cell binding domain. This in turn would lead to enhanced cell adhesion. Ideally the goal is to elaborate substrates exhibiting a long term stable protein monolayer with preserved cell adhesive properties and bioactivity for biomaterial and/or cell adhesion commercial plate applications. However, the initial restrictive objective of this paper is to first quantitatively and qualitatively investigate the reversibly (merely adsorbed) versus covalently irreversibly bound protein to the surface after the immobilization procedure. Although immobilized surface amounts were similar (close to the monolayer range) for all immobilization approaches, covalent grafting showed improved retention and stronger "tethering" of the pFN protein to the surface (roughly 40%) after SDS rinsing compared to that for mere adsorption (0%) suggesting an added value

  10. Epigenetic modification and inheritance in sexual reversal of fish

    OpenAIRE

    Shao, Changwei; Li, Qiye; Chen, Songlin; Zhang, Pei; Lian, Jinmin; Hu, Qiaomu; Sun, Bing; Jin, Lijun; Liu, Shanshan; Wang, Zongji; Zhao, Hongmei; Jin, Zonghui; Liang, Zhuo; Li, Yangzhen; Zheng, Qiumei

    2014-01-01

    Environmental sex determination (ESD) occurs in divergent, phylogenetically unrelated taxa, and in some species, co-occurs with genetic sex determination (GSD) mechanisms. Although epigenetic regulation in response to environmental effects has long been proposed to be associated with ESD, a systemic analysis on epigenetic regulation of ESD is still lacking. Using half-smooth tongue sole (Cynoglossus semilaevis) as a model—a marine fish that has both ZW chromosomal GSD and temperature-dependen...

  11. Behavior Modification in Coaching.

    Science.gov (United States)

    Lynch, Annette Rutt; Stillman, Stephen M.

    1979-01-01

    An example of behavior modification used in athletic coaching is presented. The case study involves a member of a women's basketball team and details the use of behavior modification for both weight reduction and skill improvement. (JMF)

  12. Managing Reverse Logistics or Reversing Logistics Management?

    NARCIS (Netherlands)

    M.P. de Brito (Marisa)

    2004-01-01

    textabstractIn the past, supply chains were busy fine-tuning the logistics from raw material to the end customer. Today an increasing flow of products is going back in the chain. Thus, companies have to manage reverse logistics as well.This thesis contributes to a better understanding of reverse

  13. Profiling of integral membrane proteins and their post translational modifications using high-resolution mass spectrometry

    Science.gov (United States)

    Souda, Puneet; Ryan, Christopher M.; Cramer, William A.; Whitelegge, Julian

    2011-01-01

    Integral membrane proteins pose challenges to traditional proteomics approaches due to unique physicochemical properties including hydrophobic transmembrane domains that limit solubility in aqueous solvents. A well resolved intact protein molecular mass profile defines a protein’s native covalent state including post-translational modifications, and is thus a vital measurement toward full structure determination. Both soluble loop regions and transmembrane regions potentially contain post-translational modifications that must be characterized if the covalent primary structure of a membrane protein is to be defined. This goal has been achieved using electrospray-ionization mass spectrometry (ESI-MS) with low-resolution mass analyzers for intact protein profiling, and high-resolution instruments for top-down experiments, toward complete covalent primary structure information. In top-down, the intact protein profile is supplemented by gas-phase fragmentation of the intact protein, including its transmembrane regions, using collisionally activated and/or electroncapture dissociation (CAD/ECD) to yield sequence-dependent high-resolution MS information. Dedicated liquid chromatography systems with aqueous/organic solvent mixtures were developed allowing us to demonstrate that polytopic integral membrane proteins are amenable to ESI-MS analysis, including top-down measurements. Covalent post-translational modifications are localized regardless of their position in transmembrane domains. Top-down measurements provide a more detail oriented high-resolution description of post-transcriptional and post-translational diversity for enhanced understanding beyond genomic translation. PMID:21982782

  14. Functionalization and modification of carbon nanomaterials

    Energy Technology Data Exchange (ETDEWEB)

    Diachkova, Tatyana P.; Tkachev, Alexey G.; Orlova, Nataliya V.; Orlov, Andrej Yu. [Tambov State Technical University, Tambov (Russian Federation)

    2013-07-01

    Some regularities of covalent functionalization multiwalled carbon nanotubes (MWCNTs) by oxygen- containing groups were studied. The resulting materials were characterized by electron microscopy, thermogravimetric analysis, FTIR and Raman spectroscopy. The dependence of the degree of functionalization of MWCNTs from the process conditions was stated. The advantages of the gas phase to the liquid phase oxidation were shown. The effect of pristine and functionalized MWCNTs on the properties of composites with polysulfone was studied. Pristine and functionalized MWCNTs were modified with polyaniline. The effect of the method and degree of pre-functionalization of carbon nanotubes on the regularities of the oxidative polymerization of aniline and the properties of the obtained materials was shown. Key words: multiwalled carbon nanotubes, functionalization, modification, oxidation, composites, polyaniline.

  15. Chemical modification of b-lactoglobulin by quinones

    Directory of Open Access Journals (Sweden)

    DUSAN SLADIC

    2003-05-01

    Full Text Available The avarone/avarol quinone/hydroquinone couple, as well as their derivatives show considerable antitumor activity. In this work, covalent modifications of b-lactoglobulin, isolated from cow milk, by avarone, its model compound 2-tert-butyl-1,4-benzoquinone, and several of their alkylthio derivatives were studied. The techniques applied for assaying the modifications were: UV/VIS spectrophotometry, SDS PAGE and isoelectrofocusing. The results of the SDS PAGE suggest that polymerisation of the protein occurs. The shift of the pI of the protein upon modification toward lower values indicates that lysine amino groups are the principal site of the reaction of b-lactoglobulin with the quinones.

  16. Structure and Modification of Electrode Materials for Protein Electrochemistry.

    Science.gov (United States)

    Jeuken, Lars J C

    The interactions between proteins and electrode surfaces are of fundamental importance in bioelectrochemistry, including photobioelectrochemistry. In order to optimise the interaction between electrode and redox protein, either the electrode or the protein can be engineered, with the former being the most adopted approach. This tutorial review provides a basic description of the most commonly used electrode materials in bioelectrochemistry and discusses approaches to modify these surfaces. Carbon, gold and transparent electrodes (e.g. indium tin oxide) are covered, while approaches to form meso- and macroporous structured electrodes are also described. Electrode modifications include the chemical modification with (self-assembled) monolayers and the use of conducting polymers in which the protein is imbedded. The proteins themselves can either be in solution, electrostatically adsorbed on the surface or covalently bound to the electrode. Drawbacks and benefits of each material and its modifications are discussed. Where examples exist of applications in photobioelectrochemistry, these are highlighted.

  17. Covalent DNA-protein crosslinking occurs after hyperthermia and radiation

    International Nuclear Information System (INIS)

    Cress, A.E.; Bowden, G.T.

    1983-01-01

    Covalent DNA-protein crosslinks occur in exponentially growing mouse leukemia cells (L1210) after exposure to ionizing radiation. The amount of DNA-protein crosslinks as measured by a filter binding assay is dose dependent upon X irradiation. Although hyperthermia and radiation in combination are synergistic with respect to cell lethality, the combination does not result in an increase of DNA-protein crosslinks when assayed immediately following treatments. Hyperthermia (43 degrees C/15 min) given prior to radiation does not alter the radiation dose dependency of the amount of initial crosslinking. In addition, the amount of DNA-protein crosslinking produced by heat plus radiation is independent of the length of heating the cells at 43 degrees C. The DNA-protein crosslinks produced by 50-Gy X ray alone are removed after 2 hr at 37 degrees C. However, if hyperthermia (43 degrees C/15 min) is given prior to 100-Gy X ray, the removal of DNA-protein crosslinks is delayed until 4.0 hr after radiation. Phospho-serine and phospho-threonine bonds are not produced with either radiation or the combination of hyperthermia plus radiation as judged by the resistance of the bonds to guanidine hydrochloride. However, hyperthermia plus radiation causes an increase in phosphate to nitrogen type bonding. These results show that radiation alone causes covalent DNA-protein crosslinks. Hyperthermia in combination with radiation does not increase the total amount of the crosslinks but delays the removal of the crosslinks and alters the distribution of the types of chemical bonding. These data suggest that the synergistic action on hyperthermia with radiation is more related to the rate of removal and the type of chemical bonding involved in the covalent DNA-protein crosslinks rather than the amount of DNA-protein crosslinks

  18. Macromolecular weight specificity in covalent binding of bromobenzene

    International Nuclear Information System (INIS)

    Sun, J.D.; Dent, J.G.

    1984-01-01

    Bromobenzene is a hepatotoxicant that causes centrilobular necrosis. Pretreatment of animals with 3-methylcholanthrene decreases and phenobarbital pretreatment enhances the hepatotoxic action of this compound. We have investigated the macromolecular weight specificity of the covalent interactions of bromobenzene with liver macromolecules following incubation of [ 14 C]bromobenzene in isolated hepatocytes. Hepatocytes were prepared from Fischer-344 rats treated for 3 days with 3-methylcholanthrene, phenobarbital, or normal saline. After a 1-hr incubation, total covalent binding, as measured by sodium dodecyl sulfate-equilibrium dialysis, was twofold less in hepatocytes from 3-methylcholanthrene-treated rats and sixfold greater in hepatocytes from phenobarbital-treated rats, as compared to hepatocytes from control animals. Analysis of the arylated macromolecules by electrophoresis on 15% sodium dodecyl sulfate-polyacrylamide disc gels indicated that in the first 1 to 3 min of incubation substantial amounts of covalently bound radiolabel were associated with macromolecules of between 20,000 and 40,000. The amount of radioactivity associated with these macromolecules rapidly diminished in hepatocytes from control and 3-methylcholanthrene-treated animals. In hepatocytes from phenobarbital-treated animals, the amount of radioactivity associated with macromolecules, 20,000, increased throughout the incubation. The amount of radiolabel associated with macromolecules, 20,000, increased in all incubations. When nontoxic doses of phenylmethylsulfonyl fluoride, a specific inhibitor of serine proteases, were added to control hepatocytes incubated with [ 14 C]-bromobenzene, the decrease in radioactivity associated with larger (greater than 20,000) macromolecules was inhibited and a corresponding lack of increase in radioactivity associated with smaller macromolecules was observed

  19. Tubal Ligation Reversal

    Science.gov (United States)

    ... seal off the fallopian tubes, such as the Essure or Adiana systems, generally aren't reversible. Why ... electrocautery). Some types of sterilization, such as the Essure or Adiana systems, aren't considered reversible. Risks ...

  20. The Search for Covalently Ligandable Proteins in Biological Systems

    Directory of Open Access Journals (Sweden)

    Syed Lal Badshah

    2016-09-01

    Full Text Available This commentary highlights the recent article published in Nature, June 2016, titled: “Proteome-wide covalent ligand discovery in native biological systems”. They screened the whole proteome of different human cell lines and cell lysates. Around 700 druggable cysteines in the whole proteome were found to bind the electrophilic fragments in both active and inactive states of the proteins. Their experiment and computational docking results agreed with one another. The usefulness of this study in terms of bringing a change in medicinal chemistry is highlighted here.

  1. Covalent functionalization of carbon nanotubes with tetramanganese complexes

    International Nuclear Information System (INIS)

    Meyer, Carola; Frielinghaus, Robert; Saelhoff, Anna-Katharina; Schneider, Claus M.; Besson, Claire; Floetotto, Henrik; Koegerler, Paul; Houben, Lothar

    2012-01-01

    We present first results on the covalent chemical functionalization of single-walled carbon nanotubes with polynuclear {Mn 4 } coordination complexes. Raman spectra prove that the reaction can only be achieved for tubes which have been oxidized to create carboxylic groups. HRTEM is used to show that the reaction can be carried out directly on a substrate as well. Analysis of the D/G intensity ratio for different oxidation times shows that it is possible to reduce the amount of defects created. This is important for the future application of this material in transport devices. (Copyright copyright 2012 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  2. Reaction mechanisms for on-surface synthesis of covalent nanostructures

    International Nuclear Information System (INIS)

    Björk, J

    2016-01-01

    In recent years, on-surface synthesis has become an increasingly popular strategy to form covalent nanostructures. The approach has great prospects for facilitating the manufacture of a range of fascinating materials with atomic precision. However, the on-surface reactions are enigmatic to control, currently restricting its bright perspectives and there is a great need to explore how the reactions are governed. The objective of this topical review is to summarize theoretical work that has focused on comprehending on-surface synthesis protocols through studies of reaction mechanisms. (topical review)

  3. A role for non-covalent SUMO interaction motifs in Pc2/CBX4 E3 activity.

    Directory of Open Access Journals (Sweden)

    Jacqueline C Merrill

    2010-01-01

    Full Text Available Modification of proteins by the small ubiquitin like modifier (SUMO is an essential process in mammalian cells. SUMO is covalently attached to lysines in target proteins via an enzymatic cascade which consists of E1 and E2, SUMO activating and conjugating enzymes. There is also a variable requirement for non-enzymatic E3 adapter like proteins, which can increase the efficiency and specificity of the sumoylation process. In addition to covalent attachment of SUMO to target proteins, specific non-covalent SUMO interaction motifs (SIMs that are generally short hydrophobic peptide motifs have been identified.Intriguingly, consensus SIMs are present in most SUMO E3s, including the polycomb protein, Pc2/Cbx4. However, a role for SIMs in SUMO E3 activity remains to be shown. We show that Pc2 contains two functional SIMs, both of which contribute to full E3 activity in mammalian cells, and are also required for sumoylation of Pc2 itself. Pc2 forms distinct sub-nuclear foci, termed polycomb bodies, and can recruit partner proteins, such as the corepressor CtBP. We demonstrate that mutation of the SIMs in Pc2 prevents Pc2-dependent CtBP sumoylation, and decreases enrichment of SUMO1 and SUMO2 at polycomb foci. Furthermore, mutational analysis of both SUMO1 and SUMO2 reveals that the SIM-interacting residues of both SUMO isoforms are required for Pc2-mediated sumoylation and localization to polycomb foci.This work provides the first clear evidence for a role for SIMs in SUMO E3 activity.

  4. Reverse logistics - a framework

    NARCIS (Netherlands)

    M.P. de Brito (Marisa); R. Dekker (Rommert)

    2002-01-01

    textabstractIn this paper we define and compare Reverse Logistics definitions. We start by giving an understanding framework of Reverse Logistics: the why-what-how. By this means, we put in context the driving forces for Reverse Logistics, a typology of return reasons, a classification of

  5. Self-healing polymer gels based on dynamic covalent bonds%基于动态共价键的可自愈合聚合物凝胶

    Institute of Scientific and Technical Information of China (English)

    张云飞; 邓国华

    2012-01-01

    简要介绍了动态共价键既具有普通共价键的高强度和稳定性,又能像分子间作用力(如氢键)那样可逆地断裂和重组的特点,以及基于动态共价键构筑智能凝胶材料的优势。综述了多种动态共价键,如芳香基苯并呋喃酮二聚体(diarylbibenzo furanone,DABBF)、三硫酯(trithiocarbonate,TTC)、芳基硼酸酯、酰腙键(acylhydrazone bond)、双硫键(disulfide bond)等的结构及其动态化学,以及应用它们合成聚合物凝胶的方法、凝胶的自愈合机理和性能。提出了发现和采用多种动态共价键构筑可自愈合聚合物凝胶的趋势,为此须解决多种动态共价键的相容性、凝胶自愈合机理与性能的光谱表征等问题,并加强应用研究。%Dynamic covalent bonds have high mechanical strength and stability like ordinary covalent bonds and can reversibly break and rebuild like intermolecular forces(such as hydrogen bonding).The properties of dynamic covalent bonds are introduced.The advantages of building smart gels based on dynamic covalent bonds are described.Specifically,the structure and dynamic chemistry of diarylbibenzo furanone(DABBF),trithiocarbonate(TTC),phenylboronic aciddiol ester bond,acylhydrazone bond and disulfide bond are reviewed.The methods of utilizing those dynamic covalent bonds to construct dynamic gels with self-healing properties,including the healing mechanisms,are presented.Combining two or more covalent bonds to construct dynamic gels with more complex responsiveness are proposed.Problems,such as compatibility of the dynamic covalent bonds,spectroscopic methods for characterizing self-healing mechanisms and capabilities,and application-oriented systems need to be further investigated.

  6. Tipping the balance by manipulating posttranslational modifications

    Science.gov (United States)

    Broberg, Christopher A.; Orth, Kim

    2010-01-01

    Summary Bacteria use a variety of mechanisms during infection to ensure their survival including the delivery of virulence factors via a type III secretion system into the infected cell. The factors exhibit diverse activities that in many cases mimic eukaryotic mechanisms used by the host to defend against infection. Herein we describe a class of effectors that use posttranslational modifications, some reversible and others irreversible, to manipulate host signaling systems to subvert the host response. PMID:20071215

  7. A binderless, covalently bulk modified electrochemical sensor: Application to simultaneous determination of lead and cadmium at trace level

    Energy Technology Data Exchange (ETDEWEB)

    Gunigollahalli Kempegowda, Raghu [Department of Studies in Chemistry, Bangalore University, Central College Campus, Bangalore 560001 (India); Malingappa, Pandurangappa, E-mail: mprangachem@gmail.com [Department of Studies in Chemistry, Bangalore University, Central College Campus, Bangalore 560001 (India)

    2012-05-30

    Highlights: Black-Right-Pointing-Pointer Proposed sensor is a new type of binderless covalent bulk modified electrode. Black-Right-Pointing-Pointer Surface can be easily renewed by simple mechanical polishing using emery sheets. Black-Right-Pointing-Pointer Free from modifier leaching during electrochemical measurements. Black-Right-Pointing-Pointer Provides long term storage stability with good reproducibility. Black-Right-Pointing-Pointer Nanomolar level detection limit achieved with selectivity. - Abstract: A new type of covalent binderless bulk modified electrode has been fabricated and used in the simultaneous determination of lead and cadmium ions at nanomolar level. The modification of graphitic carbon with 4-amino salicylic acid was carried out under microwave irradiation through the amide bond formation. The electrochemical behavior of the fabricated electrode has been carried out to decipher the interacting ability of the functional moieties present on the modifier molecules toward the simultaneous determination of Pb{sup 2+} and Cd{sup 2+} ions using cyclic and differential pulse anodic stripping voltammetry. The possible mode of interaction of functional groups with metal ions is proposed based on the pKa values of the modifier functionalities present on the surface of graphitic carbon particles. The analytical utility of the proposed sensor has been validated by measuring the lead and cadmium content from pretreated waste water samples of lead acid batteries.

  8. Non-covalent attachment of silver nanoclusters onto single-walled carbon nanotubes with human serum albumin as linking molecule

    Energy Technology Data Exchange (ETDEWEB)

    Rodríguez-Galván, Andrés, E-mail: andres.rodriguez@nucleares.unam.mx [Instituto de Ciencias Nucleares, Universidad Nacional Autónoma de México, Circuito Exterior C.U., 04510 México D.F. (Mexico); Instituto de Física, Dpto. Física Experimental, Universidad Nacional Autónoma de México, Coyoacán, México, DF 04510 (Mexico); Unidad de Investigación Biomédica en Cáncer INCan-UNAM, Instituto Nacional de Cancerología, México, DF 14080 (Mexico); Heredia, Alejandro [Instituto de Ciencias Nucleares, Universidad Nacional Autónoma de México, Circuito Exterior C.U., 04510 México D.F. (Mexico); Amelines-Sarria, Oscar; Rivera, Margarita [Instituto de Física, Dpto. Materia Condensada, Universidad Nacional Autónoma de México, Coyoacán, 04510 México D.F. (Mexico); and others

    2015-03-15

    The attachment of silver nanoclusters (AgNCs) onto single-walled carbon nanotubes (SWNTs) for the formation of integrated fluorescence sites has attracted much attention due their potential applications as biological probes and nanovectors in theragnosis. Here, we report the preparation through assembly of fluorescent quasi 1-D nanomaterial based on SWNTs and silver nanoclusters (AgNCs) non-covalently attached to human serum albumin as biological linker. The fluorescent SWNT–AgNCs–HSA conjugates were characterized by atomic force microscopy, high-resolution transmission electron microscopy (HRTEM), high angle annular dark field scanning TEM (HAADF-STEM), fluorescent and UV–vis spectroscopy. The above techniques confirmed that AgNCs were non-covalently attached onto the external surface of SWNTs. In addition, it was observed that the modification did not affect the optical properties of the synthesized AgNCs since the absorption spectra and fluorescence under UV irradiation (λ = 365 nm) remain the same. The effect of the functionalized systems was tested on mammal red blood cells (RBCs) and it was found that their structural integrity was compromised by the conjugates, limiting their biological and medical applications.

  9. Non-covalent attachment of silver nanoclusters onto single-walled carbon nanotubes with human serum albumin as linking molecule

    International Nuclear Information System (INIS)

    Rodríguez-Galván, Andrés; Heredia, Alejandro; Amelines-Sarria, Oscar; Rivera, Margarita

    2015-01-01

    The attachment of silver nanoclusters (AgNCs) onto single-walled carbon nanotubes (SWNTs) for the formation of integrated fluorescence sites has attracted much attention due their potential applications as biological probes and nanovectors in theragnosis. Here, we report the preparation through assembly of fluorescent quasi 1-D nanomaterial based on SWNTs and silver nanoclusters (AgNCs) non-covalently attached to human serum albumin as biological linker. The fluorescent SWNT–AgNCs–HSA conjugates were characterized by atomic force microscopy, high-resolution transmission electron microscopy (HRTEM), high angle annular dark field scanning TEM (HAADF-STEM), fluorescent and UV–vis spectroscopy. The above techniques confirmed that AgNCs were non-covalently attached onto the external surface of SWNTs. In addition, it was observed that the modification did not affect the optical properties of the synthesized AgNCs since the absorption spectra and fluorescence under UV irradiation (λ = 365 nm) remain the same. The effect of the functionalized systems was tested on mammal red blood cells (RBCs) and it was found that their structural integrity was compromised by the conjugates, limiting their biological and medical applications

  10. Photogeneration of singlet oxygen by the phenothiazine derivatives covalently bound to the surface-modified glassy carbon

    Energy Technology Data Exchange (ETDEWEB)

    Blacha-Grzechnik, Agata, E-mail: agata.blacha@polsl.pl [Faculty of Chemistry, Silesian University of Technology, Strzody 9, 44-100 Gliwice (Poland); Piwowar, Katarzyna; Krukiewicz, Katarzyna [Faculty of Chemistry, Silesian University of Technology, Strzody 9, 44-100 Gliwice (Poland); Koscielniak, Piotr; Szuber, Jacek [Institute of Electronics, Silesian University of Technology, Akademicka 16, 44-100 Gliwice (Poland); Zak, Jerzy K. [Faculty of Chemistry, Silesian University of Technology, Strzody 9, 44-100 Gliwice (Poland)

    2016-05-15

    Highlights: • The selected group of four NH{sub 2}-derivatives of phenothiazine was grafted to Glassy Carbon (GC) surface. • The grafted phenothiazines are able to generate {sup 1}O{sub 2} when activated by the radiation. • Such modified solid surfaces may find their application in the wastewater treatment. - Abstract: The selected group of four amine-derivatives of phenothiazine was covalently grafted to the glassy carbon surface in the four-step procedure consisting of the electrochemical reduction of the diazonium salt followed by the electrochemical and chemical post-modification steps. The proposed strategy involves the bonding of linker molecule to which the photosensitizer is attached. The synthesized organic layers were characterized by means of cyclic voltammetry, XPS and Raman Spectroscopy. It was shown that the phenothiazines immobilized via proposed strategy retain their photochemical properties and are able to generate {sup 1}O{sub 2} when activated by the laser radiation. The effectiveness of in situ singlet oxygen generation by those new solid photoactive materials was determined by means of UVVis spectroscopy. The reported, covalently modified solid surfaces may find their application as the singlet oxygen photogenerators in the fine chemicals’ synthesis or in the wastewater treatment.

  11. Aryloxyalkanoic Acids as Non-Covalent Modifiers of the Allosteric Properties of Hemoglobin

    Directory of Open Access Journals (Sweden)

    Abdelsattar M. Omar

    2016-08-01

    Full Text Available Hemoglobin (Hb modifiers that stereospecifically inhibit sickle hemoglobin polymer formation and/or allosterically increase Hb affinity for oxygen have been shown to prevent the primary pathophysiology of sickle cell disease (SCD, specifically, Hb polymerization and red blood cell sickling. Several such compounds are currently being clinically studied for the treatment of SCD. Based on the previously reported non-covalent Hb binding characteristics of substituted aryloxyalkanoic acids that exhibited antisickling properties, we designed, synthesized and evaluated 18 new compounds (KAUS II series for enhanced antisickling activities. Surprisingly, select test compounds showed no antisickling effects or promoted erythrocyte sickling. Additionally, the compounds showed no significant effect on Hb oxygen affinity (or in some cases, even decreased the affinity for oxygen. The X-ray structure of deoxygenated Hb in complex with a prototype compound, KAUS-23, revealed that the effector bound in the central water cavity of the protein, providing atomic level explanations for the observed functional and biological activities. Although the structural modification did not lead to the anticipated biological effects, the findings provide important direction for designing candidate antisickling agents, as well as a framework for novel Hb allosteric effectors that conversely, decrease the protein affinity for oxygen for potential therapeutic use for hypoxic- and/or ischemic-related diseases.

  12. Covalent attachment of proteins to solid supports and surfaces via Sortase-mediated ligation.

    Directory of Open Access Journals (Sweden)

    Lilyan Chan

    Full Text Available BACKGROUND: There is growing interest in the attachment of proteins to solid supports for the development of supported catalysts, affinity matrices, and micro devices as well as for the development of planar and bead based protein arrays for multiplexed assays of protein concentration, interactions, and activity. A critical requirement for these applications is the generation of a stable linkage between the solid support and the immobilized, but still functional, protein. METHODOLOGY: Solid supports including crosslinked polymer beads, beaded agarose, and planar glass surfaces, were modified to present an oligoglycine motif to solution. A range of proteins were ligated to the various surfaces using the Sortase A enzyme of S. aureus. Reactions were carried out in aqueous buffer conditions at room temperature for times between one and twelve hours. CONCLUSIONS: The Sortase A transpeptidase of S. aureus provides a general, robust, and gentle approach to the selective covalent immobilization of proteins on three very different solid supports. The proteins remain functional and accessible to solution. Sortase mediated ligation is therefore a straightforward methodology for the preparation of solid supported enzymes and bead based assays, as well as the modification of planar surfaces for microanalytical devices and protein arrays.

  13. Nanoscale zero-valent iron impregnation of covalent organic polymer grafted activated carbon for water treatment

    DEFF Research Database (Denmark)

    Mines, Paul D.; Uthuppu, Basil; Thirion, Damien

    2016-01-01

    The use of nanoscale zero valent iron (nZVI) has quickly become a leading research material for the treatment of typically hard to degrade contaminants found in groundwater. These contaminants include antibiotics, pesticides, halogenated organics, heavy metals, among others. However, the effectiv......The use of nanoscale zero valent iron (nZVI) has quickly become a leading research material for the treatment of typically hard to degrade contaminants found in groundwater. These contaminants include antibiotics, pesticides, halogenated organics, heavy metals, among others. However...... polymeric network already previously proven to stabilize nZVI and a long-standing water treatment material,1 activated carbon; we have developed an advanced material that allows for the not only the stabilization of nZVI, but also the improved degradation of various water contaminants. This was done...... by performing a series of surface modification techniques to the surface of the activated carbon, then physically grafting the covalent organic polymer to the carbon in a shell-like manner, and ultimately synthesizing nZVI in situ within the pores of both the activated carbon and the polymeric network. Not only...

  14. Investigating the Non-Covalent Functionalization and Chemical Transformation of Graphene

    Science.gov (United States)

    Sham, Chun-Hong

    Trend in device miniatures demands capabilities to produce rationally designed patterns in ever-shrinking length scale. The research community has examined various techniques to push the current lithography resolution to sub-10nm scale. One of the ideas is to utilize the natural nanoscale patterns of molecular assemblies. In this thesis, the self-assembling phenomenon of a photoactive molecule on epitaxial graphene (EG) grown on SiC was discussed. This molecular assembly enables manipulation of chemical contrast in nanoscale through UV exposure or atomic layer deposition. Future development of nanoelectronics industry will be fueled by innovations in electronics materials, which could be discovered through covalent modification of graphene. In a study reported in this thesis, silicon is deposited onto EG. After annealing, a new surface reconstruction, identified to be (3x3)-SiC, was formed. Raman spectroscopy finds no signature of graphene after annealing, indicating a complete chemical transformation of graphene. DFT calculations reveal a possible conversion mechanism. Overall, these studies provide insights for future device miniaturization; contribute to the search of novel materials and help bridging the gap between graphene and current silicon-based industrial infrastructures.

  15. Surface functionalization of polyethylene via covalent immobilization of O-stearoyl-chitosan

    International Nuclear Information System (INIS)

    Xin, Zhirong; Hou, Juan; Ding, Jiaotong; Yang, Zongfeng; Yan, Shunjie; Liu, Chan

    2013-01-01

    When used in blood-contacting field, the hemocompatibility of polyethylene (PE) needs further to be improved. In this article, O-stearoyl-chitosans (OSC) with different esterification degrees were successfully prepared via changing the ratios of chitosan and stearoyl chloride for decreasing the cationic and hydrogen bond strength, thus improving the solubility of chitosan. The PE film was grafted with carboxyl groups of acrylic acid (AA) (PE-g-PAA) by means of O 2 plasma pre-treatment and UV-induced graft polymerization, and then PE-g-PAA was used for covalent immobilization of OSC. The above surface modification was confirmed by ATR-FTIR and XPS. Effect of the UV-irradiated graft polymerization parameters, i.e., the discharge power, the plasma pretreatment time, the UV irradiation time and the monomer concentration on the grafting density of AA was investigated. Relative to the value of about 107° for the virgin sample, the water contact angle (WCA) of the PAA-grafted film was about 50°. After the further immobilization of OSC onto the PAA-grafted film, the strength of negative charge of the PAA-grafted surface was decreased by the electropositive OSC, thus presenting a WCA value of about 62° and the excellent performance of anti-platelet adhesion with respect to the virgin and PAA-grafted samples.

  16. Covalent Organic Frameworks: From Materials Design to Biomedical Application

    Directory of Open Access Journals (Sweden)

    Fuli Zhao

    2017-12-01

    Full Text Available Covalent organic frameworks (COFs are newly emerged crystalline porous polymers with well-defined skeletons and nanopores mainly consisted of light-weight elements (H, B, C, N and O linked by dynamic covalent bonds. Compared with conventional materials, COFs possess some unique and attractive features, such as large surface area, pre-designable pore geometry, excellent crystallinity, inherent adaptability and high flexibility in structural and functional design, thus exhibiting great potential for various applications. Especially, their large surface area and tunable porosity and π conjugation with unique photoelectric properties will enable COFs to serve as a promising platform for drug delivery, bioimaging, biosensing and theranostic applications. In this review, we trace the evolution of COFs in terms of linkages and highlight the important issues on synthetic method, structural design, morphological control and functionalization. And then we summarize the recent advances of COFs in the biomedical and pharmaceutical sectors and conclude with a discussion of the challenges and opportunities of COFs for biomedical purposes. Although currently still at its infancy stage, COFs as an innovative source have paved a new way to meet future challenges in human healthcare and disease theranostic.

  17. Bifunctional avidin with covalently modifiable ligand binding site.

    Directory of Open Access Journals (Sweden)

    Jenni Leppiniemi

    Full Text Available The extensive use of avidin and streptavidin in life sciences originates from the extraordinary tight biotin-binding affinity of these tetrameric proteins. Numerous studies have been performed to modify the biotin-binding affinity of (streptavidin to improve the existing applications. Even so, (streptavidin greatly favours its natural ligand, biotin. Here we engineered the biotin-binding pocket of avidin with a single point mutation S16C and thus introduced a chemically active thiol group, which could be covalently coupled with thiol-reactive molecules. This approach was applied to the previously reported bivalent dual chain avidin by modifying one binding site while preserving the other one intact. Maleimide was then coupled to the modified binding site resulting in a decrease in biotin affinity. Furthermore, we showed that this thiol could be covalently coupled to other maleimide derivatives, for instance fluorescent labels, allowing intratetrameric FRET. The bifunctional avidins described here provide improved and novel tools for applications such as the biofunctionalization of surfaces.

  18. Privileged Electrophile Sensors: A Resource for Covalent Drug Development.

    Science.gov (United States)

    Long, Marcus John Curtis; Aye, Yimon

    2017-07-20

    This Perspective delineates how redox signaling affects the activity of specific enzyme isoforms and how this property may be harnessed for rational drug design. Covalent drugs have resurged in recent years and several reports have extolled the general virtues of developing irreversible inhibitors. Indeed, many modern pharmaceuticals contain electrophilic appendages. Several invoke a warhead that hijacks active-site nucleophiles whereas others take advantage of spectator nucleophilic side chains that do not participate in enzymatic chemistry, but are poised to bind/react with electrophiles. The latest data suggest that innate electrophile sensing-which enables rapid reaction with an endogenous signaling electrophile-is a quintessential resource for the development of covalent drugs. For instance, based on recent work documenting isoform-specific electrophile sensing, isozyme non-specific drugs may be converted to isozyme-specific analogs by hijacking privileged first-responder electrophile-sensing cysteines. Because this approach targets functionally relevant cysteines, we can simultaneously harness previously untapped moonlighting roles of enzymes linked to redox sensing. Copyright © 2017 Elsevier Ltd. All rights reserved.

  19. Solvent-free covalent functionalization of nanodiamond with amines

    International Nuclear Information System (INIS)

    Basiuk, Elena V.; Santamaría-Bonfil, Adriana; Meza-Laguna, Victor; Gromovoy, Taras Yu.; Alvares-Zauco, Edgar; Contreras-Torres, Flavio F.; Rizo, Juan; Zavala, Guadalupe; Basiuk, Vladimir A.

    2013-01-01

    Covalent functionalization of pristine nanodiamond (ND) with 1,12-diaminododecane (DAD), 1,5-diaminonaphthalene (DAN), poly(ethylene glycol) diamine (PEGDA), and polyethylenimine (PEI) was carried out by employing solvent-free methodology, which is based on thermal instead of chemical activation of carboxylic groups at ND surface. A simple solubility/dispersibility test in water and isopropanol showed an increased lipophilicity of the functionalized samples. The conversion of intrinsic carboxylic groups into the corresponding amide derivatives was characterized by means of Fourier-transform infrared spectroscopy. Thermogravimetric analysis found the highest organic content of about 18% for ND-PEI, followed by ND-DAD, for which the contribution of covalently bonded diamine was estimated to be of ca. 10%. In temperature programmed desorption measurements with mass spectrometric detection, the presence of organic functionalizing groups changed both mass spectra and thermodesorption curves of ND. The changes in morphology of primary and secondary ND aggregates were characterized by scanning and transmission electron microscopy, as well as by atomic force microscopy. The current–voltage measurements under atmospheric pressure found an increased conductivity for ND-DAN, as compared to that of pristine ND, whereas for ND-DAD, ND-PEGDA and ND-PEI a dramatic decrease in conductivity due to functionalization was observed.

  20. Solvent-free covalent functionalization of nanodiamond with amines

    Energy Technology Data Exchange (ETDEWEB)

    Basiuk, Elena V., E-mail: elenagd@unam.mx [Centro de Ciencias Aplicadas y Desarrollo Tecnológico, Universidad Nacional Autónoma de México, Circuito Exterior, Ciudad Universitaria, 04510 México D.F. (Mexico); Santamaría-Bonfil, Adriana; Meza-Laguna, Victor [Centro de Ciencias Aplicadas y Desarrollo Tecnológico, Universidad Nacional Autónoma de México, Circuito Exterior, Ciudad Universitaria, 04510 México D.F. (Mexico); Gromovoy, Taras Yu. [Institute of Surface Chemistry, National Academy of Sciences of the Ukraine, Gen. Naumova 17, 03164 Kiev (Ukraine); Alvares-Zauco, Edgar [Facultad de Ciencias, Universidad Nacional Autónoma de México, Circuito Exterior, Ciudad Universitaria, 04510 México D.F. (Mexico); Contreras-Torres, Flavio F.; Rizo, Juan [Centro de Ciencias Aplicadas y Desarrollo Tecnológico, Universidad Nacional Autónoma de México, Circuito Exterior, Ciudad Universitaria, 04510 México D.F. (Mexico); Zavala, Guadalupe [Instituto de Biotecnología, Universidad Nacional Autónoma de México, Av. Universidad 2001, Col. Chamilpa, 62210, Cuernavaca, Morelos (Mexico); Basiuk, Vladimir A. [Instituto de Ciencias Nucleares, Universidad Nacional Autónoma de México, Circuito Exterior, Ciudad Universitaria, 04510 México, D.F. (Mexico)

    2013-06-15

    Covalent functionalization of pristine nanodiamond (ND) with 1,12-diaminododecane (DAD), 1,5-diaminonaphthalene (DAN), poly(ethylene glycol) diamine (PEGDA), and polyethylenimine (PEI) was carried out by employing solvent-free methodology, which is based on thermal instead of chemical activation of carboxylic groups at ND surface. A simple solubility/dispersibility test in water and isopropanol showed an increased lipophilicity of the functionalized samples. The conversion of intrinsic carboxylic groups into the corresponding amide derivatives was characterized by means of Fourier-transform infrared spectroscopy. Thermogravimetric analysis found the highest organic content of about 18% for ND-PEI, followed by ND-DAD, for which the contribution of covalently bonded diamine was estimated to be of ca. 10%. In temperature programmed desorption measurements with mass spectrometric detection, the presence of organic functionalizing groups changed both mass spectra and thermodesorption curves of ND. The changes in morphology of primary and secondary ND aggregates were characterized by scanning and transmission electron microscopy, as well as by atomic force microscopy. The current–voltage measurements under atmospheric pressure found an increased conductivity for ND-DAN, as compared to that of pristine ND, whereas for ND-DAD, ND-PEGDA and ND-PEI a dramatic decrease in conductivity due to functionalization was observed.

  1. Evaluation of covalency of ions in lead-free perovskite-type dielectric oxides

    Directory of Open Access Journals (Sweden)

    Naohisa Takesue

    2017-10-01

    Full Text Available Electronic states of ions in lead-free perovskite-type dielectric oxides have been investigated with a first-principle cluster calculation. For this calculation a double-perovskite cluster model based upon the simple cubic ABO3 was used; A and B are both the cations, and O is the oxygen anion. Systematic variations of ionic species for A and B, and lengths of the model cube edge were given to the model. Results of charge transfers of the ions show that their magnitudes depend on the edge length; the lager length leads to the higher transfer magnitude. This tendency implies spatial tolerance of the ions to the clusters, and are expected to correlate with electric polarizability and dipole reversibility of this kind of oxides. The density of states and the overlap population indicate that the higher cation valence causes the higher covalency of the anions. Considering all results together provides us an idea to obtain lead-free high-performance ferroelectrics, as high as the lead-based solid solutions.

  2. Methacrylate-bonded covalent-organic framework monolithic columns for high performance liquid chromatography.

    Science.gov (United States)

    Liu, Li-Hua; Yang, Cheng-Xiong; Yan, Xiu-Ping

    2017-01-06

    Covalent-organic frameworks (COFs) are a newfangled class of intriguing microporous materials. Considering their unique properties, COFs should be promising as packing materials for high performance liquid chromatography (HPLC). However, the irregular shape and sub-micrometer size of COFs synthesized via the traditional methods render the main obstacles for the application of COFs in HPLC. Herein, we report the preparation of methacrylate-bonded COF monolithic columns for HPLC to overcome the above obstacles. The prepared COF bonded monolithic columns not only show good homogeneity and permeability, but also give high column efficiency, good resolution and precision for HPLC separation of small molecules including polycyclic aromatic hydrocarbons, phenols, anilines, nonsteroidal anti-inflammatory drugs and benzothiophenes. Compared with the bare polymer monolithic column, the COF bonded monolithic columns show enhanced hydrophobic, π-π and hydrogen bond interactions in reverse phase HPLC. The results reveal the great potential of COF bonded monoliths for HPLC and COFs in separation sciences. Copyright © 2016 Elsevier B.V. All rights reserved.

  3. Selective removal of 2,4-dichlorophenol from contaminated water using non-covalent imprinted microspheres

    International Nuclear Information System (INIS)

    Li Ying; Li Xin; Li Yuqi; Qi Jingyao; Bian Jiang; Yuan Yixing

    2009-01-01

    A molecularly imprinted polymer (MIP) for selective removal of 2,4-dichlorophenol (2,4-DCP) in water was prepared as microspheres by the reverse microemulsion polymerization method based on the non-covalent interactions between 2,4-DCP, oleic acid, and divinylbenzene in acetonitrile. Microspheres have been characterized by Fourier transform infrared spectrometer (FTIR) and energy dispersive X-ray spectrometer (EDS) studies with evidence of 2,4-DCP linkage in polymer particles and scanning electron microscopy (SEM) to study their morphological properties. The proper adsorption and selective recognition ability of the MIP were studied by an equilibrium-adsorption method. The MIP showed outstanding affinity towards 2,4-DCP in aqueous solution and the optimum pH value for binding has been found around the neutral range. The molecular recognition of 2,4-DCP was analyzed in detail by using molecular modeling software. In addition, by investigating the variation in the adsorption ability of the MIP, it clearly showed excellent reproducibility. - Molecular imprinting has potential as a remediation technology in water treatment.

  4. The non-covalent decoration of self-assembling protein fibers.

    Science.gov (United States)

    Mahmoud, Zahra N; Grundy, Daniel J; Channon, Kevin J; Woolfson, Derek N

    2010-10-01

    The design of self-assembling fibers presents challenges in basic science, and has potential for developing materials for applications in areas such as tissue engineering. A contemporary issue in the field is the construction of multi-component, functionalized systems. Previously, we have developed peptide-based fibers, the SAF system, that comprises two complementary peptides, which affords considerable control over assembly and morphology. Here we present a straightforward route to functionalizing the SAFs with small molecules and, subsequently, other moieties. This is achieved via non-covalent recruitment of charged peptide tags, which offers advantages such as further control, reversibility, and future prospects for developing recombinant tags. We demonstrate the concept by appending fluorescent labels and biotin (and thence gold nanoparticles) to the peptides, and visualising the resulting decorated SAFs by light and electron microscopy. The peptide tags bind in the nm-mum range, and show specificity compared with control peptides, and for the SAFs over similar alpha-helix-based peptide fibers. 2010 Elsevier Ltd. All rights reserved.

  5. Self-assembling triblock proteins for biofunctional surface modification

    Science.gov (United States)

    Fischer, Stephen E.

    Despite the tremendous promise of cell/tissue engineering, significant challenges remain in engineering functional scaffolds to precisely regulate the complex processes of tissue growth and development. As the point of contact between the cells and the scaffold, the scaffold surface plays a major role in mediating cellular behaviors. In this dissertation, the development and utility of self-assembling, artificial protein hydrogels as biofunctional surface modifiers is described. The design of these recombinant proteins is based on a telechelic triblock motif, in which a disordered polyelectrolyte central domain containing embedded bioactive ligands is flanked by two leucine zipper domains. Under moderate conditions of temperature and pH, the leucine zipper end domains form amphiphilic alpha-helices that reversibly associate into homo-trimeric aggregates, driving hydrogel formation. Moreover, the amphiphilic nature of these helical domains enables surface adsorption to a variety of scaffold materials to form biofunctional protein coatings. The nature and stability of these coatings in various solution conditions, and their interaction with mammalian cells is the primary focus of this dissertation. In particular, triblock protein coatings functionalized with cell recognition sequences are shown to produce well-defined surfaces with precise control over ligand density. The impact of this is demonstrated in multiple cell types through ligand density-dependent cell-substrate interactions. To improve the stability of these physically self-assembled coatings, two covalent crosslinking strategies are described---one in which a zero-length chemical crosslinker (EDC) is utilized and a second in which disulfide bonds are engineered into the recombinant proteins. These targeted crosslinking approaches are shown to increase the stability of surface adsorbed protein layers with minimal effect on the presentation of many bioactive ligands. Finally, to demonstrate the versatility

  6. Radical covalent organic frameworks: a general strategy to immobilize open-accessible polyradicals for high-performance capacitive energy storage.

    Science.gov (United States)

    Xu, Fei; Xu, Hong; Chen, Xiong; Wu, Dingcai; Wu, Yang; Liu, Hao; Gu, Cheng; Fu, Ruowen; Jiang, Donglin

    2015-06-01

    Ordered π-columns and open nanochannels found in covalent organic frameworks (COFs) could render them able to store electric energy. However, the synthetic difficulty in achieving redox-active skeletons has thus far restricted their potential for energy storage. A general strategy is presented for converting a conventional COF into an outstanding platform for energy storage through post-synthetic functionalization with organic radicals. The radical frameworks with openly accessible polyradicals immobilized on the pore walls undergo rapid and reversible redox reactions, leading to capacitive energy storage with high capacitance, high-rate kinetics, and robust cycle stability. The results suggest that channel-wall functional engineering with redox-active species will be a facile and versatile strategy to explore COFs for energy storage. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  7. Covalent Organic Framework Functionalized with 8-Hydroxyquinoline as a Dual-Mode Fluorescent and Colorimetric pH Sensor.

    Science.gov (United States)

    Chen, Long; He, Linwei; Ma, Fuyin; Liu, Wei; Wang, Yaxing; Silver, Mark A; Chen, Lanhua; Zhu, Lin; Gui, Daxiang; Diwu, Juan; Chai, Zhifang; Wang, Shuao

    2018-05-09

    Real-time and accurate detection of pH in aqueous solution is of great significance in chemical, environmental, and engineering-related fields. We report here the use of 8-hydroxyquinoline-functionalized covalent organic framework (COF-HQ) for dual-mode pH sensing. In the fluorescent mode, the emission intensity of COF-HQ weakened as the pH decreased, and also displayed a good linear relationship against pH in the range from 1 to 5. In addition, COF-HQ showed discernible color changes from yellow to black as the acidity increased and can be therefore used as a colorimetric pH sensor. All these changes are reversible and COF-HQ can be recycled for multiple detection runs owing to its high hydrolytical stability. It can be further assembled into a mixed matrix membrane for practical applications.

  8. Reversible flowchart languages and the structured reversible program theorem

    DEFF Research Database (Denmark)

    Yokoyama, Tetsuo; Axelsen, Holger Bock; Glück, Robert

    2008-01-01

    Many irreversible computation models have reversible counterparts, but these are poorly understood at present. We introduce reversible flowcharts with an assertion operator and show that any reversible flowchart can be simulated by a structured reversible flowchart using only three control flow...... operators. Reversible flowcharts are r- Turing-complete, meaning that they can simuluate reversible Turing machines without garbage data. We also demonstrate the injectivization of classical flowcharts into reversible flowcharts. The reversible flowchart computation model provides a theoretical...

  9. On the genetic modification of psychology, personality, and behavior.

    Science.gov (United States)

    Neitzke, Alex B

    2012-12-01

    I argue that the use of heritable modifications for psychology, personality, and behavior should be limited to the reversal or prevention of relatively unambiguous instances of pathology or likely harm (e.g. sociopathy). Most of the likely modifications of psychological personality would not be of this nature, however, and parents therefore should not have the freedom to make such modifications to future children. I argue by examining the viewpoints of both the individual and society. For individuals, modifications would interfere with their capacity for self-determination in a way that undermines the very concept of self-determination. I argue that modification of psychology and personality is unlike present parenting in morally significant ways. For society, modification offers a medium for power to manipulate the makeup of persons and populations, possibly causing biological harm to the species and altering our conceptions of social responsibility.

  10. Recovery of Picloram and 2,4-Dichlorophenoxyacetic Acid from Aqueous Samples by Reversed-Phase Solid-Phase Extraction

    Science.gov (United States)

    Martha J.M. Wells; Jerry L. Michael

    1987-01-01

    Extensive preparation of samples before chromatographic analysis is usually the most time-consuming process in the determination of many organic compounds in environmental matrices. In the past, removal of some organic from aqueous solution was commonly done by liquid/liquid extraction. However, the introduction of stable, covalently bonded reversed-phase sorbents now...

  11. Reversible aggregation of lysozyme in a biodegradable amphiphilic multiblock copolymer.

    Science.gov (United States)

    van de Weert, Marco; van Dijkhuizen-Radersma, Riemke; Bezemer, Jeroen M; Hennink, Wim E; Crommelin, Daan J A

    2002-07-01

    Lysozyme-loaded poly(ethylene glycol terephthalate)-poly(butylene terephthalate) (PEGT/PBT) films were prepared using a water-in-oil emulsification solvent evaporation method. Infrared spectroscopic analysis of the dried films indicated the presence of non-covalent lysozyme aggregates in the polymer matrix. The use of methanol to enhance the drying rate of the films increased the relative amount of aggregates. Surprisingly, quantitative in-vitro release of fully active, non-aggregated lysozyme was observed, indicating that lysozyme forms reversible aggregates during encapsulation in PEGT/PBT films.

  12. Oxidative modification of ferritin induced by methylglyoxal

    Directory of Open Access Journals (Sweden)

    Sung Ho An

    2012-03-01

    Full Text Available Methylglyoxal (MG was identified as an intermediate innon-enzymatic glycation and increased levels were reported inpatients with diabetes. In this study, we evaluated the effects ofMG on the modification of ferritin. When ferritin wasincubated with MG, covalent crosslinking of the proteinincreased in a time- and MG dose-dependent manner.Reactive oxygen species (ROS scavengers, N-acetyl-L-cysteineand thiourea suppressed the MG-mediated ferritinmodification. The formation of dityrosine was observed inMG-mediated ferritin aggregates and ROS scavengers inhibitedthe formation of dityrosine. During the reaction betweenferritin and MG, the generation of ROS was increased as afunction of incubation time. These results suggest that ROSmay play a role in the modification of ferritin by MG. Thereaction between ferritin and MG led to the release of ironions from the protein. Ferritin exposure to MG resulted in aloss of arginine, histidine and lysine residues. It was assumedthat oxidative damage to ferritin caused by MG may induce anincrease in the iron content in cells, which is deleterious tocells. This mechanism, in part, may provide an explanation orthe deterioration of organs under diabetic conditions. [BMBreports 2012; 45(3: 147-152

  13. Covalent Organic Framework Electrocatalysts for Clean Energy Conversion.

    Science.gov (United States)

    Lin, Chun-Yu; Zhang, Detao; Zhao, Zhenghang; Xia, Zhenhai

    2018-02-01

    Covalent organic frameworks (COFs) are promising for catalysis, sensing, gas storage, adsorption, optoelectricity, etc. owning to the unprecedented combination of large surface area, high crystallinity, tunable pore size, and unique molecular architecture. Although COFs are in their initial research stage, progress has been made in the design and synthesis of COF-based electrocatalysis for the oxygen reduction reaction, oxygen evolution reaction, hydrogen evolution reaction, and CO 2 reduction in energy conversion and fuel generation. Design principles are also established for some of the COF materials toward rational design and rapid screening of the best electrocatalysts for a specific application. Herein, the recent advances in the design and synthesis of COF-based catalysts for clean energy conversion and storage are presented. Future research directions and perspectives are also being discussed for the development of efficient COF-based electrocatalysts. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  14. Non-Covalent Organocatalyzed Domino Reactions Involving Oxindoles: Recent Advances

    Directory of Open Access Journals (Sweden)

    Tecla Gasperi

    2017-09-01

    Full Text Available The ubiquitous presence of spirooxindole architectures with several functionalities and stereogenic centers in bioactive molecules has been appealing for the development of novel methodologies seeking their preparation in high yields and selectivities. Expansion and refinement in the field of asymmetric organocatalysis have made possible the development of straightforward strategies that address these two requisites. In this review, we illustrate the current state-of-the-art in the field of spirooxindole synthesis through the use of non-covalent organocatalysis. We aim to provide a concise overview of very recent methods that allow to the isolation of unique, densely and diversified spirocyclic oxindole derivatives with high structural diversity via the use of cascade, tandem and domino processes.

  15. Near universal support for covalent immobilisation of enzymes for biotechnology

    International Nuclear Information System (INIS)

    Elnashar, M.M.; Millner, P.A.; Gibson, T.D.

    2005-01-01

    Carrageenan [1], natural polymer, has been modified to be used as a universal/near universal support to immobilise enzymes, where the gel remained stable at 70 degree C for 24 h at a wide range of buffers and ph s and its mechanical strength was 400% greater than the unmodified gel. The new matrix successfully immobilised covalently eight commercially used enzymes including hydrolases, Upases, oxidoreductases, proteases and dehydrogenases. It also acted as a self buffering system in case of hydrolases and stopped enzyme's product inhibition. The apparent Km values of immobilised enzymes were found in many cases to be much less than those of the free enzymes. Another interesting correlation was observed where the great lowering of the apparent Km with immobilised enzymes was directly proportional to the substrate molecular weight. In economic terms, the new matrix is at least two orders of magnitude cheaper than supports such as Eupergit C

  16. Electronic basis of hardness and phase transformations (covalent crystals)

    International Nuclear Information System (INIS)

    Gilman, J J

    2008-01-01

    Several electronic parameters measure the stabilities of covalent crystals, including minimum energy band-gap densities, inverse polarizabilities, plasma frequencies, transverse vibrational frequencies and elastic shear moduli. Convenient is the band-gap density (energy/volume; called the 'bond modulus'). For a given bonding type, the indentation hardness is proportional to the bond modulus. Examples are the group IV elements, III-V compounds; and II-VI compounds. The motion of dislocation kinks requires the excitation of bonding electrons into anti-bonding states. The bond modulus measures this together with the work done by the applied stress when a kink moves. In addition to hardness, the bond modulus measures the compressive strain (pressure) needed to transform an ambient structure into a more dense structure. Activation of such transformations also requires the excitation of bonding electrons into anti-bonding states together with the work done by the compressive stress

  17. Covalent bond orders and atomic valences from correlated wavefunctions

    Science.gov (United States)

    Ángyán, János G.; Rosta, Edina; Surján, Péter R.

    1999-01-01

    A comparison is made between two alternative definitions for covalent bond orders: one derived from the exchange part of the two-particle density matrix and the other expressed as the correlation of fluctuations (covariance) of the number of electrons between the atomic centers. Although these definitions lead to identical formulae for mono-determinantal SCF wavefunctions, they predict different bond orders for correlated wavefunctions. It is shown that, in this case, the fluctuation-based definition leads to slightly lower values of the bond order than does the exchange-based definition, provided one uses an appropriate space-partitioning technique like that of Bader's topological theory of atoms in a molecule; however, use of Mulliken partitioning in this context leads to unphysical behaviour. The example of H 2 is discussed in detail.

  18. Introduction to reversible computing

    CERN Document Server

    Perumalla, Kalyan S

    2013-01-01

    Few books comprehensively cover the software and programming aspects of reversible computing. Filling this gap, Introduction to Reversible Computing offers an expanded view of the field that includes the traditional energy-motivated hardware viewpoint as well as the emerging application-motivated software approach. Collecting scattered knowledge into one coherent account, the book provides a compendium of both classical and recently developed results on reversible computing. It explores up-and-coming theories, techniques, and tools for the application of rever

  19. Permit application modifications

    Energy Technology Data Exchange (ETDEWEB)

    NONE

    1995-11-01

    This document contains the Permit Application Modifications for the Y-12 Industrial Landfill V site on the Oak Ridge Reservation. These modifications include the assessment of stability of the proposed Landfill V under static and loading conditions. Analyses performed include the general slope stability, veneer stability of the bottom liner and cover system, and a liquefaction potential assessment of the foundation soils.

  20. The management of modifications

    International Nuclear Information System (INIS)

    Bernard, C.

    1992-01-01

    Description of the management methods of modifications at EDF. To maintain safety standards of the nuclear power station the 'Direction de l'Equipment' and the 'Direction du Parc en Exploitation' have jointly fixed the modalities of management for all modifications and recorded them in a 'Practical Guide'

  1. Permit application modifications

    International Nuclear Information System (INIS)

    1995-11-01

    This document contains the Permit Application Modifications for the Y-12 Industrial Landfill V site on the Oak Ridge Reservation. These modifications include the assessment of stability of the proposed Landfill V under static and loading conditions. Analyses performed include the general slope stability, veneer stability of the bottom liner and cover system, and a liquefaction potential assessment of the foundation soils

  2. Covalent DNA-protein crosslinking occurs after hyperthermia and radiation

    International Nuclear Information System (INIS)

    Cress, A.E.; Bowden, G.T.

    1983-01-01

    Covalent DNA-protein crosslinks occur in exponentially growing mouse leukemia cells (L1210) after exposure to ionizing radiation. The amount of DNA-protein crosslinks as measured by a filter binding assay is dose dependent upon x irradiation. Although hyperthermia and radiation in combination are synergistic with respect to cell lethality, the combination does not result in an increase of DNA-protein crosslinks when assayed immediately following treatments. Hyperthermia (43 0 C/15 min) given prior to radiation dose not alter the radiation dose dependency of the amount of initial crosslinking. In addition, the amount of DNA-protein crosslinking produced by heat plus radiation is independent of the length of heating the cells at 43 0 C. The DNA-protein crosslinks produced y 50-Gy x ray alone are removed after 2 hr at 37 0 C. However, if hyperthermia (43 0 C/15 min) is given prior to 100-Gy x ray, the removal of DNA-protein crosslinks is delayed until 4.0 hr after radiation. Phospho-serine and phospho-threonine bonds are not produced with either radiation or the combination of hyperthermia plus radiation as judged by the resistance of the bonds to guanidine hydrochloride. However, hyperthermia plus radiation causes an increase in phosphate to nitrogen type bonding. These results show that radiation alone causes covalent DNA-protein crosslinks. Hyperthermia in combination with radiation does not increase the total amount of the crosslinks but delays the removal of the crosslinks and alters the distribution of the types of chemical bonding

  3. Covalent-ionically cross-linked polyetheretherketone proton exchange membrane for direct methanol fuel cell

    CSIR Research Space (South Africa)

    Luo, H

    2010-08-01

    Full Text Available cross-linked PEEK-WC membrane, this covalent-ionically cross-linked PEEK-WC membrane exhibits extremely reduced water uptake and methanol permeability, but just slightly sacrificed proton conductivity. The proton conductivity of the covalent...

  4. Covalently bound conjugates of albumin and heparin: Synthesis, fractionation and characterization

    NARCIS (Netherlands)

    Hennink, Wim E.; Feijen, Jan; Ebert, Charles D.; Kim, Sung Wan

    1983-01-01

    Covalently bound conjugates of human serum albumin and heparin were prepared as compounds which could improve the blood-compatibility of polymer surfaces either by preadsorption or by covalent coupling of the conjugates onto blood contacting surfaces. The conjugates (10–16 weight % of heparin) were

  5. Covalently Immobilised Cytochrome C Imaged by In Situ Scanning Tunnelling Microscopy

    DEFF Research Database (Denmark)

    Andersen, Jens Enevold Thaulov; Olesen, Klaus G.; Danilov, Alexey I.

    1997-01-01

    In situ scanning tunnelling microscopy (STM) imaging of cytochrome c (cyt c) on polycrystalline Pt surfaces and on Au(lll) was achieved first by covalent immobilisation of 3-aminopropyltriethoxysilane (3-APTS) brought to react with oxide present on the Pt surfaces. Covalently bound 3-APTS forms...

  6. Application of the Covalent Bond Classification Method for the Teaching of Inorganic Chemistry

    Science.gov (United States)

    Green, Malcolm L. H.; Parkin, Gerard

    2014-01-01

    The Covalent Bond Classification (CBC) method provides a means to classify covalent molecules according to the number and types of bonds that surround an atom of interest. This approach is based on an elementary molecular orbital analysis of the bonding involving the central atom (M), with the various interactions being classified according to the…

  7. The role of double covalent flavin binding in chito-oligosaccharide oxidase from Fusarium graminearum

    NARCIS (Netherlands)

    Heuts, Dominic P. H. M.; Winter, Remko T.; Damsma, Gerke E.; Janssen, Dick B.; Fraaije, Marco W.

    2008-01-01

    ChitO (chito-oligosaccharide oxidase) from Fusarium graminearum catalyses the regioselective oxidation of N-acetylated oligosaccharides. The enzyme harbours an FAD cofactor that is covalently attached to His(94) and Cys(154). The functional role of this unusual bi-covalent flavin-protein linkage was

  8. Reversibility of female sterilization.

    Science.gov (United States)

    Siegler, A M; Hulka, J; Peretz, A

    1985-04-01

    The discussion considers the current status of reversibility of sterilization in the US and describes clinical and experimental efforts for developing techniques designed for reversibility. It focuses on regret following sterilization, reversal potential of current sterilization techniques, patient selection, current reversal techniques, results of sterilization procedures, experimental approaches to reversal of current techniques of sterilization, and sterilization procedures devised for reversibility, in humans and in animals. Request is the 1st stage of reversal, but a request for sterilization reversal (SR) does not always mean regret for a decision made at the time. Frequently it is a wish to restore fertility because life circumstances have changed after a sterilization that was ppropriate at the time it was performed. Schwyhart and Kutner reviewed 22 studies published between 1949-69 in which they found that the percentage of patients regretting the procedure ranged from 1.3-15%. Requests for reversal remain low in most countries, but if sterilization becomes a more popular method of contraception, requests will also increase. The ideal operation considered as a reversaible method of sterilization should include an easy, reliable outpatient method of tubal occlusion with miniml risk or patient discomfort that subsequently could be reversed without the need for a major surgical intervention. Endoscopic methods have progressed toward the 1st objective. A recent search of the literature uncovered few series of SR of more than 50 cases. The 767 operations found were analyzed with regard to pregnancy outcome. The precent of live births varied from 74-78.8%, and the occurance of tubal pregnancies ranged from 1.7-6.5%. All of the confounding variables in patient selection and small numbers of reported procedures preclude any conclusion about the different techniques or the number of operations that give a surgeon a level of expertise. Few authors classify their

  9. Quantum reverse hypercontractivity

    Energy Technology Data Exchange (ETDEWEB)

    Cubitt, Toby [Department of Computer Science, University College London, London, United Kingdom and Centre for Quantum Information and Foundations, DAMTP, University of Cambridge, Cambridge (United Kingdom); Kastoryano, Michael [NBIA, Niels Bohr Institute, University of Copenhagen, 2100 Copenhagen (Denmark); Montanaro, Ashley [School of Mathematics, University of Bristol, Bristol (United Kingdom); Temme, Kristan [Institute for Quantum Information and Matter, California Institute of Technology, Pasadena, California 91125 (United States)

    2015-10-15

    We develop reverse versions of hypercontractive inequalities for quantum channels. By generalizing classical techniques, we prove a reverse hypercontractive inequality for tensor products of qubit depolarizing channels. We apply this to obtain a rapid mixing result for depolarizing noise applied to large subspaces and to prove bounds on a quantum generalization of non-interactive correlation distillation.

  10. Atrioventricular Pacemaker Lead Reversal

    Directory of Open Access Journals (Sweden)

    Mehmet K Aktas, MD

    2007-01-01

    Full Text Available During cardiac surgery temporary epicardial atrial and ventricular leads are placed in case cardiac pacing is required postoperatively. We present the first reported series of patients with reversal of atrioventricular electrodes in the temporary pacemaker without any consequent deleterious hemodynamic effect. We review the electrocardiographic findings and discuss the findings that lead to the discovery of atrioventricular lead reversal.

  11. Modification of membrane sulfhydryl groups in bacteriostatic action of nitrite

    International Nuclear Information System (INIS)

    Buchman, G.W. III; Hansen, J.N.

    1987-01-01

    The mechanism by which nitrite inhibits outgrowing spores of bacillus cereus T was examined by using techniques developed earlier for nitrite analogs. The morphological stage of inhibition, cooperativity effects, effect of pH on inhibition, kinetics of protection against tritiated iodoacetate incorporation into membrane sulfhydryl groups, and protection against the bacteriocidal effect of carboxymethylation of iodoacetate indicate that nitrite acts as a membrane-directed sulfhydryl agent. The mechanism by which nitrite modifies the chemical reactivity of the sulfhyrdyl group could be either direct covalent modification or inactivation through communication with another modified membrane component. Profiles of pH effects suggest that the active agent is the protonated form of nitrite. The nitrite concentrations which modify membrane sulfhydryl activity coincide with those which have a bacteriostatic effect. These results are consistent with membrane sulfhydryl modification as a component of the mechanism of nitrite-induced bacteriostasis in this aerobic sporeformer

  12. Biotin Switch Assays for Quantitation of Reversible Cysteine Oxidation.

    Science.gov (United States)

    Li, R; Kast, J

    2017-01-01

    Thiol groups in protein cysteine residues can be subjected to different oxidative modifications by reactive oxygen/nitrogen species. Reversible cysteine oxidation, including S-nitrosylation, S-sulfenylation, S-glutathionylation, and disulfide formation, modulate multiple biological functions, such as enzyme catalysis, antioxidant, and other signaling pathways. However, the biological relevance of reversible cysteine oxidation is typically underestimated, in part due to the low abundance and high reactivity of some of these modifications, and the lack of methods to enrich and quantify them. To facilitate future research efforts, this chapter describes detailed procedures to target the different modifications using mass spectrometry-based biotin switch assays. By switching the modification of interest to a biotin moiety, these assays leverage the high affinity between biotin and avidin to enrich the modification. The use of stable isotope labeling and a range of selective reducing agents facilitate the quantitation of individual as well as total reversible cysteine oxidation. The biotin switch assay has been widely applied to the quantitative analysis of S-nitrosylation in different disease models and is now also emerging as a valuable research tool for other oxidative cysteine modifications, highlighting its relevance as a versatile, robust strategy for carrying out in-depth studies in redox proteomics. © 2017 Elsevier Inc. All rights reserved.

  13. Modifications to POISSON

    International Nuclear Information System (INIS)

    Harwood, L.H.

    1981-01-01

    At MSU we have used the POISSON family of programs extensively for magnetic field calculations. In the presently super-saturated computer situation, reducing the run time for the program is imperative. Thus, a series of modifications have been made to POISSON to speed up convergence. Two of the modifications aim at having the first guess solution as close as possible to the final solution. The other two aim at increasing the convergence rate. In this discussion, a working knowledge of POISSON is assumed. The amount of new code and expected time saving for each modification is discussed

  14. Preparation of organic monolithic columns in polytetrafluoroethylene tubes for reversed-phase liquid chromatography

    International Nuclear Information System (INIS)

    Catalá-Icardo, M.; Torres-Cartas, S.; Meseguer-Lloret, S.; Gómez-Benito, C.; Carrasco-Correa, E.; Simó-Alfonso, E.F.; Ramis-Ramos, G.; Herrero-Martínez, J.M.

    2017-01-01

    In this work, a method for the preparation and anchoring of polymeric monoliths in a polytetrafluoroethylene (PTFE) tubing as a column housing for microbore HPLC is described. In order to assure a covalent attachment of the monolith to the inner wall of the PTFE tube, a two-step procedure was developed. Two surface etching reagents, a commercial sodium naphthalene solution (Fluoroetch"®), or mixtures of H_2O_2 and H_2SO_4, were tried and compared. Then, the obtained hydroxyl groups on the PTFE surface were modified by methacryloylation. Attenuated total reflectance Fourier-transform infrared (ATR-FTIR) spectroscopy and scanning electron microscopy (SEM) confirmed the successful modification of the tubing wall and the stable anchorage of monolith to the wall, respectively. Special emphasis was also put on the reduction of the unwanted effects of shrinking of monolith during polymerization, by using an external proper mold and by selecting the adequate monomers in order to increase the flexibility of the polymer. Poly(glycidyl methacrylate-co-divinylbenzene) monoliths were in situ synthesized by thermal polymerization within the confines of surface-vinylized PTFE tubes. The modified PTFE tubing tightly held the monolith, and the monolithic column exhibited good pressure resistance up to 20 MPa. The column performance was also evaluated via the isocratic separation of a series of alkylbenzenes in the reversed-phase mode. The optimized monolithic columns gave plate heights ranged between 70 and 80 μm. The resulting monoliths were also satisfactorily applied to the separation of proteins. - Highlights: • Successful surface etching of PTFE inner wall tubing was done. • The modified PTFE support was next methacryloylated with GMA. • Organic polymeric monolith was in situ prepared in the functionalized PTFE tube. • The monolithic columns gave suitable pressure resistance and separation of proteins.

  15. Preparation of organic monolithic columns in polytetrafluoroethylene tubes for reversed-phase liquid chromatography

    Energy Technology Data Exchange (ETDEWEB)

    Catalá-Icardo, M., E-mail: mocaic@qim.upv.es [Research Institute for Integrated Management of Coastal Areas, Universitat Politècnica de València, Paranimf 1, 46730, Grao de Gandía, Valencia (Spain); Torres-Cartas, S.; Meseguer-Lloret, S.; Gómez-Benito, C. [Research Institute for Integrated Management of Coastal Areas, Universitat Politècnica de València, Paranimf 1, 46730, Grao de Gandía, Valencia (Spain); Carrasco-Correa, E.; Simó-Alfonso, E.F.; Ramis-Ramos, G. [Department of Analytical Chemistry, Universitat de València, Dr. Moliner 50, 46100, Burjassot, Valencia (Spain); Herrero-Martínez, J.M., E-mail: jmherrer@uv.es [Department of Analytical Chemistry, Universitat de València, Dr. Moliner 50, 46100, Burjassot, Valencia (Spain)

    2017-04-01

    In this work, a method for the preparation and anchoring of polymeric monoliths in a polytetrafluoroethylene (PTFE) tubing as a column housing for microbore HPLC is described. In order to assure a covalent attachment of the monolith to the inner wall of the PTFE tube, a two-step procedure was developed. Two surface etching reagents, a commercial sodium naphthalene solution (Fluoroetch{sup ®}), or mixtures of H{sub 2}O{sub 2} and H{sub 2}SO{sub 4}, were tried and compared. Then, the obtained hydroxyl groups on the PTFE surface were modified by methacryloylation. Attenuated total reflectance Fourier-transform infrared (ATR-FTIR) spectroscopy and scanning electron microscopy (SEM) confirmed the successful modification of the tubing wall and the stable anchorage of monolith to the wall, respectively. Special emphasis was also put on the reduction of the unwanted effects of shrinking of monolith during polymerization, by using an external proper mold and by selecting the adequate monomers in order to increase the flexibility of the polymer. Poly(glycidyl methacrylate-co-divinylbenzene) monoliths were in situ synthesized by thermal polymerization within the confines of surface-vinylized PTFE tubes. The modified PTFE tubing tightly held the monolith, and the monolithic column exhibited good pressure resistance up to 20 MPa. The column performance was also evaluated via the isocratic separation of a series of alkylbenzenes in the reversed-phase mode. The optimized monolithic columns gave plate heights ranged between 70 and 80 μm. The resulting monoliths were also satisfactorily applied to the separation of proteins. - Highlights: • Successful surface etching of PTFE inner wall tubing was done. • The modified PTFE support was next methacryloylated with GMA. • Organic polymeric monolith was in situ prepared in the functionalized PTFE tube. • The monolithic columns gave suitable pressure resistance and separation of proteins.

  16. Accommodating for plant modifications

    International Nuclear Information System (INIS)

    Weirich, P.H.

    1977-01-01

    Modification to a nuclear power plant may have different causes: 1) new instructions by the authorities; 2) changes of the marginal conditions on the construction site; 3) progress in the technological development. - Examples from different plants are supposed to demonstrate how such changes influence the planning or the construction and how they are integrated in the process of preparation. A distinction can be made between modifications before the completion of the submission of the order, during the phase of preparatory planning and during the construction phase. Of great importance are especially modifications made after the beginning of the construction works, since, in general, there is little scope for technical modifications and since consequences for the time schedule are to be expected. (orig.) [de

  17. Structural dynamic modification

    Indian Academy of Sciences (India)

    and stiffness matrices) andaor modal parameters, in order to acquire some ... For the above reasons, another modification approach is presented here ... The data necessary to solve the direct problem are dynamic behaviour of the original.

  18. Pragmatic Graph Rewriting Modifications

    OpenAIRE

    Rodgers, Peter; Vidal, Natalia

    1999-01-01

    We present new pragmatic constructs for easing programming in visual graph rewriting programming languages. The first is a modification to the rewriting process for nodes the host graph, where nodes specified as 'Once Only' in the LHS of a rewrite match at most once with a corresponding node in the host graph. This reduces the previously common use of tags to indicate the progress of matching in the graph. The second modification controls the application of LHS graphs, where those specified a...

  19. A fundamental trade-off in covalent switching and its circumvention by enzyme bifunctionality in glucose homeostasis.

    Science.gov (United States)

    Dasgupta, Tathagata; Croll, David H; Owen, Jeremy A; Vander Heiden, Matthew G; Locasale, Jason W; Alon, Uri; Cantley, Lewis C; Gunawardena, Jeremy

    2014-05-09

    Covalent modification provides a mechanism for modulating molecular state and regulating physiology. A cycle of competing enzymes that add and remove a single modification can act as a molecular switch between "on" and "off" and has been widely studied as a core motif in systems biology. Here, we exploit the recently developed "linear framework" for time scale separation to determine the general principles of such switches. These methods are not limited to Michaelis-Menten assumptions, and our conclusions hold for enzymes whose mechanisms may be arbitrarily complicated. We show that switching efficiency improves with increasing irreversibility of the enzymes and that the on/off transition occurs when the ratio of enzyme levels reaches a value that depends only on the rate constants. Fluctuations in enzyme levels, which habitually occur due to cellular heterogeneity, can cause flipping back and forth between on and off, leading to incoherent mosaic behavior in tissues, that worsens as switching becomes sharper. This trade-off can be circumvented if enzyme levels are correlated. In particular, if the competing catalytic domains are on the same protein but do not influence each other, the resulting bifunctional enzyme can switch sharply while remaining coherent. In the mammalian liver, the switch between glycolysis and gluconeogenesis is regulated by the bifunctional 6-phosphofructo-2-kinase/fructose-2,6-bisphosphatase (PFK-2/FBPase-2). We suggest that bifunctionality of PFK-2/FBPase-2 complements the metabolic zonation of the liver by ensuring coherent switching in response to insulin and glucagon.

  20. Modification of JRR-2

    International Nuclear Information System (INIS)

    Miyasaka, Yasuhiko

    1978-01-01

    This report gives an outline of some of the main modifications carried out around the Reactor Core on the Research Reactor JRR-2, at the Tokai Research Establishment of JAERI. The JRR-2 was shut down in December 1973, to improve it in heavy water leakage from the metal packing between core tank and support ring, corrosion of the lower shielding plug, and fault in the control-rod mechanism. Main modifications were a standing seal weld at the support ring to stop heavy water leakage, replacement of the reactor top shield and improvement of the helium system. The control-rod assemblies and the refueling devices were replaced by the newly designed ones also. In addition to the modification plan, the irradiated air exhaust system was improved to reduce radioactive argon gas release through the stack. Works were completed successfully in September 1975. But a light water leakage occurred at the stand pipe below the light water tank on November 11, 1975, which was repaired in about 4 months. When considering the operation of above 5,000 hours after the modification, however, the quality of the modification work may be said to be quite satisfactory. The present report in which works to the completion are described may be valuable as a record of reactor modification which is a new experience at JAERI. (auth.)

  1. Investigating MCTS Modifications in General Video Game Playing

    DEFF Research Database (Denmark)

    Frydenberg, Frederik; Andersen, Kasper; Risi, Sebastian

    2015-01-01

    -style video games. This paper investigates of how well these modifications perform in general video game playing using the general video game AI (GVG-AI) framework and introduces a new MCTS modification called UCT reverse penalty that penalizes the MCTS controller for exploring recently visited children......While Monte Carlo tree search (MCTS) methods have shown promise in a variety of different board games, more complex video games still present significant challenges. Recently, several modifications to the core MCTS algorithm have been proposed with the hope to increase its effectiveness on arcade....... The results of our experiments show that a combination of two MCTS modifications can improve the performance of the vanilla MCTS controller, but the effectiveness of the modifications highly depends on the particular game being played....

  2. Synthesis and strong optical limiting response of graphite oxide covalently functionalized with gallium phthalocyanine

    Science.gov (United States)

    Li, Yong-Xi; Zhu, Jinhui; Chen, Yu; Zhang, Jinjuan; Wang, Jun; Zhang, Bin; He, Ying; Blau, Werner J.

    2011-05-01

    A soluble graphite oxide (GO) axially substituted gallium phthalocyanine (PcGa) hybrid material (GO-PcGa) was for the first time synthesized by the reaction of tBu4PcGaCl with GO in anhydrous DMSO at 110 °C in the presence of K2CO3. The formation of a Ga-O bond between PcGa and GO has been confirmed by x-ray photoelectron spectroscopy. In contrast to GO, the D and G bands of GO-PcGa in the Raman spectrum are shifted to the lower wavenumbers by Δν = 11 and 18 cm - 1, respectively. At the same level of concentration of 0.1 g l - 1, GO-PcGa exhibit much larger nonlinear optical extinction coefficients and strong optical limiting performance than GO, tBu4PcGaCl and C60 at both 532 and 1064 nm, implying a remarkable accumulation effect as a result of the covalent link between GO and PcGa. GO-PcGa possesses three main mechanisms for the nonlinear optical response—nonlinear light scattering, two-photon absorption and reverse saturable absorption for the 532 nm pulses and nonlinear light scattering for the 1064 nm pulses. tBu4PcGaCl does not make any significant contribution to the optical limiting at 1064 nm, while GO-PcGa has a much greater optical limiting response than GO at this wavelength, this suggesting that the PcGa moiety could certainly play an unknown but important role in the GO-PcGa material system.

  3. Covalent attachment of polymeric monolith to polyether ether ketone (PEEK) tubing.

    Science.gov (United States)

    Lv, Chunguang; Heiter, Jaana; Haljasorg, Tõiv; Leito, Ivo

    2016-08-17

    A new method of reproducible preparation of vinylic polymeric monolithic columns with a key step of covalently anchoring the monolith to PEEK surface is described. In order to chemically attach the polymer monolith to the tube wall, methacrylate functional groups were introduced onto PEEK surface by a three-step procedure, including surface etching, surface reduction and surface methacryloylation. The chemical state of the modified tubing surface was characterized by attenuated total reflectance infrared (ATR-IR) spectroscopy. It was found that the etching step is the key to successfully modifying the PEEK tubing surface. Poly(styrene-co-divinylbenzene) monoliths were in situ synthesized by thermally initiated free radical copolymerization within the confines of surface-vinylized PEEK tubings of dimensions close to ones conventionally used in HPLC and UHPLC (1.6 mm internal diameter, 10.0-12.5 cm length). Adhesion test was done by measuring the operating pressure drop, which the prepared stationary phases can withstand. Good pressure resistance, up to 140 bar/10 cm (flow rate 0.5 mL min(-1), acetonitrile as a mobile phase), indicates strong bonding of monolith to the tubing wall. The monolithic material was proven to have a permeability of 1.7 × 10 (-14) m(2), applying acetonitrile-water 70:30 (v/v) as a mobile phase. The column performance was reproducible from column to column and was evaluated via the isocratic separation of a series of alkylbenzenes in the reversed-phase mode (acetonitrile-water 70:30, v/v). The numbers of plates per meter at optimal flow rate were found to be between 26 000 and 32 000 for the different analytes. Copyright © 2016 Elsevier B.V. All rights reserved.

  4. Covalent surface modification of prions: a mass spectrometry-based means of detecting distinctive structural features of prion strains

    Science.gov (United States)

    Prions (PrPSc) are molecular pathogens that are able to convert the isosequential normal cellular prion protein (PrPC) into a prion. The only demonstrated differences between PrPC and PrPSc is conformational, they are isoforms. A given host can be infected by more than one kind or strain of prion. F...

  5. False-Positive Rate Determination of Protein Target Discovery using a Covalent Modification- and Mass Spectrometry-Based Proteomics Platform

    Science.gov (United States)

    Strickland, Erin C.; Geer, M. Ariel; Hong, Jiyong; Fitzgerald, Michael C.

    2014-01-01

    Detection and quantitation of protein-ligand binding interactions is important in many areas of biological research. Stability of proteins from rates of oxidation (SPROX) is an energetics-based technique for identifying the proteins targets of ligands in complex biological mixtures. Knowing the false-positive rate of protein target discovery in proteome-wide SPROX experiments is important for the correct interpretation of results. Reported here are the results of a control SPROX experiment in which chemical denaturation data is obtained on the proteins in two samples that originated from the same yeast lysate, as would be done in a typical SPROX experiment except that one sample would be spiked with the test ligand. False-positive rates of 1.2-2.2 % and analysis of the isobaric mass tag (e.g., iTRAQ®) reporter ions used for peptide quantitation. Our results also suggest that technical replicates can be used to effectively eliminate such false positives that result from this random error, as is demonstrated in a SPROX experiment to identify yeast protein targets of the drug, manassantin A. The impact of ion purity in the tandem mass spectral analyses and of background oxidation on the false-positive rate of protein target discovery using SPROX is also discussed.

  6. The anti-browning agent sulfite inactivates Agaricus bisporus tyrosinase through covalent modification of the copper-B site

    NARCIS (Netherlands)

    Kuijpers, T.F.M.; Gruppen, H.; Sforza, S.; Berkel, van W.J.H.; Vincken, J.P.

    2013-01-01

    Sulfite salts are widely used as antibrowning agents in food processing. Nevertheless, the exact mechanism by which sulfite prevents enzymatic browning has remained unknown. Here, we show that sodium hydrogen sulfite (NaHSO3 ) irreversibly blocks the active site of tyrosinase from the edible

  7. An algebra of reversible computation.

    Science.gov (United States)

    Wang, Yong

    2016-01-01

    We design an axiomatization for reversible computation called reversible ACP (RACP). It has four extendible modules: basic reversible processes algebra, algebra of reversible communicating processes, recursion and abstraction. Just like process algebra ACP in classical computing, RACP can be treated as an axiomatization foundation for reversible computation.

  8. Human Rights and Behavior Modification

    Science.gov (United States)

    Roos, Philip

    1974-01-01

    Criticisms of behavior modification, which charge that it violates ethical and legal principles, are discussed and reasons are presented to explain behavior modification's susceptibility to attack. (GW)

  9. Coval: improving alignment quality and variant calling accuracy for next-generation sequencing data.

    Directory of Open Access Journals (Sweden)

    Shunichi Kosugi

    Full Text Available Accurate identification of DNA polymorphisms using next-generation sequencing technology is challenging because of a high rate of sequencing error and incorrect mapping of reads to reference genomes. Currently available short read aligners and DNA variant callers suffer from these problems. We developed the Coval software to improve the quality of short read alignments. Coval is designed to minimize the incidence of spurious alignment of short reads, by filtering mismatched reads that remained in alignments after local realignment and error correction of mismatched reads. The error correction is executed based on the base quality and allele frequency at the non-reference positions for an individual or pooled sample. We demonstrated the utility of Coval by applying it to simulated genomes and experimentally obtained short-read data of rice, nematode, and mouse. Moreover, we found an unexpectedly large number of incorrectly mapped reads in 'targeted' alignments, where the whole genome sequencing reads had been aligned to a local genomic segment, and showed that Coval effectively eliminated such spurious alignments. We conclude that Coval significantly improves the quality of short-read sequence alignments, thereby increasing the calling accuracy of currently available tools for SNP and indel identification. Coval is available at http://sourceforge.net/projects/coval105/.

  10. The covalence effect of energy levels of ZnS:Mn2+

    International Nuclear Information System (INIS)

    Dong-Yang, Li; Mao-Lu, Du; Yi, Huang

    2013-01-01

    The contribution of the different covalence for t 2 and e orbitals must be considered in the investigation of the optical and magnetic properties of the transition metal ion in II–VI and III–V semiconductors. In present paper, two covalent parameters N t and N e associated with t 2 and e orbitals have been adopted to describe the covalence. The energy matrices considering the different covalence for t 2 and e orbitals have been provided for d 5 ions in crystal. These matrices show that the contribution from the Racah parameter A cannot be neglected in calculation of energy-level of d 5 ions in covalent crystal. The calculated results using the matrix show that the energy levels of 4 E and 4 A 1 states split, and the energy-level difference between 4 E and 4 A 1 states increases with increase of the different covalence between t 2 and e orbitals. These energy levels are always degenerate, when the different covalence for t 2 and e orbitals is neglected. By using the energy matrices, the energy-level of ZnS:Mn 2+ has been calculated. The calculated energy levels of ZnS:Mn 2+ are in good agreement with the experiments

  11. COVALENT IMMOBILIZATION OF INVERTASE ON EPOXY-ACTIVATED POLYANILINE FILMS

    Directory of Open Access Journals (Sweden)

    Loredana Vacareanu

    2013-08-01

    Full Text Available The growing interest in manufacturing and use of biosensors is their rapid and selective detection of the target analyte. The immobilization of the enzymes, onto the appropriate matrix is the key-step in the construction of biosensing devices, considerably affecting its performance. In this study, new polyaniline bearing epoxy groups was synthesized by electrochemical polymerization reactions, as adherent, green film deposited on electrode surface, and was further used as immobilization matrix for invertase enzyme. The immobilization was carried out by condensation reactions between the amino groups of the enzyme molecules and the epoxy groups of polyaniline film. The covalent attachment was achieved by simple immersing the epoxy-activated polyaniline in acetate buffer solution (10 mM, pH 6.0 containing 2mg/mL invertase, for 24 h at 4 ºC, by continuous stirring. The polyaniline films thus obtained were analyzed before and after the invertase attachment, by using FT-IR spectroscopy and SEM microscopy. The presence of the invertase was evaluated by measuring their activity, using UV-Vis spectroscopy, in the presence of a known amount of sucrose as a substrate. These tests, performed for three times under the same conditions, revealed that even after five washes of the polyaniline /invertase electrode to remove the unbounded enzyme, the enzyme remain attached on the polyaniline film, being able to hydrolyze the sucrose presented in the assay solutions.

  12. Characterising non-covalent interactions with the Cambridge Structural Database.

    Science.gov (United States)

    Lommerse, J P; Taylor, R

    1997-02-01

    This review describes how the CSD can be used to study non-covalent interactions. Several different types of information may be obtained. First, the relative frequencies of various interactions can be studied; for example, we have shown that the terminal oxygen atoms of phosphate groups accept hydrogen bonds far more often than the linkage oxygens. Secondly, information can be obtained about the geometries of nonbonded contacts; for example, hydrogen bonds to P-O groups rarely form along the extension of the P-O bond, whereas short contacts between oxygen and carbon-bound iodine show a strong preference for linear C-I ... O angles. Thirdly, the CSD can be searched for novel interactions which may be exploited in inhibitor design; for example, the I ... O contacts just mentioned, and N-H ... pi hydrogen bonds. Finally, the CSD can suggest synthetic targets for medicinal chemistry; for example, molecules containing delocalised electron deficient groups such as trimethylammonium, pyridinium, thaizolium and dinitrophenyl have a good chance of binding to an active-site tryptophan. Although the CSD contains small-molecule crystal structures, not protein-ligand complexes, there is considerable evidence that the contacts seen in the two types of structures are similar. We have illustrated this a number of times in the present review and additional evidence has been given previously by Klebe. The major advantages of the CSD are its size, diversity and experimental accuracy. For these reasons, it is a useful tool for modellers engaged in rational inhibitor design.

  13. Selective Covalent Conjugation of Phosphorothioate DNA Oligonucleotides with Streptavidin

    Directory of Open Access Journals (Sweden)

    Christof M. Niemeyer

    2011-08-01

    Full Text Available Protein-DNA conjugates have found numerous applications in the field of diagnostics and nanobiotechnology, however, their intrinsic susceptibility to DNA degradation by nucleases represents a major obstacle for many applications. We here report the selective covalent conjugation of the protein streptavidin (STV with phosphorothioate oligonucleotides (psDNA containing a terminal alkylthiolgroup as the chemically addressable linking unit, using a heterobifunctional NHS-/maleimide crosslinker. The psDNA-STV conjugates were synthesized in about 10% isolated yields. We demonstrate that the terminal alkylthiol group selectively reacts with the maleimide while the backbone sulfur atoms are not engaged in chemical conjugation. The novel psDNA-STV conjugates retain their binding capabilities for both biotinylated macromolecules and the complementary nucleic acid. Moreover, the psDNA-STV conjugate retained its binding capacity for complementary oligomers even after a nuclease digestion step, which effectively degrades deoxyribonucleotide oligomers and thus the binding capability of regular DNA-STV conjugates. The psDNA-STV therefore hold particular promise for applications e.g. in proteome research and novel biosensing devices, where interfering endogenous nucleic acids need to be removed from analytes by nuclease digestion.

  14. Self-Suspended Suspensions of Covalently Grafted Hairy Nanoparticles

    KAUST Repository

    Choudhury, Snehashis

    2015-03-17

    © 2015 American Chemical Society. Dispersions of small particles in liquids have been studied continuously for almost two centuries for their ability to simultaneously advance understanding of physical properties of fluids and their widespread use in applications. In both settings, the suspending (liquid) and suspended (solid) phases are normally distinct and uncoupled on long length and time scales. In this study, we report on the synthesis and physical properties of a novel family of covalently grafted nanoparticles that exist as self-suspended suspensions with high particle loadings. In such suspensions, we find that the grafted polymer chains exhibit unusual multiscale structural transitions and enhanced conformational stability on subnanometer and nanometer length scales. On mesoscopic length scales, the suspensions display exceptional homogeneity and colloidal stability. We attribute this feature to steric repulsions between grafted chains and the space-filling constraint on the tethered chains in the single-component self-suspended materials, which inhibits phase segregation. On macroscopic length scales, the suspensions exist as neat fluids that exhibit soft glassy rheology and, counterintuitively, enhanced elasticity with increasing temperature. This feature is discussed in terms of increased interpenetration of the grafted chains and jamming of the nanoparticles. (Chemical Presented).

  15. Hydrolytic Stability of Boronate Ester-Linked Covalent Organic Frameworks

    KAUST Repository

    Li, Huifang

    2018-01-30

    The stability of covalent organic frameworks (COFs) is essential to their applications. However, the common boronate ester-linked COFs are susceptible to attack by nucleophiles (such as water molecules) at the electron-deficient boron sites. To provide an understanding of the hydrolytic stability of the representative boronate ester-linked COF-5 and of the associated hydrolysis mechanisms, density functional theory (DFT) calculations were performed to characterize the hydrolysis reactions of the molecule formed by the condensation of 1,4-phenylenebis(boronic acid) (PBBA) and 2,3,6,7,10,11-hexahydroxytriphenylene (HHTP) monomers; two cases were considered, one dealing with the freestanding molecule and the other with the molecule interacting with COF layers. It was found that the boronate ester (B–O) bond dissociation, which requires one H2O molecule, has a relatively high energy barrier of 22.3 kcal mol−1. However, the presence of an additional H2O molecule significantly accelerates hydrolysis by reducing the energy barrier by a factor of 3. Importantly, the hydrolysis of boronate ester bonds situated in a COF environment follows reaction pathways that are different and have increased energy barriers. These results point to an enhanced hydrolytic stability of COF-5 crystals.

  16. Unsynchronized resonance of covalent bonds in the superconducting state

    International Nuclear Information System (INIS)

    Costa, Marconi B.S.; Bastos, Cristiano C.; Pavao, Antonio C.

    2012-01-01

    Daft calculations performed on different cluster models of cuprates (LaBa 2 Cu 3 O 6.7 , La 1.85 Sr 0.15 CuO 4 , YBa 2 Cu 3 O 7 , TlBa 2 Ca 2 Cu 3 O 8.78 , HgBa 2 Ca 2 Cu 3 O 8.27 ), metallic systems (Nb 3 Ge, MgB 2 ) and the pnictide LaO 0.92 F 0.08 FeAs made evident the occurrence of un synchronized resonance of covalent bonds in the superconducting state, as predicted by Paling's resonating valence bond Rb) theory. For cuprates, the un synchronized resonance involves electron transfer between Cu atoms accompanied by a decrease in the charge of the La, Sr, Y and Ca atoms. For MgB 2 , electron transfer occurs in the Mg layer, while the B layer behaves as charge reservoir. For Nb 3 Ge, unsynchronized resonance occurs among the Ge atoms, which should be responsible for charge transfer. For LaO 0.92 F 0.08 FeAs, the results suggest that both La-O and Fe-As layers are involved in the mechanism of superconductivity. The identification of unsynchronized resonances in these systems provides evidence which supports RVB as a suitable theory for high-temperature superconductivity (high-TC). (author)

  17. Extending density functional embedding theory for covalently bonded systems.

    Science.gov (United States)

    Yu, Kuang; Carter, Emily A

    2017-12-19

    Quantum embedding theory aims to provide an efficient solution to obtain accurate electronic energies for systems too large for full-scale, high-level quantum calculations. It adopts a hierarchical approach that divides the total system into a small embedded region and a larger environment, using different levels of theory to describe each part. Previously, we developed a density-based quantum embedding theory called density functional embedding theory (DFET), which achieved considerable success in metals and semiconductors. In this work, we extend DFET into a density-matrix-based nonlocal form, enabling DFET to study the stronger quantum couplings between covalently bonded subsystems. We name this theory density-matrix functional embedding theory (DMFET), and we demonstrate its performance in several test examples that resemble various real applications in both chemistry and biochemistry. DMFET gives excellent results in all cases tested thus far, including predicting isomerization energies, proton transfer energies, and highest occupied molecular orbital-lowest unoccupied molecular orbital gaps for local chromophores. Here, we show that DMFET systematically improves the quality of the results compared with the widely used state-of-the-art methods, such as the simple capped cluster model or the widely used ONIOM method.

  18. Sex reversal in vertebrates

    OpenAIRE

    2016-01-01

    This special topic issue of Sexual Development gives an overview of sex reversal in vertebrates, from fishes naturally changing their sex, to rodents escaping the mammalian SRY-determining system. It offers eight up-to-date reviews on specific subjects in sex reversal, considering fishes, amphibians, reptiles, birds, marsupials, and placental mammals, including humans. The broad scope of represented animals makes this ideal for students and researchers, especially those interested in the...

  19. On thermodynamic and microscopic reversibility

    International Nuclear Information System (INIS)

    Crooks, Gavin E

    2011-01-01

    The word 'reversible' has two (apparently) distinct applications in statistical thermodynamics. A thermodynamically reversible process indicates an experimental protocol for which the entropy change is zero, whereas the principle of microscopic reversibility asserts that the probability of any trajectory of a system through phase space equals that of the time reversed trajectory. However, these two terms are actually synonymous: a thermodynamically reversible process is microscopically reversible, and vice versa

  20. Reversal of subtidal dune asymmetries caused by seasonally reversing wind-driven currents in Torres Strait, northeastern Australia

    Science.gov (United States)

    Harris, Peter T.

    1991-07-01

    Large subtidal sand dunes (sandwaves) located in Adolphus Channel, Torres Strait, have been observed to reverse their asymmetric orientation between September-February. This has been attributed to a reversal in wind-driven currents, which flow westward during the SE trade season (April-November) and eastwards during the NW monsoon season [December-March: HARRIS (1989) Continental Shelf Research, 9, 981-1002]. Observations in September 1988 and February 1989 from another area of dunes in Torres Strait corroborate this asymmetry reversal pattern. The results indicate that such reversals may be common in Torres Strait and in other areas where subtidal bedforms are subject to modification by superimposed, seasonally reversing, wind-driven currents.

  1. Surface passivation for tight-binding calculations of covalent solids

    International Nuclear Information System (INIS)

    Bernstein, N

    2007-01-01

    Simulation of a cluster representing a finite portion of a larger covalently bonded system requires the passivation of the cluster surface. We compute the effects of an explicit hybrid orbital passivation (EHOP) on the atomic structure in a model bulk, three-dimensional, narrow gap semiconductor, which is very different from the wide gap, quasi-one-dimensional organic molecules where most passivation schemes have been studied in detail. The EHOP approach is directly applicable to minimal atomic orbital basis methods such as tight-binding. Each broken bond is passivated by a hybrid created from an explicitly expressed linear combination of basis orbitals, chosen to represent the contribution of the missing neighbour, e.g. a sp 3 hybrid for a single bond. The method is tested by computing the forces on atoms near a point defect as a function of cluster geometry. We show that, compared to alternatives such as pseudo-hydrogen passivation, the force on an atom converges to the correct bulk limit more quickly as a function of cluster radius, and that the force is more stable with respect to perturbations in the position of the cluster centre. The EHOP method also obviates the need for parameterizing the interactions between the system atoms and the passivating atoms. The method is useful for cluster calculations of non-periodic defects in large systems and for hybrid schemes that simulate large systems by treating finite regions with a quantum-mechanical model, coupled to an interatomic potential description of the rest of the system

  2. Covalent dimerization of ribulose bisphosphate carboxylase subunits by UV radiation

    Energy Technology Data Exchange (ETDEWEB)

    Ferreira, R.M.B. [Universidade Tecnica, Lisbon (Portugal). Inst. Superior de Agronomia]|[Universidade Nova de Lisboa, Oeiras (Portugal). Instituto de Tecnologia Quimica e Biologica; Franco, E.; Teixeira, A.R.N. [Universidade Tecnica, Lisbon (Portugal). Inst. Superior de Agronomia

    1996-08-15

    The effect of UV radiation (UV-A, UV-B and UV-C) on ribulose bisphosphate carboxylase from a variety of plant species was examined. The exposition of plant leaves or the pure enzyme to UV radiation produced a UV-dependent accumulation of a 65 kDa polypeptide (P65). Different approaches were utilized to elucidate the origin and structure of P65: electrophoretic and fluorographic analyses of {sup 35}S-labelled ribulose biphosphate carboxylase exposed to UV radiation and immunological experiments using antibodies specific for P65, for the large and small subunits of ribulose biphosphate carboxylase and for high-molecular-mass aggregates of the enzyme. These studies revealed that P65 is a dimer, formed by the covalent, non-disulphide linkage of one small subunit with one large subunit of ribulose biphosphate carboxylase. For short periods of time (<1 h), the amount of P65 formed increased with the duration of the exposure to the UV radiation and with the energy of the radiation applied. Prolonged exposure to UV radiation (1-6 h) resulted in the formation of high-molecular-mass aggregates of ribulose biphosphate carboxylase. Formation of P65 was shown to depend on the native state of the protein, was stimulated by inhibitors of enzyme activity, and was inhibited by activators of enzyme activity. A UV-independent accumulation of P65 was also achieved by the in vitro incubation of plant crude extracts. However, the UV-dependent and the UV-independent formation of P65 seemed to occur by distinct molecular mechanisms. The UV-dependent accumulation of P65 was immunologically detected in all species examined, including Lemna minor, Arum italicum, Brassica oleracea, Triticum aestivum, Zea mays, Pisum sativum and Phaseolus vulgaris, suggesting that it may constitute a universal response to UV radiation, common to all photosynthetic tissues. (Author).

  3. Covalent dimerization of ribulose bisphosphate carboxylase subunits by UV radiation

    International Nuclear Information System (INIS)

    Ferreira, R.M.B.; Universidade Nova de Lisboa, Oeiras; Franco, E.; Teixeira, A.R.N.

    1996-01-01

    The effect of UV radiation (UV-A, UV-B and UV-C) on ribulose bisphosphate carboxylase from a variety of plant species was examined. The exposition of plant leaves or the pure enzyme to UV radiation produced a UV-dependent accumulation of a 65 kDa polypeptide (P65). Different approaches were utilized to elucidate the origin and structure of P65: electrophoretic and fluorographic analyses of 35 S-labelled ribulose biphosphate carboxylase exposed to UV radiation and immunological experiments using antibodies specific for P65, for the large and small subunits of ribulose biphosphate carboxylase and for high-molecular-mass aggregates of the enzyme. These studies revealed that P65 is a dimer, formed by the covalent, non-disulphide linkage of one small subunit with one large subunit of ribulose biphosphate carboxylase. For short periods of time (<1 h), the amount of P65 formed increased with the duration of the exposure to the UV radiation and with the energy of the radiation applied. Prolonged exposure to UV radiation (1-6 h) resulted in the formation of high-molecular-mass aggregates of ribulose biphosphate carboxylase. Formation of P65 was shown to depend on the native state of the protein, was stimulated by inhibitors of enzyme activity, and was inhibited by activators of enzyme activity. A UV-independent accumulation of P65 was also achieved by the in vitro incubation of plant crude extracts. However, the UV-dependent and the UV-independent formation of P65 seemed to occur by distinct molecular mechanisms. The UV-dependent accumulation of P65 was immunologically detected in all species examined, including Lemna minor, Arum italicum, Brassica oleracea, Triticum aestivum, Zea mays, Pisum sativum and Phaseolus vulgaris, suggesting that it may constitute a universal response to UV radiation, common to all photosynthetic tissues. (Author)

  4. Use of Functionalized Carbon Nanotubes for Covalent Attachment of Nanotubes to Silicon

    Science.gov (United States)

    Tour, James M.; Dyke, Christopher A.; Maya, Francisco; Stewart, Michael P.; Chen, Bo; Flatt, Austen K.

    2012-01-01

    The purpose of the invention is to covalently attach functionalized carbon nanotubes to silicon. This step allows for the introduction of carbon nanotubes onto all manner of silicon surfaces, and thereby introduction of carbon nano - tubes covalently into silicon-based devices, onto silicon particles, and onto silicon surfaces. Single-walled carbon nanotubes (SWNTs) dispersed as individuals in surfactant were functionalized. The nano - tube was first treated with 4-t-butylbenzenediazonium tetrafluoroborate to give increased solubility to the carbon nanotube; the second group attached to the sidewall of the nanotube has a silyl-protected terminal alkyne that is de-protected in situ. This gives a soluble carbon nanotube that has functional groups appended to the sidewall that can be attached covalently to silicon. This reaction was monitored by UV/vis/NJR to assure direct covalent functionalization.

  5. Construction and repair of highly ordered 2D covalent networks by chemical equilibrium regulation.

    Science.gov (United States)

    Guan, Cui-Zhong; Wang, Dong; Wan, Li-Jun

    2012-03-21

    The construction of well-ordered 2D covalent networks via the dehydration of di-borate aromatic molecules was successfully realized through introducing a small amount of water into a closed reaction system to regulate the chemical equilibrium.

  6. Nucleation and Growth of Covalent Organic Frameworks from Solution: The Example of COF-5

    KAUST Repository

    Li, Haoyuan; Chavez, Anton D.; Li, Huifang; Li, Hong; Dichtel, William R.; Bredas, Jean-Luc

    2017-01-01

    The preparation of two-dimensional covalent organic frameworks (2D COFs) with large crystalline domains and controlled morphology is necessary for realizing the full potential of their atomically precise structures and uniform, tailorable porosity

  7. Local Electronic Structure of a Single-Layer Porphyrin-Containing Covalent Organic Framework

    KAUST Repository

    Chen, Chen; Joshi, Trinity; Li, Huifang; Chavez, Anton D.; Pedramrazi, Zahra; Liu, Pei-Nian; Li, Hong; Dichtel, William R.; Bredas, Jean-Luc; Crommie, Michael F.

    2017-01-01

    We have characterized the local electronic structure of a porphyrin-containing single-layer covalent organic framework (COF) exhibiting a square lattice. The COF monolayer was obtained by the deposition of 2,5-dimethoxybenzene-1,4-dicarboxaldehyde

  8. Reversible Communicating Processes

    Directory of Open Access Journals (Sweden)

    Geoffrey Brown

    2016-02-01

    Full Text Available Reversible distributed programs have the ability to abort unproductive computation paths and backtrack, while unwinding communication that occurred in the aborted paths. While it is natural to assume that reversibility implies full state recovery (as with traditional roll-back recovery protocols, an interesting alternative is to separate backtracking from local state recovery. For example, such a model could be used to create complex transactions out of nested compensable transactions where a programmer-supplied compensation defines the work required to "unwind" a transaction. Reversible distributed computing has received considerable theoretical attention, but little reduction to practice; the few published implementations of languages supporting reversibility depend upon a high degree of central control. The objective of this paper is to demonstrate that a practical reversible distributed language can be efficiently implemented in a fully distributed manner. We discuss such a language, supporting CSP-style synchronous communication, embedded in Scala. While this language provided the motivation for the work described in this paper, our focus is upon the distributed implementation. In particular, we demonstrate that a "high-level" semantic model can be implemented using a simple point-to-point protocol.

  9. Covalent Crosslinking of Porous Poly(Ionic Liquid) Membrane via a Triazine Network

    OpenAIRE

    Täuber, Karoline; Dani, Alessandro; Yuan, Jiayin

    2017-01-01

    Porous poly(ionic liquid) membranes that were prepared via electrostatic cross-linking were subsequently covalently cross-linked via formation of a 1,3,5-triazine network. The additional covalent cross-links do not affect the pore size and pore size distribution of the membranes and stabilize them towards salt solutions of high ionic strength, enabling the membranes to work in a broader environmental window.

  10. The Chemistry and Biochemistry of Heme c: Functional Bases for Covalent Attachment

    OpenAIRE

    Bowman, Sarah E. J.; Bren, Kara L.

    2008-01-01

    A discussion of the literature concerning the synthesis, function, and activity of heme c-containing proteins is presented. Comparison of the properties of heme c, which is covalently bound to protein, is made to heme b, which is bound noncovalently. A question of interest is why nature uses biochemically expensive heme c in many proteins when its properties are expected to be similar to heme b. Considering the effects of covalent heme attachment on heme conformation and on the proximal histi...

  11. Tissue Plasminogen Activator Binding to Superparamagnetic Iron Oxide Nanoparticle—Covalent Versus Adsorptive Approach

    Science.gov (United States)

    Friedrich, Ralf P.; Zaloga, Jan; Schreiber, Eveline; Tóth, Ildikó Y.; Tombácz, Etelka; Lyer, Stefan; Alexiou, Christoph

    2016-06-01

    Functionalized superparamagnetic iron oxide nanoparticles are frequently used to develop vehicles for drug delivery, hyperthermia, and photodynamic therapy and as tools used for magnetic separation and purification of proteins or for biomolecular imaging. Depending on the application, there are various possible covalent and non-covalent approaches for the functionalization of particles, each of them shows different advantages and disadvantages for drug release and activity at the desired location.

  12. Contribution of the covalent and the Van der Waals force to the nuclear binding

    International Nuclear Information System (INIS)

    Rosina, M.; Povh, B.

    1994-01-01

    The contribution of the covalent and the Van der Waals force to the nuclear binding is estimated in a simplified model for medium distance of about 1 fm. It is shown how colour effects suppress these two forces as compared to the case of the forces between atoms. The covalent and the Van der Waals force represent a minor though noticeable component of the nuclear force. (orig.)

  13. The covalent effect on the energy levels of d3 ions in tetragonal compounds

    International Nuclear Information System (INIS)

    Li, Dong-Yang; Du, Mao-Lu

    2015-01-01

    For d 3 ions in covalent compounds with tetragonal symmetry, this paper presents a complete energy matrix, in which the different covalence of t 2 and e orbitals is considered not only in the electrostatic repulsions part of energy matrix elements but also in the crystal-field potential part of energy matrix elements. With taking and no taking the crystal field parameter B 00 0 into account, the effect of covalence on the energy levels of d 3 ions system were investigated, respectively. The investigation shows that it is very necessary for considering the different covalence of t 2 and e orbitals in both electrostatic repulsions part and crystal-field potential part when the optical properties of d 3 ions in strong covalent compounds with tetragonal symmetry is investigated. On the other hand, the crystal field parameter B 00 0 has a significant effect on the energy levels, and should be considered in investigations of d 3 ions in strong covalent compounds with tetragonal symmetry. Application to calculating the energy levels for Co 2+ in CdGa 2 Se 4 , the calculated results are in agreement with the experiment data

  14. Non-covalently functionalized carbon nanostructures for synthesizing carbon-based hybrid nanomaterials.

    Science.gov (United States)

    Li, Haiqing; Song, Sing I; Song, Ga Young; Kim, Il

    2014-02-01

    Carbon nanostructures (CNSs) such as carbon nanotubes, graphene sheets, and nanodiamonds provide an important type of substrate for constructing a variety of hybrid nanomaterials. However, their intrinsic chemistry-inert surfaces make it indispensable to pre-functionalize them prior to immobilizing additional components onto their surfaces. Currently developed strategies for functionalizing CNSs include covalent and non-covalent approaches. Conventional covalent treatments often damage the structure integrity of carbon surfaces and adversely affect their physical properties. In contrast, the non-covalent approach offers a non-destructive way to modify CNSs with desired functional surfaces, while reserving their intrinsic properties. Thus far, a number of surface modifiers including aromatic compounds, small-molecular surfactants, amphiphilic polymers, and biomacromolecules have been developed to non-covalently functionalize CNS surfaces. Mediated by these surface modifiers, various functional components such as organic species and inorganic nanoparticles were further decorated onto their surfaces, resulting in versatile carbon-based hybrid nanomaterials with broad applications in chemical engineering and biomedical areas. In this review, the recent advances in the generation of such hybrid nanostructures based on non-covalently functionalized CNSs will be reviewed.

  15. Economic impact of reversion

    International Nuclear Information System (INIS)

    2005-01-01

    Estimations of the Norwegian hydropower production and various reversion models' market value have been made. The value of the Norwegian hydropower production until 01.01.2007 is estimated to about Nok 289 billion after taxes, or about 2,42 Nok/kWh medium production, given an expected future electricity price of around 0,25 Nok/kWh and a discount rate at 6,5 percent in nominal terms after taxes. The estimate is slightly above the level of prices for Norwegian hydropower plants in the last 8-10 years. The value of reversion in private plants which today have a limited licence time is estimated to Nok 5,5 billion. The value of reversion in public-owned Norwegian hydropower plants are about Nok 21 billion with a 60 year licence period from 01.01.2007, and about 12 billion for 75 years (ml)

  16. Site specific modification of the human plasma proteome by methylglyoxal

    International Nuclear Information System (INIS)

    Kimzey, Michael J.; Kinsky, Owen R.; Yassine, Hussein N.; Tsaprailis, George; Stump, Craig S.; Monks, Terrence J.; Lau, Serrine S.

    2015-01-01

    Increasing evidence identifies dicarbonyl stress from reactive glucose metabolites, such as methylglyoxal (MG), as a major pathogenic link between hyperglycemia and complications of diabetes. MG covalently modifies arginine residues, yet the site specificity of this modification has not been thoroughly investigated. Sites of MG adduction in the plasma proteome were identified using LC–MS/MS analysis in vitro following incubation of plasma proteins with MG. Treatment of plasma proteins with MG yielded 14 putative MG hotspots from five plasma proteins (albumin [nine hotspots], serotransferrin, haptoglobin [2 hotspots], hemopexin, and Ig lambda-2 chain C regions). The search results revealed two versions of MG-arginine modification, dihydroxyimidazolidine (R + 72) and hydroimidazolone (R + 54) adducts. One of the sites identified was R257 in human serum albumin, which is a critical residue located in drug binding site I. This site was validated as a target for MG modification by a fluorescent probe displacement assay, which revealed significant drug dissociation at 300 μM MG from a prodan–HSA complex (75 μM). Moreover, twelve human plasma samples (six male, six female, with two type 2 diabetic subjects from both genders) were analyzed using multiple reaction monitoring (MRM) tandem mass spectrometry and revealed the presence of the MG-modified albumin R257 peptide. These data provide insights into the nature of the site-specificity of MG modification of arginine, which may be useful for therapeutic treatments that aim to prevent MG-mediated adverse responses in patients. - Highlights: • Methylglyoxal (MG) selectively modifies arginine sites in human plasma proteome. • Dihydroxyimidazolidine and hydroimidazolone adducts on serum albumin identified • MG modification on albumin R257 associated with loss of drug site I binding capacity • MRM-tandem mass spectrometry enables sensitive detection of albumin MG-R257. • Site-specific MG modification may

  17. Site specific modification of the human plasma proteome by methylglyoxal

    Energy Technology Data Exchange (ETDEWEB)

    Kimzey, Michael J.; Kinsky, Owen R. [Southwest Environmental Health Sciences Center, Department of Pharmacology & Toxicology, College of Pharmacy, The University of Arizona, Tucson, AZ 85721 (United States); Yassine, Hussein N. [Department of Medicine, The University of Arizona, Tucson, AZ 85721 (United States); Tsaprailis, George [Southwest Environmental Health Sciences Center, Department of Pharmacology & Toxicology, College of Pharmacy, The University of Arizona, Tucson, AZ 85721 (United States); Stump, Craig S. [Department of Medicine, The University of Arizona, Tucson, AZ 85721 (United States); Southern Arizona VA Health Care System, Tucson, AZ 85723 (United States); Monks, Terrence J. [Southwest Environmental Health Sciences Center, Department of Pharmacology & Toxicology, College of Pharmacy, The University of Arizona, Tucson, AZ 85721 (United States); Lau, Serrine S., E-mail: lau@pharmacy.arizona.edu [Southwest Environmental Health Sciences Center, Department of Pharmacology & Toxicology, College of Pharmacy, The University of Arizona, Tucson, AZ 85721 (United States)

    2015-12-01

    Increasing evidence identifies dicarbonyl stress from reactive glucose metabolites, such as methylglyoxal (MG), as a major pathogenic link between hyperglycemia and complications of diabetes. MG covalently modifies arginine residues, yet the site specificity of this modification has not been thoroughly investigated. Sites of MG adduction in the plasma proteome were identified using LC–MS/MS analysis in vitro following incubation of plasma proteins with MG. Treatment of plasma proteins with MG yielded 14 putative MG hotspots from five plasma proteins (albumin [nine hotspots], serotransferrin, haptoglobin [2 hotspots], hemopexin, and Ig lambda-2 chain C regions). The search results revealed two versions of MG-arginine modification, dihydroxyimidazolidine (R + 72) and hydroimidazolone (R + 54) adducts. One of the sites identified was R257 in human serum albumin, which is a critical residue located in drug binding site I. This site was validated as a target for MG modification by a fluorescent probe displacement assay, which revealed significant drug dissociation at 300 μM MG from a prodan–HSA complex (75 μM). Moreover, twelve human plasma samples (six male, six female, with two type 2 diabetic subjects from both genders) were analyzed using multiple reaction monitoring (MRM) tandem mass spectrometry and revealed the presence of the MG-modified albumin R257 peptide. These data provide insights into the nature of the site-specificity of MG modification of arginine, which may be useful for therapeutic treatments that aim to prevent MG-mediated adverse responses in patients. - Highlights: • Methylglyoxal (MG) selectively modifies arginine sites in human plasma proteome. • Dihydroxyimidazolidine and hydroimidazolone adducts on serum albumin identified • MG modification on albumin R257 associated with loss of drug site I binding capacity • MRM-tandem mass spectrometry enables sensitive detection of albumin MG-R257. • Site-specific MG modification may

  18. Dynamic Covalent Chemistry of Carbon Dioxide: Opportunities to Address Environmental Issues.

    Science.gov (United States)

    Septavaux, Jean; Germain, Geoffroy; Leclaire, Julien

    2017-07-18

    Extraction and purification of basic chemicals from complex mixtures has been a persistent issue throughout the development of the chemical sciences. The chemical industry and academic research have grown over the centuries by following a deconstruction-reconstruction approach, reminiscent of the metabolism process. Chemists have designed and optimized extraction, purification, and transformation processes of molecules from natural deposits (fossil fuels, biomass, ores), in order to reassemble them into complex adducts. These highly selective and cost-effective techniques arose from developments in physical chemistry but also in supramolecular chemistry, long before the term was even coined. Thanks to the extremely diverse toolbox currently available to the scientific community, artificial molecular systems of increasing complexity can be built and integrated into high-technology products. If humanity has proven through the ages how gifted it can be at this deconstruction-reconstruction game, which has transformed the natural world to a human-shaped one, it has been confronted for more than a century by a new challenge: the deconstruction and reconstruction from a new type of deposit, the waste resulting from the mass production of disposable manufactured goods. In this Account, we will explore the potential contribution of controlled molecular and supramolecular self-assembly phenomena to the challenge of selective and efficient capture of valuable target molecules from mixtures found in postconsumer waste. While it may appear paradoxical to add more molecular ingredients to an already compositionally complex system in order to address a purification issue, we will compare the selectivity, yield, and cost of such an atypical procedure with traditional physical techniques. In the context of carbon dioxide capture or release, we will specifically focus on the coupling between this reversible covalent fixation of the gas by amines and an additional chemical

  19. Reversible deep disposal

    International Nuclear Information System (INIS)

    2009-10-01

    This presentation, given by the national agency of radioactive waste management (ANDRA) at the meeting of October 8, 2009 of the high committee for the nuclear safety transparency and information (HCTISN), describes the concept of deep reversible disposal for high level/long living radioactive wastes, as considered by the ANDRA in the framework of the program law of June 28, 2006 about the sustainable management of radioactive materials and wastes. The document presents the social and political reasons of reversibility, the technical means considered (containers, disposal cavities, monitoring system, test facilities and industrial prototypes), the decisional process (progressive development and blocked off of the facility, public information and debate). (J.S.)

  20. Identification of cysteine-644 as the covalent site of attachment of dexamethasone 21-mesylate to murine glucocorticoid receptors in WEHI-7 cells

    International Nuclear Information System (INIS)

    Smith, L.I.; Bodwell, J.E.; Mendel, D.B.; Ciardelli, T.; North, W.G.; Munck, A.

    1988-01-01

    Dexamethasone 21-mesylate is a highly specific synthetic glucocorticoid derivative that binds covalently to glucocorticoid receptors via sulfhydryl groups. The authors have identified the amino acid that reacts with the dexamethasone 21-mesylate by using enzymatic digestion and microsequencing for radiolabel. Nonactivated glucocorticoid receptors obtained from labeling intact WEHI-7 mouse thymoma cells with [ 3 H]dexamethasone 21-mesylate were immunopurified and analyzed by sodium dodecyl sulfate-polyacrylamide gel electrophoresis. Trypsin digestion followed by reversed-phase high-performance liquid chromatography (reversed-phase HPLC) produced a single [ 3 H]dexamethasone 21-mesylate labeled peptide. Automated Edman degradation of this peptide revealed that the [ 3 H]dexamethasone 21-mesylate was located at position 5 from the amino terminus. Dual-isotope labeling studies with [ 3 H]dexamethasone 21-mesylate and [ 35 S]methionine demonstrated that this peptide contained methionine. Staphylococcus aureus V8 protease digestion of [ 3 H]dexamethasone 21-mesylate labeled steroid-binding subunits generated a different radiolabeled peptide containing label at position 7 from the amino terminus. On the basis of the published amino acid sequence of the murine glucocorticoid receptor, their data clearly identify cysteine-644 as the single residue in the steroid-binding domain that covalently binds dexamethasone 21-mesylate. They have confirmed this finding by demonstrating that a synthetic peptide representing the amino acid sequence 640-650 of the murine glucocorticoid receptor behaves in an identical manner on reversed-phase HPLC as the trypsin-generated peptide from intact cells

  1. A concise methodology for the estimation of elemental concentration effects on mesoscale cohesion of non-ferrous covalent glasses: The case of Se(80−xGe(20−xInx=0,5,10,15

    Directory of Open Access Journals (Sweden)

    Georgios S.E. Antipas

    2015-09-01

    Full Text Available The link between the electronic state and the mesoscale of covalent glasses is not settled. A functional means of addressing the mesoscale is via generalizing glass properties (e.g. such as cohesion on the basis of atomic clusters. Derivation of the most representative such cluster formations is not streamlined, however. Here, numerical pair correlation and ab initio energetic datasets are presented for the case of amorphous Selenium-rich covalent glasses, which were obtained via a new, concise methodology, relating mesoscopic cohesion to local atomic order and to the system׳s electronic structure. The methodology consisted of selecting clusters on the basis of the variation of atomic environment statistics of total coordination, partial coordination by the matrix element and cluster number density along the radial direction of a Reverse Monte Carlo supercell, the latter attained by fitting total scattering data.

  2. Thermosensory reversal effect quantified

    NARCIS (Netherlands)

    Bergmann Tiest, W.M.; Kappers, A.M.L.

    2008-01-01

    At room temperature, some materials feel colder than others due to differences in thermal conductivity, heat capacity and geometry. When the ambient temperature is well above skin temperature, the roles of 'cold' and 'warm' materials are reversed. In this paper, this effect is quantified by

  3. Thermosensory reversal effect quantified

    NARCIS (Netherlands)

    Bergmann Tiest, W.M.; Kappers, A.M.L.

    2008-01-01

    At room temperature, some materials feel colder than others due to differences in thermal conductivity, heat capacity and geometry. When the ambient temperature is well above skin temperature, the roles of ‘cold’ and ‘warm’ materials are reversed. In this paper, this effect is quantified by

  4. Time reversal communication system

    Science.gov (United States)

    Candy, James V.; Meyer, Alan W.

    2008-12-02

    A system of transmitting a signal through a channel medium comprises digitizing the signal, time-reversing the digitized signal, and transmitting the signal through the channel medium. The channel medium may be air, earth, water, tissue, metal, and/or non-metal.

  5. Engineering Encounters: Reverse Engineering

    Science.gov (United States)

    McGowan, Veronica Cassone; Ventura, Marcia; Bell, Philip

    2017-01-01

    This column presents ideas and techniques to enhance your science teaching. This month's issue shares information on how students' everyday experiences can support science learning through engineering design. In this article, the authors outline a reverse-engineering model of instruction and describe one example of how it looked in our fifth-grade…

  6. Sex Reversal in Birds.

    Science.gov (United States)

    Major, Andrew T; Smith, Craig A

    2016-01-01

    Sexual differentiation in birds is controlled genetically as in mammals, although the sex chromosomes are different. Males have a ZZ sex chromosome constitution, while females are ZW. Gene(s) on the sex chromosomes must initiate gonadal sex differentiation during embryonic life, inducing paired testes in ZZ individuals and unilateral ovaries in ZW individuals. The traditional view of avian sexual differentiation aligns with that expounded for other vertebrates; upon sexual differentiation, the gonads secrete sex steroid hormones that masculinise or feminise the rest of the body. However, recent studies on naturally occurring or experimentally induced avian sex reversal suggest a significant role for direct genetic factors, in addition to sex hormones, in regulating sexual differentiation of the soma in birds. This review will provide an overview of sex determination in birds and both naturally and experimentally induced sex reversal, with emphasis on the key role of oestrogen. We then consider how recent studies on sex reversal and gynandromorphic birds (half male:half female) are shaping our understanding of sexual differentiation in avians and in vertebrates more broadly. Current evidence shows that sexual differentiation in birds is a mix of direct genetic and hormonal mechanisms. Perturbation of either of these components may lead to sex reversal. © 2016 S. Karger AG, Basel.

  7. Elastomers with Reversible Nanoporosity

    DEFF Research Database (Denmark)

    Szewczykowski, Piotr Przemyslaw; Andersen, K.; Schulte, Lars

    2009-01-01

    nanostructure and displays liquid-filled cavities. Upon several cycles of swelling and drying the cavities open and close in a reversible fashion. When exposed to a nonsolvent, the material remains collapsed. This discriminating behavior of liquid-material interaction holds potential for the use...

  8. Structure of the red fluorescent protein from a lancelet (Branchiostoma lanceolatum): a novel GYG chromophore covalently bound to a nearby tyrosine

    Energy Technology Data Exchange (ETDEWEB)

    Pletnev, Vladimir Z., E-mail: vzpletnev@gmail.com; Pletneva, Nadya V.; Lukyanov, Konstantin A.; Souslova, Ekaterina A.; Fradkov, Arkady F.; Chudakov, Dmitry M.; Chepurnykh, Tatyana; Yampolsky, Ilia V. [Russian Academy of Sciences, Moscow (Russian Federation); Wlodawer, Alexander [National Cancer Institute, Frederick, MD 21702 (United States); Dauter, Zbigniew [National Cancer Institute, Argonne, IL 60439 (United States); Pletnev, Sergei, E-mail: vzpletnev@gmail.com [National Cancer Institute, Argonne, IL 60439 (United States); SAIC-Frederick, Argonne, IL 60439 (United States); Russian Academy of Sciences, Moscow (Russian Federation)

    2013-09-01

    The crystal structure of the novel red emitting fluorescent protein from lancelet Branchiostoma lanceolatum (Chordata) revealed an unusual five residues cyclic unit comprising Gly58-Tyr59-Gly60 chromophore, the following Phe61 and Tyr62 covalently bound to chromophore Tyr59. A key property of proteins of the green fluorescent protein (GFP) family is their ability to form a chromophore group by post-translational modifications of internal amino acids, e.g. Ser65-Tyr66-Gly67 in GFP from the jellyfish Aequorea victoria (Cnidaria). Numerous structural studies have demonstrated that the green GFP-like chromophore represents the ‘core’ structure, which can be extended in red-shifted proteins owing to modifications of the protein backbone at the first chromophore-forming position. Here, the three-dimensional structures of green laGFP (λ{sub ex}/λ{sub em} = 502/511 nm) and red laRFP (λ{sub ex}/λ{sub em} ≃ 521/592 nm), which are fluorescent proteins (FPs) from the lancelet Branchiostoma lanceolatum (Chordata), were determined together with the structure of a red variant laRFP-ΔS83 (deletion of Ser83) with improved folding. Lancelet FPs are evolutionarily distant and share only ∼20% sequence identity with cnidarian FPs, which have been extensively characterized and widely used as genetically encoded probes. The structure of red-emitting laRFP revealed three exceptional features that have not been observed in wild-type fluorescent proteins from Cnidaria reported to date: (i) an unusual chromophore-forming sequence Gly58-Tyr59-Gly60, (ii) the presence of Gln211 at the position of the conserved catalytic Glu (Glu222 in Aequorea GFP), which proved to be crucial for chromophore formation, and (iii) the absence of modifications typical of known red chromophores and the presence of an extremely unusual covalent bond between the Tyr59 C{sup β} atom and the hydroxyl of the proximal Tyr62. The impact of this covalent bond on the red emission and the large Stokes shift (

  9. Enzymatic modification of starch

    DEFF Research Database (Denmark)

    Jensen, Susanne Langgård

    In the food industry approaches for using bioengineering are investigated as alternatives to conventional chemical and physical starch modification techniques in development of starches with specific properties. Enzyme-assisted post-harvest modification is an interesting approach to this, since...... it is considered a clean and energy saving technology. This thesis aimed to investigate the effect of using reaction conditions, simulating an industrial process, for enzymatic treatment of starch with branching enzyme (BE) from Rhodothermus obamensis. Thus treatements were conducted at 70°C using very high...... substrate concentration (30-40% dry matter (DM)) and high enzyme activity (750-2250 BE units (BEU)/g sample). Starches from various botanical sources, representing a broad range of properties, were used as substrates. The effects of the used conditions on the BE-reaction were evaluated by characterization...

  10. Geometrically Consistent Mesh Modification

    KAUST Repository

    Bonito, A.

    2010-01-01

    A new paradigm of adaptivity is to execute refinement, coarsening, and smoothing of meshes on manifolds with incomplete information about their geometry and yet preserve position and curvature accuracy. We refer to this collectively as geometrically consistent (GC) mesh modification. We discuss the concept of discrete GC, show the failure of naive approaches, and propose and analyze a simple algorithm that is GC and accuracy preserving. © 2010 Society for Industrial and Applied Mathematics.

  11. Radiation modification of materials

    International Nuclear Information System (INIS)

    Pikaev, A.K.

    1987-01-01

    Industrial and radiation chemical processes of material modification based on cross-linking of polymers as a result of radiation are considered. Among them are production of cables and rods with irradiated modified insulation, production of hardened and thermo-shrinkaging polymer products (films, tubes, fashioned products), production of radiation cross-linked polyethylene foam, technology of radiation vulcanization of elastomers. Attention is paid to radiation plants on the basis of γ-sources and electron acceleratos as well as to radiation conditions

  12. Particle Distribution Modification by Low Amplitude Modes

    International Nuclear Information System (INIS)

    White, R.B.; Gorelenkov, N.; Heidbrink, W.W.; Van Zeeland, M.A.

    2009-01-01

    Modification of a high energy particle distribution by a spectrum of low amplitude modes is investigated using a guiding center code. Only through resonance are modes effective in modifying the distribution. Diagnostics are used to illustrate the mode-particle interaction and to find which effects are relevant in producing significant resonance, including kinetic Poincare plots and plots showing those orbits with time averaged mode-particle energy transfer. Effects of pitch angle scattering and drag are studied, as well as plasma rotation and time dependence of the equilibrium and mode frequencies. A specific example of changes observed in a DIII-D deuterium beam distribution in the presence of low amplitude experimentally validated Toroidal Alfven (TAE) eigenmodes and Reversed Shear Alfven (RSAE) eigenmodes is examined in detail. Comparison with experimental data shows that multiple low amplitude modes can account for significant modification of high energy beam particle distributions. It is found that there is a stochastic threshold for beam profile modification, and that the experimental amplitudes are only slightly above this threshold.

  13. Behavior Modification in the Classroom

    Science.gov (United States)

    Whitman, Mryon; Whitman, Joan

    1971-01-01

    This article presents the theoretical rationale for behavior modification, principally through its comparison with traditional psychotherapies, and suggests some behavior modification techniques for the classroom management of maladaptive behavior. (Author)

  14. Photochemical properties and sensor applications of modified yellow fluorescent protein (YFP) covalently attached to the surfaces of etched optical fibers (EOFs).

    Science.gov (United States)

    Veselov, Alexey A; Abraham, Bobin George; Lemmetyinen, Helge; Karp, Matti T; Tkachenko, Nikolai V

    2012-01-01

    Fluorescent proteins have the inherent ability to act as sensing components which function both in vitro and inside living cells. We describe here a novel study on a covalent site-specific bonding of fluorescent proteins to form self-assembled monolayers (SAMs) on the surface of etched optical fibers (EOFs). Deposition of fluorescent proteins on EOFs gives the opportunity to increase the interaction of guided light with deposited molecules relative to plane glass surfaces. The EOF modification is carried out by surface activation using 3-aminopropylthrimethoxysilane (APTMS) and bifunctional crosslinker sulfosuccinimidyl 4-[N-maleimidomethyl]cyclohexane-1-carboxylate (sulfo-SMCC) which exposes sulfhydryl-reactive maleimide groups followed by covalent site-specific coupling of modified yellow fluorescent protein (YFP). Steady-state and fluorescence lifetime measurements confirm the formation of SAM. The sensor applications of YPF SAMs on EOF are demonstrated by the gradual increase of emission intensity upon addition of Ca(2+) ions in the concentration range from a few tens of micromolars up to a few tens of millimolars. The studies on the effect of pH, divalent cations, denaturing agents, and proteases reveal the stability of YFP on EOFs at normal physiological conditions. However, treatments with 0.5% SDS at pH 8.5 and protease trypsin are found to denaturate or cleave the YFP from fiber surfaces.

  15. A study on poly (N-vinyl-2-pyrrolidone covalently bonded NiTi surface for inhibiting protein adsorption

    Directory of Open Access Journals (Sweden)

    Hongyan Yu

    2016-12-01

    Full Text Available Near equiatomic NiTi alloys have been extensively applied as biomaterials owing to its unique shape memory effect, superelasticity and biocompatibility. It has been demonstrated that surfaces capable of preventing plasma protein adsorption could reduce the reactivity of biomaterials with human blood. This motivated a lot of researches on the surface modification of NiTi alloy. In the present work, following heat and alkaline treatment and silanization by trichlorovinylsilane (TCVS, coating of poly (N-vinyl-2-pyrrolidone (PVP was produced on the NiTi alloy by gamma ray induced chemical bonding. The structures and properties of modified NiTi were characterized and in vitro biocompatibility of plasma protein adsorption was investigated. The results indicated that heat treatment at 823 K for 1 h could result in the formation of a protective TiO2 layer with “Ni-free” zone on NiTi surface. It was found that PVP was covalently bonded on NiTi surface to create a hydrophilic layer for inhibiting protein adsorption on the surface. The present work offers a green approach to introduce a bioorganic surface on metal and other polymeric or inorganic substrates by gamma irradiation.

  16. The Effect of Covalently-Attached ATRP-Synthesized Polymers on Membrane Stability and Cytoprotection in Human Erythrocytes.

    Science.gov (United States)

    Clafshenkel, William P; Murata, Hironobu; Andersen, Jill; Creeger, Yehuda; Koepsel, Richard R; Russell, Alan J

    2016-01-01

    Erythrocytes have been described as advantageous drug delivery vehicles. In order to ensure an adequate circulation half-life, erythrocytes may benefit from protective enhancements that maintain membrane integrity and neutralize oxidative damage of membrane proteins that otherwise facilitate their premature clearance from circulation. Surface modification of erythrocytes using rationally designed polymers, synthesized via atom-transfer radical polymerization (ATRP), may further expand the field of membrane-engineered red blood cells. This study describes the fate of ATRP-synthesized polymers that were covalently attached to human erythrocytes as well as the effect of membrane engineering on cell stability under physiological and oxidative conditions in vitro. The biocompatible, membrane-reactive polymers were homogenously retained on the periphery of modified erythrocytes for at least 24 hours. Membrane engineering stabilized the erythrocyte membrane and effectively neutralized oxidative species, even in the absence of free-radical scavenger-containing polymers. The targeted functionalization of Band 3 protein by NHS-pDMAA-Cy3 polymers stabilized its monomeric form preventing aggregation in the presence of the crosslinking reagent, bis(sulfosuccinimidyl)suberate (BS3). A free radical scavenging polymer, NHS-pDMAA-TEMPO˙, provided additional protection of surface modified erythrocytes in an in vitro model of oxidative stress. Preserving or augmenting cytoprotective mechanisms that extend circulation half-life is an important consideration for the use of red blood cells for drug delivery in various pathologies, as they are likely to encounter areas of imbalanced oxidative stress as they circuit the vascular system.

  17. The Effect of Covalently-Attached ATRP-Synthesized Polymers on Membrane Stability and Cytoprotection in Human Erythrocytes.

    Directory of Open Access Journals (Sweden)

    William P Clafshenkel

    Full Text Available Erythrocytes have been described as advantageous drug delivery vehicles. In order to ensure an adequate circulation half-life, erythrocytes may benefit from protective enhancements that maintain membrane integrity and neutralize oxidative damage of membrane proteins that otherwise facilitate their premature clearance from circulation. Surface modification of erythrocytes using rationally designed polymers, synthesized via atom-transfer radical polymerization (ATRP, may further expand the field of membrane-engineered red blood cells. This study describes the fate of ATRP-synthesized polymers that were covalently attached to human erythrocytes as well as the effect of membrane engineering on cell stability under physiological and oxidative conditions in vitro. The biocompatible, membrane-reactive polymers were homogenously retained on the periphery of modified erythrocytes for at least 24 hours. Membrane engineering stabilized the erythrocyte membrane and effectively neutralized oxidative species, even in the absence of free-radical scavenger-containing polymers. The targeted functionalization of Band 3 protein by NHS-pDMAA-Cy3 polymers stabilized its monomeric form preventing aggregation in the presence of the crosslinking reagent, bis(sulfosuccinimidylsuberate (BS3. A free radical scavenging polymer, NHS-pDMAA-TEMPO˙, provided additional protection of surface modified erythrocytes in an in vitro model of oxidative stress. Preserving or augmenting cytoprotective mechanisms that extend circulation half-life is an important consideration for the use of red blood cells for drug delivery in various pathologies, as they are likely to encounter areas of imbalanced oxidative stress as they circuit the vascular system.

  18. Laccase aided modification of nanofibrillated cellulose with dodecyl gallate

    Directory of Open Access Journals (Sweden)

    Päivi Saastamoinen

    2012-11-01

    Full Text Available Nanofibrillated cellulose, NFC, is an interesting wood fibre-based material that could be utilized in coatings, foams, composites, packages, dispersions, and emulsions, due to its high tensile strength and barrier properties, light weight, and stabilizing features. To improve applicability and properties of NFC, modification of its surface properties is often needed. In this study, the applicability of laccase-aided surface modification with hydrophobic dodecyl gallate (DOGA on unbleached NFC was investigated. Also, laccase-catalyzed polymerization of DOGA and other phenolic compounds with lignin moieties was investigated by matrix-assisted laser desorption/ionization time-of-flight mass spectroscopy (MALDI-TOF MS. NFC modified with T. hirsuta-based laccase and DOGA showed decreased hydrophilicity, as compared with the native NFC, when coated on a paper surface. When dried as free-standing films, the surface properties of chemo-enzymatically modified NFC resembled those of the native NFC. The effect of modification was thus greatly influenced by different surface formation in differently prepared samples. Also, changing of the dispersion properties of DOGA by enzymatic polymerization affected the surface properties of the dried NFC samples. Covalent bonding between DOGA and NFC was not the main factor affecting the surface properties of the NFC in free-standing films or coatings.

  19. The significant role of covalency in determining the ground state of cobalt phthalocyanines molecule

    Directory of Open Access Journals (Sweden)

    Jing Zhou

    2016-03-01

    Full Text Available To shed some light on the metal 3d ground state configuration of cobalt phthalocyanines system, so far in debate, we present an investigation by X-ray absorption spectroscopy (XAS at Co L2,3 edge and theoretical calculation. The density functional theory calculations reveal highly anisotropic covalent bond between central cobalt ion and nitrogen ligands, with the dominant σ donor accompanied by weak π-back acceptor interaction. Our combined experimental and theoretical study on the Co-L2,3 XAS spectra demonstrate a robust ground state of 2A1g symmetry that is built from 73% 3d7 character and 27% 3 d 8 L ¯ ( L ¯ denotes a ligand hole components, as the first excited-state with 2Eg symmetry lies about 158 meV higher in energy. The effect of anisotropic and isotropic covalency on the ground state was also calculated and the results indicate that the ground state with 2A1g symmetry is robust in a large range of anisotropic covalent strength while a transition of ground state from 2A1g to 2Eg configuration when isotropic covalent strength increases to a certain extent. Here, we address a significant anisotropic covalent effect of short Co(II-N bond on the ground state and suggest that it should be taken into account in determining the ground state of analogous cobalt complexes.

  20. Reversed field pinch diagnostics

    International Nuclear Information System (INIS)

    Weber, P.G.

    1986-01-01

    The Reversed Field Pinch (RFP) is a toroidal, axisymmetric magnetic confinement configuration characterized by a magnetic field configuration in which the toroidal magnetic field is of similar strength to the poloidal field, and is reversed at the edge compared to the center. The RFP routinely operates at high beta, and is a strong candidate for a compact fusion device. Relevant attributes of the configuration will be presented, together with an overview of present and planned experiments and their diagnostics. RFP diagnostics are in many ways similar to those of other magnetic confinement devices (such as tokamaks); these lectures will point out pertinent differences, and will present some diagnostics which provide special insights into unique attributes of the RFP

  1. Posterior Reversible Encephalopathy (PRES)

    International Nuclear Information System (INIS)

    Moron E, Fanny E; Diaz Marchan, Pedro

    2005-01-01

    The Posterior Reversible Encephalopathy Syndrome (PRES) is a clinical Syndrome composed of cephalea, alteration in vision and convulsions, usually observed in patients with sudden elevation of arterial pressure. The imagenologic evidence shows reversible vasogenic brain edema without stroke. Its location is predominantly posterior; it affects the cortex and the subcortical white matter of the occipital, parietal and temporal lobes. The treatment with antihypertensive drugs and the removing of immunosupressor medication are generally associated with complete neurological recovery; this is reflected also in the images which return to their basal condition. The untreated hypertension, on the other side, can result in a progressive defect of the autoregulation system of the central nervous system with cerebral hemorrhage, irreversible brain stroke, coma and death

  2. Biomaterials modification by ion beam

    International Nuclear Information System (INIS)

    Zhang Tonghe; Yi Zhongzhen; Zhang Xu; Wu Yuguang

    2001-01-01

    Ion beam technology is one of best ways for the modification of biomaterials. The results of ion beam modification of biomaterials are given. The method and results of improved biocompatibility are indicated by ion beam technology. The future development of ion beam modification of biomaterials is discussed

  3. Surface Modifications of Support Partitions for Stabilizing Biomimetic Membrane Arrays

    DEFF Research Database (Denmark)

    Perry, Mark; Hansen, Jesper Schmidt; Jensen, Karin Bagger Stibius

    2011-01-01

    with a high signal-to-noise (s/n) ratio. We demonstratesd this by reconstituting gA and α-hemolysin (α-HL) into BLM arrays. The improvement in membrane array lifetime and s/n ratio demonstrates that surface plasma polymerization of the supporting partition can be used to increase the stability of biomimetic......Black lipid membrane (BLM) formation across apertures in an ethylene tetra-fluoroethylene (ETFE) partition separating two aqueous compartments is an established technique for the creation of biomimetic membranes. Recently multi-aperture BLM arrays have attracted interest and in order to increase...... BLM array stability we studied the effect of covalently modifying the partition substrate using surface plasma polymerization with hydrophobic n-hexene, 1-decene and hexamethyldisiloxane (HMDSO) as modification groups. Average lifetimes across singlesided HMDSO modified partitions or using 1-decene...

  4. Simple surface modification of poly(dimethylsiloxane) for DNA hybridization

    Science.gov (United States)

    Zhou, Jinwen; Voelcker, Nicolas H.; Ellis, Amanda V.

    2010-01-01

    Here, we present a simple chemical modification of poly(dimethylsiloxane) (PDMS) by curing a mixture of 2 wt% undecylenic acid (UDA) in PDMS prepolymer on a gold-coated glass slide. This gold slide had been previously pretreated with a self-assembled hydrophilic monolayer of 3-mercaptopropionic acid (MPA). During curing of the UDA∕PDMS prepolymer, the hydrophilic UDA carboxyl moieties diffuses toward the hydrophilic MPA carboxyl moieties on the gold surface. This diffusion of the UDA within the PDMS prepolymer to the surface is a direct result of surface energy minimization. Once completely cured, the PDMS is peeled off the gold substrate, thereby exposing the interfacial carboxyl groups. These groups are then available for subsequent attachment of 5′-amino terminated DNA oligonucleotides via amide linkages. Our results show that the covalently tethered oligonucleotides can successfully capture fluorescein-labeled complementary oligonucleotides via hybridization, which are visualized using fluorescence microscopy. PMID:21264061

  5. Thermophysical properties of solid lithium hydride and its isotopic modifications

    International Nuclear Information System (INIS)

    Mel'nikova, T.N.

    1981-01-01

    The theory of the anharmonic lattice is used to calculate the thermophysical properties (thermal expansivity, lattice constant, compressibility, and elastic moduli) of all the isotopic modifications of solid lithium hydride sup(6,7)Li(H,D,T) at temperatures up to the melting point. A general analysis of isotopic effects is carried out; in particular the reverse isotopic effect in the lattice constant is explained and the isotopic effect in melting is discussed. The results of the calculations agree with available experimental data and can be used for those isotopic modifications of lithium hydride for which there exist no experimental results. (author)

  6. Reversible infantile mitochondrial diseases.

    Science.gov (United States)

    Boczonadi, Veronika; Bansagi, Boglarka; Horvath, Rita

    2015-05-01

    Mitochondrial diseases are usually severe and progressive conditions; however, there are rare forms that show remarkable spontaneous recoveries. Two homoplasmic mitochondrial tRNA mutations (m.14674T>C/G in mt-tRNA(Glu)) have been reported to cause severe infantile mitochondrial myopathy in the first months of life. If these patients survive the first year of life by extensive life-sustaining measures they usually recover and develop normally. Another mitochondrial disease due to deficiency of the 5-methylaminomethyl-2-thiouridylate methyltransferase (TRMU) causes severe liver failure in infancy, but similar to the reversible mitochondrial myopathy, within the first year of life these infants may also recover completely. Partial recovery has been noted in some other rare forms of mitochondrial disease due to deficiency of mitochondrial tRNA synthetases and mitochondrial tRNA modifying enzymes. Here we summarize the clinical presentation of these unique reversible mitochondrial diseases and discuss potential molecular mechanisms behind the reversibility. Understanding these mechanisms may provide the key to treatments of potential broader relevance in mitochondrial disease, where for the majority of the patients no effective treatment is currently available.

  7. Positioning paper on reversibility

    International Nuclear Information System (INIS)

    2016-01-01

    After having recalled the legal framework adopted in 2006 for the deep geological storage of radioactive wastes, and briefly introduced the concept of reversibility, this publication presents the principle of geological storage, presents high and medium level and long life wastes, highlights the ethical necessity to deal with these radioactive wastes, outlines that geological storage is the generally admitted and adopted solution at the international level, and presents additional means implemented for radioactive waste management. It presents the Cigeo project as the technical answer to the issue of radioactive waste storage, describes the Cigeo development process, its current status and its development planning, and justifies the choice of this technical solution, notably from an ethical point of view. It addresses the issue of reversibility and proposes an overview of the various tools and means which aim at guaranteeing this reversibility. Appendices propose figures illustrating the Cigeo project and its development process, and a rather detailed Power Point presentation of the project by the ANDRA (history, object, planning, installations, and so on)

  8. Alfven eigenmodes in shear reversed plasmas

    International Nuclear Information System (INIS)

    Breizman, B.N.; Berk, H.L.; Pekker, M.S.; Sharapov, S.E.; Hawkes, N.C.; Borba, D.N.; Pinches, S.D.

    2003-01-01

    Experiments on JT-60U and JET have shown that plasma configurations with shear reversal are prone to the excitation of unusual Alfven Eigenmodes by energetic particles. These modes emerge outside the TAE frequency gap, where one might expect them to be strongly damped. The modes often appear in bunches and they exhibit a quasi-periodic pattern of predominantly upward frequency sweeping (Alfven Cascades) as the safety factor q changes in time. This work presents a theory that explains the key features of the observed unusual modes including their connection to TAE's as well as the modifications of TAE's themselves near the shear reversal point. The developed theory has been incorporated into a reduced numerical model and verified with full geometry codes. JET experimental data on Alfven spectroscopy have been simulated to infer the mode numbers and the evolution of q min in the discharge. This analysis confirms the values of q that characterize the internal transport barrier triggering in reversed shear plasmas. (author)

  9. Covalent Chemical 5'-Functionalization of RNA with Diazo Reagents.

    Science.gov (United States)

    Gampe, Christian M; Hollis-Symynkywicz, Micah; Zécri, Frédéric

    2016-08-22

    Functionalization of RNA at the 5'-terminus is important for analytical and therapeutic purposes. Currently, these RNAs are synthesized de novo starting with a chemically functionalized 5'-nucleotide, which is incorporated into RNA using chemical synthesis or biochemical techniques. Methods for direct chemical modification of native RNA would provide an attractive alternative but are currently underexplored. Herein, we report that diazo compounds can be used to selectively alkylate the 5'-phosphate of ribo(oligo)nucleotides to give RNA labelled through a native phosphate ester bond. We applied this method to functionalize oligonucleotides with biotin and an orthosteric inhibitor of the eukaryotic initiation factor 4E (eIF4E), an enzyme involved in mRNA recognition. The modified RNA binds to eIF4E, demonstrating the utility of this labelling technique to modulate biological activity of RNA. This method complements existing techniques and may be used to chemically introduce a broad range of functional handles at the 5'-end of RNA. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  10. Genetic modification and genetic determinism

    Science.gov (United States)

    Resnik, David B; Vorhaus, Daniel B

    2006-01-01

    In this article we examine four objections to the genetic modification of human beings: the freedom argument, the giftedness argument, the authenticity argument, and the uniqueness argument. We then demonstrate that each of these arguments against genetic modification assumes a strong version of genetic determinism. Since these strong deterministic assumptions are false, the arguments against genetic modification, which assume and depend upon these assumptions, are therefore unsound. Serious discussion of the morality of genetic modification, and the development of sound science policy, should be driven by arguments that address the actual consequences of genetic modification for individuals and society, not by ones propped up by false or misleading biological assumptions. PMID:16800884

  11. Predicting the impact of feed spacer modification on biofouling by hydraulic characterization and biofouling studies in membrane fouling simulators

    KAUST Repository

    Siddiqui, Amber; Lehmann, S.; Bucs, Szilard; Fresquet, M.; Fel, L.; Prest, E.I.E.C.; Ogier, J.; Schellenberg, C.; van Loosdrecht, M.C.M.; Kruithof, J.C.; Vrouwenvelder, Johannes S.

    2016-01-01

    Feed spacers are an essential part of spiral-wound reverse osmosis (RO) and nanofiltration (NF) membrane modules. Geometric modification of feed spacers is a potential option to reduce the impact of biofouling on the performance of membrane systems

  12. Data in support of covalent attachment of tyrosinase onto cyanuric chloride crosslinked magnetic nanoparticles

    Directory of Open Access Journals (Sweden)

    Kourosh Abdollahi

    2016-12-01

    Full Text Available Preparation and characterization of cross linked amine-functionalized magnetic nanoparticles as an appropriate support for covalent immobilization on tyrosinase was presented in the study "Covalent immobilization of tyrosinase onto cyanuric chloride crosslinked amine-functionalized superparamagnetic nanoparticles: synthesis and characterization of the recyclable nanobiocatalyst" (Abdollahi et al., 2016 [1]. Herein, complementary data regarding X-ray powder diffraction (XRD to characterize the synthesized magnetic nanoparticles, and transmission electron microscopy (TEM to determine the size and morphology of tyrosinase immobilized magnetic nanoparticles (tyrosinase-MNPs were reported. The purification results of the extracted tyrosinase from mushroom Agaricus bisporus were provided in a purification table. The covalent immobilization of tyrosinase onto cyanuric chloride functionalized magnetic nanoparticles was proved by performing thermo-gravimetric and energy-dispersive X-ray spectroscopy analyses. The operational stability of immobilized tyrosinase was investigated by incubating tyrosinase-MNPs at different pH and temperatures.

  13. Unanticipated C=C bonds in covalent monolayers on silicon revealed by NEXAFS.

    Science.gov (United States)

    Lee, Michael V; Lee, Jonathan R I; Brehmer, Daniel E; Linford, Matthew R; Willey, Trevor M

    2010-02-02

    Interfaces are crucial to material properties. In the case of covalent organic monolayers on silicon, molecular structure at the interface controls the self-assembly of the monolayers, which in turn influences the optical properties and electrical transport. These properties intrinsically affect their application in biology, tribology, optics, and electronics. We use near-edge X-ray absorption fine structure spectroscopy to show that the most basic covalent monolayers formed from 1-alkenes on silicon retain a double bond in one-fifth to two-fifths of the resultant molecules. Unsaturation in the predominantly saturated monolayers will perturb the regular order and affect the dependent properties. The presence of unsaturation in monolayers produced by two different methods also prompts the re-evaluation of other radical-based mechanisms for forming covalent monolayers on silicon.

  14. Applications of covalent organic frameworks (COFs): From gas storage and separation to drug delivery

    Institute of Scientific and Technical Information of China (English)

    Ming-Xue Wu; Ying-Wei Yang

    2017-01-01

    Covalent organic frameworks (COFs) are an emerging class of porous covalent organic structures whose backbones were composed of light elements (B,C,N,O,Si) and linked by robust covalent bonds to endow such material with desirable properties,i.e.,inherent porosity,well-defined pore aperture,ordered channel structure,large surface area,high stability,and multi-dimension.As expected,the abovementioned properties of COFs broaden the applications of this class of materials in various fields such as gas storage and separation,catalysis,optoelectronics,sensing,small molecules adsorption,and drug delivery.In this review,we outlined the synthesis of COFs and highlighted their applications ranging from the initial gas storage and separation to drug delivery.

  15. On-surface synthesis of covalent coordination polymers on micrometer scale

    Institute of Scientific and Technical Information of China (English)

    Mathieu Koudia; Elena Nardi; Olivier Siri; Mathieu Abel

    2017-01-01

    On-surface synthesis under ultrahigh vacuum provides a promising strategy to control matter at the atomic level,with important implications for the design of new two-dimensional materials having remarkable electronic,magnetic,or catalytic properties.This strategy must address the problem of limited extension of the domains due to the irreversible nature of covalent bonds,which prevents the ripening of defects.We show here that extended materials can be produced by a controlled co-deposition process.In particular,co-deposition of quinoid zwitterion molecules with iron atoms on a Ag(111) surface held at 570 K allows the formation of micrometer-sized domains based on covalent coordination bonds.This work opens up the construction of micrometer-scale single-layer covalent coordination materials under vacuum conditions.

  16. Novel covalently linked insulin dimer engineered to investigate the function of insulin dimerization

    DEFF Research Database (Denmark)

    Vinther, Tine N.; Norrman, Mathias; Strauss, Holger M.

    2012-01-01

    An ingenious system evolved to facilitate insulin binding to the insulin receptor as a monomer and at the same time ensure sufficient stability of insulin during storage. Insulin dimer is the cornerstone of this system. Insulin dimer is relatively weak, which ensures dissociation into monomers...... in the circulation, and it is stabilized by hexamer formation in the presence of zinc ions during storage in the pancreatic ß-cell. Due to the transient nature of insulin dimer, direct investigation of this important form is inherently difficult. To address the relationship between insulin oligomerization...... and insulin stability and function, we engineered a covalently linked insulin dimer in which two monomers were linked by a disulfide bond. The structure of this covalent dimer was identical to the self-association dimer of human insulin. Importantly, this covalent dimer was capable of further oligomerization...

  17. Status of time reversal invariance

    International Nuclear Information System (INIS)

    Henley, E.M.

    1989-01-01

    Time Reversal Invariance is introduced, and theories for its violation are reviewed. The present experimental and theoretical status of Time Reversal Invariance and tests thereof will be presented. Possible future tests will be discussed. 30 refs., 2 figs., 1 tab

  18. Introduction to time reversal theory

    International Nuclear Information System (INIS)

    Henley, E.M.

    1987-01-01

    Theory and reaction mechanisms relevant to time reversal invariance are reviewed. Consequences of time reversal invariance are presented under the headings of CP tests, electromagnetic moments, weak emissions or absorptions, and scattering reactions. 8 refs., 4 figs

  19. The Causes of Preference Reversal.

    OpenAIRE

    Tversky, Amos; Slovic, Paul; Kahneman, Daniel

    1990-01-01

    Observed preference reversal cannot be adequately explained by violations of independence, the reduction axiom, or transitivity. The primary cause of preference reversal is the failure of procedure invariance, especially the overpricing of low-probability, high-payoff bets. This result violates regret theory and generalized (nonindependent) utility models. Preference reversal and a new reversal involving time preferences are explained by scale compatibility, which implies that payoffs are wei...

  20. Geomagnetic Field During a Reversal

    Science.gov (United States)

    Heirtzler, J. R.

    2003-01-01

    It has frequently been suggested that only the geomagnetic dipole, rather than higher order poles, reverse during a geomagnetic field reversal. Under this assumption the geomagnetic field strength has been calculated for the surface of the Earth for various steps of the reversal process. Even without an eminent a reversal of the field, extrapolation of the present secular change (although problematic) shows that the field strength may become zero in some geographic areas within a few hundred years.

  1. A Study on Reverse Logistics

    OpenAIRE

    Reddy, Dhananjaya

    2011-01-01

    In the competitive world of manufacturing, companies are often searching for new ways to improve their process, customer satisfaction and stay ahead in the game with their competitors. Reverse logistics has been considered a strategy to bring these things to life for the past decade or so. This thesis work tries to shed some light on the basics of reverse logistics and how reverse logistics can be used as a management strategy. This paper points out the fundamentals of reverse logistics and l...

  2. Molecular Simulation Studies of Covalently and Ionically Grafted Nanoparticles

    Science.gov (United States)

    Hong, Bingbing

    Solvent-free covalently- or ionically-grafted nanoparticles (CGNs and IGNs) are a new class of organic-inorganic hybrid composite materials exhibiting fluid-like behaviors around room temperature. With similar structures to prior systems, e.g. nanocomposites, neutral or charged colloids, ionic liquids, etc, CGNs and IGNs inherit the functionality of inorganic nanopariticles, the facile processibility of polymers, as well as conductivity and nonvolatility from their constituent materials. In spite of the extensive prior experimental research having covered synthesis and measurements of thermal and dynamic properties, little progress in understanding of these new materials at the molecular level has been achieved, because of the lack of simulation work in this new area. Atomistic and coarse-grained molecular dynamics simulations have been performed in this thesis to investigate the thermodynamics, structure, and dynamics of these systems and to seek predictive methods predictable for their properties. Starting from poly(ethylene oxide) oligomers (PEO) melts, we established atomistic models based on united-atom representations of methylene. The Green-Kubo and Einstein-Helfand formulas were used to calculate the transport properties. The simulations generate densities, viscosities, diffusivities, in good agreement with experimental data. The chain-length dependence of the transport properties suggests that neither Rouse nor reptation models are applicable in the short-chain regime investigated. Coupled with thermodynamic integration methods, the models give good predictions of pressure-composition-density relations for CO 2 + PEO oligomers. Water effects on the Henry's constant of CO 2 in PEO have also been investigated. The dependence of the calculated Henry's constants on the weight percentage of water falls on a temperature-dependent master curve, irrespective of PEO chain length. CGNs are modeled by the inclusion of solid-sphere nanoparticles into the atomistic

  3. Combination of computational methods, adsorption isotherms and selectivity tests for the conception of a mixed non-covalent-semi-covalent molecularly imprinted polymer of vanillin.

    Science.gov (United States)

    Puzio, Kinga; Delépée, Raphaël; Vidal, Richard; Agrofoglio, Luigi A

    2013-08-06

    A novel molecularly imprinted polymer (MIP) for vanillin was prepared by photo initiated polymerization in dichloromethane using a mixed semi-covalent and non-covalent imprinting strategy. Taking polymerisable syringaldehyde as "dummy" template, acrylamide was chosen as functional monomer on B3LYP/6-31+G(d,p) density functional theory computational method basis with counterpoise. The binding parameters for the recognition of vanillin on imprinted polymers were studied with three different isotherm models (Langmuir, bi-Langmuir and Langmuir-Freundlich) and compared. The results indicate an heterogeneity of binding sites. It was found and proved by DFT calculations that the specific binding of vanillin in the cavities is due to non-covalent interactions of the template with the hydroxyphenyl- and the amide-moieties. The binding geometry of vanillin in the MIP cavity was also modelled. The obtained MIP is highly specific for vanillin (with an imprinting factor of 7.4) and was successfully applied to the extraction of vanillin from vanilla pods, red wine spike with vanillin, natural and artificial vanilla sugar with a recovery of 80%. Copyright © 2013 Elsevier B.V. All rights reserved.

  4. Geomagnetic Reversals during the Phanerozoic.

    Science.gov (United States)

    McElhinny, M W

    1971-04-09

    An antalysis of worldwide paleomagnetic measurements suggests a periodicity of 350 x 10(6) years in the polarity of the geomagnetic field. During the Mesozoic it is predominantly normal, whereas during the Upper Paleozoic it is predominantly reversed. Although geomagnetic reversals occur at different rates throughout the Phanerozoic, there appeaars to be no clear correlation between biological evolutionary rates and reversal frequency.

  5. Preparation and fluorescent recognition properties for fluoride of a nanostructured covalently bonded europium hybrid material

    Institute of Scientific and Technical Information of China (English)

    余旭东; 李景印; 李亚娟; 耿丽君; 甄小丽; 于涛

    2015-01-01

    A novel covalently bonded Eu3+-based silica hybrid material was designed and its spectrophotometric anion sensing prop-erty was studied. The fluorescent receptor (europium complex) was covalently grafted to the silica matrix via a sol-gel approach. FTIR, UV-vis spectra, scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray diffraction (XRD) and photoluminescent spectra were characterized, and the results revealed that the hybrid material with nanosphere structure displayed excellent photophysical property. In addition, the selective anion sensing property of the hybrid material was studied by UV-vis and fluorescence spectra. The results showed that the hybrid material exhibited a smart response with fluoride anions.

  6. Covalent electron transfer chemistry of graphene with diazonium salts.

    Science.gov (United States)

    Paulus, Geraldine L C; Wang, Qing Hua; Strano, Michael S

    2013-01-15

    Graphene is an atomically thin, two-dimensional allotrope of carbon with exceptionally high carrier mobilities, thermal conductivity, and mechanical strength. From a chemist's perspective, graphene can be regarded as a large polycyclic aromatic molecule and as a surface without a bulk contribution. Consequently, chemistries typically performed on organic molecules and surfaces have been used as starting points for the chemical functionalization of graphene. The motivations for chemical modification of graphene include changing its doping level, opening an electronic band gap, charge storage, chemical and biological sensing, making new composite materials, and the scale-up of solution-processable graphene. In this Account, we focus on graphene functionalization via electron transfer chemistries, in particular via reactions with aryl diazonium salts. Because electron transfer chemistries depend on the Fermi energy of graphene and the density of states of the reagents, the resulting reaction rate depends on the number of graphene layers, edge states, defects, atomic structure, and the electrostatic environment. We limit our Account to focus on pristine graphene over graphene oxide, because free electrons in the latter are already bound to oxygen-containing functionalities and the resulting chemistries are dominated by localized reactivity and defects. We describe the reaction mechanism of diazonium functionalization of graphene and show that the reaction conditions determine the relative degrees of chemisorption and physisorption, which allows for controlled modulation of the electronic properties of graphene. Finally we discuss different applications for graphene modified by this chemistry, including as an additive in polymer matrices, as biosensors when coupled with cells and biomolecules, and as catalysts when combined with nanoparticles.

  7. Nano-mechanics of Tunable Adhesion using Non Covalent Forces

    Energy Technology Data Exchange (ETDEWEB)

    Kenneth Liechti

    2012-09-08

    The objective of this program was to examine, via experiment and atomistic and continuum analysis, coordinated noncovalent bonding over a range of length scales with a view to obtaining modulated, patterned and reversible bonding at the molecular level. The first step in this project was to develop processes for depositing self-assembled monolayers (SAMs) bearing carboxylic acid and amine moieties on Si (111) surfaces and probe tips of an interfacial force microscope (IFM). This allowed the adhesive portion of the interactions between functionalized surfaces to be fully captured in the force-displacement response (force profiles) that are measured by the IFM. The interactionswere extracted in the form of traction-separation laws using combined molecular and continuum stress analyses. In this approach, the results of molecular dynamics analyses of SAMs subjected to simple stress states are used to inform continuum models of their stress-strain behavior. Continuum analyses of the IFM experiment were then conducted, which incorporate the stress-strain behavior of the SAMs and traction-separation relations that represent the interactions between the tip and functionalized Si surface. Agreement between predicted and measured force profiles was taken to imply that the traction-separation relations have been properly extracted. Scale up to larger contact areas was considered by forming Si/SAM/Si sandwiches and then separating them via fracture experiments. The mode 1 traction-separation relations have been extracted using fracture mechanics concepts under mode 1 and mixed-mode conditions. Interesting differences were noted between the three sets of traction-separation relations.

  8. Reversal Strategies for NOACs

    DEFF Research Database (Denmark)

    Husted, Steen; Verheugt, Freek; Comuth, Willemijn

    2015-01-01

    , coagulation factor concentrates or NOAC-specific antidotes could be used. Coagulation factor concentrates can be used in patients with haemophilia and to reverse the effect of VKAs but, in NOAC-treated patients, results are inconsistent and these agents could potentially have pro-thrombotic effects. Specific...... antidotes for NOACs are expected to be on the market soon. Phase III clinical trials with a humanized antibody fragment directed against dabigatran (idarucizumab) and recombinant, modified factor Xa (andexanet alfa) are ongoing. A molecule (aripazine) with broad activity against various anticoagulants...

  9. Reversible brazing process

    Science.gov (United States)

    Pierce, Jim D.; Stephens, John J.; Walker, Charles A.

    1999-01-01

    A method of reversibly brazing surfaces together. An interface is affixed to each surface. The interfaces can be affixed by processes such as mechanical joining, welding, or brazing. The two interfaces are then brazed together using a brazing process that does not defeat the surface to interface joint. Interfaces of materials such as Ni-200 can be affixed to metallic surfaces by welding or by brazing with a first braze alloy. The Ni-200 interfaces can then be brazed together using a second braze alloy. The second braze alloy can be chosen so that it minimally alters the properties of the interfaces to allow multiple braze, heat and disassemble, rebraze cycles.

  10. Reversibly Bistable Flexible Electronics

    KAUST Repository

    Alfaraj, Nasir

    2015-05-01

    Introducing the notion of transformational silicon electronics has paved the way for integrating various applications with silicon-based, modern, high-performance electronic circuits that are mechanically flexible and optically semitransparent. While maintaining large-scale production and prototyping rapidity, this flexible and translucent scheme demonstrates the potential to transform conventionally stiff electronic devices into thin and foldable ones without compromising long-term performance and reliability. In this work, we report on the fabrication and characterization of reversibly bistable flexible electronic switches that utilize flexible n-channel metal-oxide-semiconductor field-effect transistors. The transistors are fabricated initially on rigid (100) silicon substrates before they are peeled off. They can be used to control flexible batches of light-emitting diodes, demonstrating both the relative ease of scaling at minimum cost and maximum reliability and the feasibility of integration. The peeled-off silicon fabric is about 25 µm thick. The fabricated devices are transferred to a reversibly bistable flexible platform through which, for example, a flexible smartphone can be wrapped around a user’s wrist and can also be set back to its original mechanical position. Buckling and cyclic bending of such host platforms brings a completely new dimension to the development of flexible electronics, especially rollable displays.

  11. Enzymatic Modification of Sphingomyelin

    DEFF Research Database (Denmark)

    Due to its major role in maintaining the water-retaining properties of the epidermis, ceramide is of great commercial potential in cosmetic and pharmaceuticals such as hair and skin care products. Currently, chemical synthesis of ceramide is a costly process, and developments of alternative cost......-efficient, high yield production methods are of great interest. In the present study, the potential of producing ceramide through the enzymatic hydrolysis of sphingomyelin have been studied. sphingomyelin is a ubiquitous membrane-lipid and rich in dairy products or by-products. It has been verified...... that sphingomyelin modification gives a feasible approach to the potential production of ceramide. The reaction system has been improved through system evaluation and the optimization of several important factors, and phospholipase C from Clostridium perfringens shows higher activity towards the hydrolysis reaction...

  12. Unitarity and time reversal in the Glauber model

    International Nuclear Information System (INIS)

    Lazard, C.; Lombard, R.J.

    1984-12-01

    It has been pointed out by Formanek (1976-1980) that for incident energies above the particle production threshold the usual Glauber formulation of particle-nucleus scattering violates unitarity and time reversal invariance. We propose a simple method for recovering T-invariance and we discuss unitarity in view of the proposed modification. Numerical estimates are given to check the importance of T-invariance effects

  13. Stochastic behaviour of particle orbits in field reversed geometries

    International Nuclear Information System (INIS)

    Finn, J.M.

    1979-01-01

    Studies of stochastic or ergodic behaviour of beam particle orbits in axisymmetric systems with field reversal produced by ion rings or by neutral injection are presented. In the former case a large class of orbits is ergodic, whereas in the latter most are integrable. Effects of ergodic behaviour on particle confinement, equilibrium, magnetic compression, and stability are discussed. The modification, due to ergodic orbits of the stability criterion for low frequency (ω << ωsub(ci)) resonant instabilities is presented. (author)

  14. FRX-C Large Source Modification

    International Nuclear Information System (INIS)

    Chrien, R.E.; Tuszewski, M.; Yavornik, E.J.

    1985-01-01

    The FRX-C Large Source Modification (LSM) consists of a larger discharge tube and a larger radius coil connected to the existing FRX-C collector plates and capacitor banks. The objectives of LSM are to (1) study the size dependences of processes governing FRC formation and poloidal flux trapping in order to improve the design of larger field-reversed theta pinch devices, (2) increase the parameter s (number of local ion gyroradii between the field null and separatrix) to seek access to predicted new regimes of improved confinement and possible instability, (3) search for evidence of internal tilt instability at higher values of s where the mode is predicted to grow more rapidly, and (4) observe the effect of s and larger size on FRC confinement. In this paper we will discuss the construction of LSM, the experimental plan, and preliminary experimental results

  15. Covalent attachment of antagonists to the a7 nicotinic acetylcholine receptor: synthesis and reactivity of substituted maleimides

    DEFF Research Database (Denmark)

    Ambrus, Joseph I; Halliday, Jill I; Kanizaj, Nicholas

    2012-01-01

    The 3-methylmaleimide congeners of the natural product methyllycaconitine (MLA) and an analogue covalently attach to functional cysteine mutants of the a7 nicotinic acetylcholine receptor (nAChR).......The 3-methylmaleimide congeners of the natural product methyllycaconitine (MLA) and an analogue covalently attach to functional cysteine mutants of the a7 nicotinic acetylcholine receptor (nAChR)....

  16. Combination of supramolecular cross-linking with covalent cross-linking through epoxide ring-opening including gel studies

    NARCIS (Netherlands)

    Hofmeier, H.; El-Ghayoury, A.; Schubert, U.S.

    2003-01-01

    Terpolymers based on poly(methyl methacrylate), containing terpyridine-moieties as well as epoxide groups, were synthesized via free-radical polymeri-zation. The products were cross-linked non-covalently with iron(II) ions and cova-lently by treatment with AlCl3. Both steps could be combined in

  17. Combination of supramolecular cross-linking with covalent cross-linking through epoxide ring-opening including gel studies

    NARCIS (Netherlands)

    Hofmeier, H.; El-Ghayoury, A.; Schubert, U.S.

    2003-01-01

    Terpolymers based on poly(methyl methacrylate), containing terpyridinemoieties as well as epoxide groups, were synthesized via free-radical polymerization. The products were cross-linked non-covalently with iron(II) ions and covalently by treatment with AlCl3. Both steps could be combined in

  18. Surface Modification of Photoresist SU-8 for Low Autofluorescence and Bioanalytical Applications

    DEFF Research Database (Denmark)

    Cao, Cuong; Birtwell, Sam W.; Høgberg, Jonas

    2011-01-01

    This paper reports a surface modification of epoxy-based negative photoresist SU-8 for reducing its autofluorescence while enhancing its biofunctionality. By covalently depositing a thin layer of 20 nm Au nanoparticles (AuNPs) onto the SU-8 surface, we found that the AuNPs-coated SU-8 surface...... is much less fluorescent than the untreated SU-8. Moreover, DNA probes can easily be immobilized on the Au surface and are thermally stable over a wide range of temperature. These improvements will benefit bioanalytical applications such as DNA hybridization and solid-phase PCR (SP-PCR)....

  19. Novel covalently linked insulin dimer engineered to investigate the function of insulin dimerization.

    Directory of Open Access Journals (Sweden)

    Tine N Vinther

    Full Text Available An ingenious system evolved to facilitate insulin binding to the insulin receptor as a monomer and at the same time ensure sufficient stability of insulin during storage. Insulin dimer is the cornerstone of this system. Insulin dimer is relatively weak, which ensures dissociation into monomers in the circulation, and it is stabilized by hexamer formation in the presence of zinc ions during storage in the pancreatic β-cell. Due to the transient nature of insulin dimer, direct investigation of this important form is inherently difficult. To address the relationship between insulin oligomerization and insulin stability and function, we engineered a covalently linked insulin dimer in which two monomers were linked by a disulfide bond. The structure of this covalent dimer was identical to the self-association dimer of human insulin. Importantly, this covalent dimer was capable of further oligomerization to form the structural equivalent of the classical hexamer. The covalently linked dimer neither bound to the insulin receptor, nor induced a metabolic response in vitro. However, it was extremely thermodynamically stable and did not form amyloid fibrils when subjected to mechanical stress, underlining the importance of oligomerization for insulin stability.

  20. Immobilization of β-glucosidase onto mesoporous silica support: Physical adsorption and covalent binding of enzyme

    Directory of Open Access Journals (Sweden)

    Ivetić Darjana Ž.

    2014-01-01

    Full Text Available This paper investigates β-glucosidase immobilization onto mesoporous silica support by physical adsorption and covalent binding. The immobilization was carried out onto micro-size silica aggregates with the average pore size of 29 nm. During physical adsorption the highest yield of immobilized β-glucosidase was obtained at initial protein concentration of 0.9 mg ml-1. Addition of NaCl increased 1.7-fold, while Triton X-100 addition decreased 6-fold yield of adsorption in comparison to the one obtained without any addition. Covalently bonded β-glucosidase, via glutaraldehyde previously bonded to silanized silica, had higher yield of immobilized enzyme as well as higher activity and substrate affinity in comparison to the one physically adsorbed. Covalent binding did not considerably changed pH and temperature stability of obtained biocatalyst in range of values that are commonly used in reactions in comparison to unbounded enzyme. Furthermore, covalent binding provided biocatalyst which retained over 70% of its activity after 10 cycles of reuse. [Projekat Ministarstva nauke Republike Srbije, br. III 45021

  1. Assessing Covalency in Cerium and Uranium Hexachlorides: A Correlated Wavefunction and Density Functional Theory Study

    Directory of Open Access Journals (Sweden)

    Reece Beekmeyer

    2015-11-01

    Full Text Available The electronic structure of a series of uranium and cerium hexachlorides in a variety of oxidation states was evaluated at both the correlated wavefunction and density functional (DFT levels of theory. Following recent experimental observations of covalency in tetravalent cerium hexachlorides, bonding character was studied using topological and integrated analysis based on the quantum theory of atoms in molecules (QTAIM. This analysis revealed that M–Cl covalency was strongly dependent on oxidation state, with greater covalency found in higher oxidation state complexes. Comparison of M–Cl delocalisation indices revealed a discrepancy between correlated wavefunction and DFT-derived values. Decomposition of these delocalisation indices demonstrated that the origin of this discrepancy lay in ungerade contributions associated with the f-manifold which we suggest is due to self-interaction error inherent to DFT-based methods. By all measures used in this study, extremely similar levels of covalency between complexes of U and Ce in the same oxidation state was found.

  2. Mechanisms for Covalent Immobilization of Horseradish Peroxidase on Ion-Beam-Treated Polyethylene

    Directory of Open Access Journals (Sweden)

    Alexey V. Kondyurin

    2012-01-01

    Full Text Available The surface of polyethylene was modified by plasma immersion ion implantation. Structure changes including carbonization and oxidation were observed. High surface energy of the modified polyethylene was attributed to the presence of free radicals on the surface. The surface energy decay with storage time after treatment was explained by a decay of the free radical concentration while the concentration of oxygen-containing groups increased with storage time. Horseradish peroxidase was covalently attached onto the modified surface by the reaction with free radicals. Appropriate blocking agents can block this reaction. All aminoacid residues can take part in the covalent attachment process, providing a universal mechanism of attachment for all proteins. The native conformation of attached protein is retained due to hydrophilic interactions in the interface region. The enzymatic activity of covalently attached protein remained high. The long-term activity of the modified layer to attach protein is explained by stabilisation of unpaired electrons in sp2 carbon structures. A high concentration of free radicals can give multiple covalent bonds to the protein molecule and destroy the native conformation and with it the catalytic activity. The universal mechanism of protein attachment to free radicals could be extended to various methods of radiation damage of polymers.

  3. Protein tetrazinylation via diazonium coupling for covalent and catalyst-free bioconjugation.

    Science.gov (United States)

    Zhang, Jie; Men, Yuwen; Lv, Shanshan; Yi, Long; Chen, Jian-Feng

    2015-12-21

    An efficient and bench-stable reagent was synthesized for direct and covalent introduction of tetrazines onto target protein or virus surfaces, which can be further modified based on tetrazine-ene ligation to achieve fluorescence labelling or PEGylation under mild conditions.

  4. Covalent immobilization of redox protein within the mesopores of transparent conducting electrodes

    Czech Academy of Sciences Publication Activity Database

    Müller, V.; Rathouský, Jiří; Fattakhova-Rohlfing, D.

    2014-01-01

    Roč. 116, JAN 2014 (2014), s. 1-8 ISSN 0013-4686 R&D Projects: GA ČR GA104/08/0435 Institutional support: RVO:61388955 Keywords : Covalent immobilization * Porous electrodes * Redox proteins Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 4.504, year: 2014

  5. Recent advances in covalent, site-specific protein immobilization [version 1; referees

    DEFF Research Database (Denmark)

    Meldal, Morten Peter; Schoffelen, Sanne

    2016-01-01

    The properties of biosensors, biomedical implants, and other materials based on immobilized proteins greatly depend on the method employed to couple the protein molecules to their solid support. Covalent, site-specific immobilization strategies are robust and can provide the level of control...

  6. Identification of target cells by immunohistochemical detection of covalently rearranged estradiol in rehydrated paraffin sections.

    Science.gov (United States)

    Jungblut, P W; Sierralta, W D

    1998-04-01

    Estradiol is released from the binding niche of the receptor and covalently arrested in the molecular vicinity by the Mannich reaction during target fixation in acetic acid/formaldehyde. The exposed steroid is freely accessible for appropriate antibodies. It can be visualized in sections by the second antibody/enzyme technique in high resolution and without enhancements.

  7. Covalent functionalization of graphene oxide with polyglycerol and their use as templates for anchoring magnetic nanoparticles

    NARCIS (Netherlands)

    Pham, Tuan Anh; Kumar, Nanjundan Ashok; Jeong, Yeon Tae

    An efficient strategy for the preparation of water-dispersible hybrid material containing graphene oxide and polyglycerol for the first time is demonstrated. Pristine graphite was firstly oxidized to obtain graphene oxide with hydroxyl functional groups. Then, the covalent grafting of polyglycerol

  8. Direct covalent coupling of proteins to nanostructured plasma polymers: a route to tunable cell adhesion

    Czech Academy of Sciences Publication Activity Database

    Melnichuk, I.; Choukourov, A.; Bilek, M.; Weiss, A.; Vandrovcová, Marta; Bačáková, Lucie; Hanuš, J.; Kousal, J.; Shelemin, A.; Solař, P.; Slavínská, D.; Biederman, H.

    2015-01-01

    Roč. 351, Oct 1 (2015), s. 537-545 ISSN 0169-4332 R&D Projects: GA MZd(CZ) NT13297 Institutional support: RVO:67985823 Keywords : covalent binding * plasma polymers * MG-63 osteoblasts Subject RIV: CD - Macromolecular Chemistry Impact factor: 3.150, year: 2015

  9. Formation of Me–O–Si covalent bonds at the interface between polysilazane and stainless steel

    Energy Technology Data Exchange (ETDEWEB)

    Amouzou, Dodji, E-mail: adodji@gmail.com [Research Centre in Physics of Matter and Radiation (PMR), University of Namur, Rue de Bruxelles 61, 5000 Namur (Belgium); Fourdrinier, Lionel; Maseri, Fabrizio [CRM-Group, Boulevard de Colonster, B 57, 4000 Liège (Belgium); Sporken, Robert [Research Centre in Physics of Matter and Radiation (PMR), University of Namur, Rue de Bruxelles 61, 5000 Namur (Belgium)

    2014-11-30

    Highlights: • Natural metal-oxides, hydroxides are detected on the top surface of steel substrates we tested. • Polysilazane reacts with hydroxide functional groups on steel substrates to form Cr–O–Si and Fe–O–Si covalent bonds. • Covalent bonding between steel and polysilazane at the interface was probed using spectroscopic techniques. - Abstract: In earlier works, we demonstrated the potential of polysilazane (PSZ) coatings for a use as insulating layers in Cu(In,Ga)Se{sub 2} (CIGS) solar cells prepared on steels substrates and showed a good adhesion between PSZ coatings and both AISI316 and AISI430 steels. In the present paper, spectroscopic techniques are used to elucidate the reason of such adhesion. X-ray Photoelectron Spectroscopy (XPS) was used to investigate surfaces for the two steel substrates and showed the presence of metal oxides and metal hydroxides at the top surface. XPS has been also used to probe interfaces between substrates and PSZ, and metallosiloxane (Me–O–Si) covalent bonds have been detected. These results were confirmed by Infra-Red Reflection Absorption Spectroscopy (IRRAS) analyses since vibrations related to Cr–O–Si and Fe–O–Si compounds were detected. Thus, the good adhesion between steel substrates and PSZ coatings was explained by covalent bonding through chemical reactions between PSZ precursors and hydroxide functional groups present on top surface of the two types of steel. Based on these results, an adhesion mechanism between steel substrates and PSZ coatings is proposed.

  10. Gel Electrolytes of Covalent Network Polybenzimidazole and Phosphoric Acid by Direct Casting

    DEFF Research Database (Denmark)

    Kirkebæk, Andreas; Aili, David; Henkensmeier, Dirk

    2017-01-01

    for preparing mechanically robust covalent network polybenzimidazole membranes containing up to 95 wt% phosphoric acid. Diamino-terminal pre-polymers of different chain lengths are first prepared, followed by addition of a trifunctional carboxylic acid. The crude solutions are cast and subsequently heat treated...

  11. Carbohydrate as covalent crosslink in human inter-alpha-trypsin inhibitor

    DEFF Research Database (Denmark)

    Jessen, T E; Faarvang, K L; Ploug, M

    1988-01-01

    The primary structure of inter-alpha-trypsin inhibitor is partially elucidated, but controversy about the construction of the polypeptide backbone still exists. We present evidence suggesting that inter-alpha-trypsin inhibitor represents a novel plasma protein structure with two separate polypept...... polypeptide chains covalently crosslinked only by carbohydrate (chondroitin sulphate)....

  12. Metal–organic covalent network chemical vapor deposition for gas separation

    NARCIS (Netherlands)

    Boscher, N.D.; Wang, M.; Perrotta, A.; Heinze, K.; Creatore, A.; Gleason, K.K.

    2016-01-01

    The chemical vapor deposition (CVD) polymerization of metalloporphyrin building units is demonstrated to provide an easily up-scalable one-step method toward the deposition of a new class of dense and defect-free metal–organic covalent network (MOCN) layers. The resulting hyper-thin and flexible

  13. Covalent binding of organophosphorothioates to albumin: A new perspective for OP-pesticide biomonitoring?

    NARCIS (Netherlands)

    Noort, D.; Hulst, A.G.; Zuylen, A. van; Rijssel, E. van; Schans, M.J. van der

    2009-01-01

    We here report on the covalent binding of various organophosphorothioate (OPT) pesticides to albumin at in vitro exposure levels that did not give rise to butyrylcholinesterase inhibition. Adduct formation occurred at the Tyr-411 residue of albumin, as was firmly corroborated by LC-tandem MS

  14. Stabilization of 5A1 urease by covalent attachement to wool | Ahmed ...

    African Journals Online (AJOL)

    The investigation of five bacterial strains for urease production referred that Bacillus licheniformis 5A1 had the highest urease activity (10.3U/ml/min) after 24h. The enzyme was covalently coupled to different carriers via glutaraldehyde, and wool gave the highest immobilization yield (76.4%) and retained 85% of the original ...

  15. Origin of the Distinct Diffusion Behaviors of Cu and Ag in Covalent and Ionic Semiconductors.

    Science.gov (United States)

    Deng, Hui-Xiong; Luo, Jun-Wei; Li, Shu-Shen; Wei, Su-Huai

    2016-10-14

    It is well known that Cu diffuses faster than Ag in covalent semiconductors such as Si, which has prevented the replacement of Ag by Cu as a contact material in Si solar cells for reducing the cost. Surprisingly, in more ionic materials such as CdTe, Ag diffuses faster than Cu despite that it is larger than Cu, which has prevented the replacement of Cu by Ag in CdTe solar cells to improve the performance. But, so far, the mechanisms behind these distinct diffusion behaviors of Cu and Ag in covalent and ionic semiconductors have not been addressed. Here we reveal the underlying mechanisms by combining the first-principles calculations and group theory analysis. We find that the symmetry controlled s-d coupling plays a critical role in determining the diffusion behaviors. The s-d coupling is absent in pure covalent semiconductors but increases with the ionicity of the zinc blende semiconductors, and is larger for Cu than for Ag, owing to its higher d orbital energy. In conjunction with Coulomb interaction and strain energy, the s-d coupling is able to explain all the diffusion behaviors from Cu to Ag and from covalent to ionic hosts. This in-depth understanding enables us to engineer the diffusion of impurities in various semiconductors.

  16. Discovery of covalent inhibitors for MIF tautomerase via cocrystal structures with phantom hits from virtual screening

    Energy Technology Data Exchange (ETDEWEB)

    McLean, Larry R.; Zhang, Ying; Li, Hua; Li, Ziyu; Lukasczyk, Ulrike; Choi, Yong-Mi; Han, Zuoning; Prisco, Joy; Fordham, Jeremy; Tsay, Joseph T.; Reiling, Stephan; Vaz, Roy J.; Li, Yi; (Sanofi)

    2010-10-28

    Biochemical and X-ray crystallographic studies confirmed that hydroxyquinoline derivatives identified by virtual screening were actually covalent inhibitors of the MIF tautomerase. Adducts were formed by N-alkylation of the Pro-1 at the catalytic site with a loss of an amino group of the inhibitor.

  17. Regio- and Stereospecific Conversion of 4-Alkylphenols by the Covalent Flavoprotein Vanillyl-Alcohol Oxidase

    NARCIS (Netherlands)

    Heuvel, Robert H.H. van den; Fraaije, Marco W.; Laane, Colja; Berkel, Willem J.H. van

    1998-01-01

    The regio- and stereospecific conversion of prochiral 4-alkylphenols by the covalent flavoprotein vanillyl-alcohol oxidase was investigated. The enzyme was active, with 4-alkylphenols bearing aliphatic side chains of up to seven carbon atoms. Optimal catalytic efficiency occurred with 4-ethylphenol

  18. The yeast cell fusion protein Prm1p requires covalent dimerization to promote membrane fusion.

    Directory of Open Access Journals (Sweden)

    Alex Engel

    2010-05-01

    Full Text Available Prm1p is a multipass membrane protein that promotes plasma membrane fusion during yeast mating. The mechanism by which Prm1p and other putative regulators of developmentally controlled cell-cell fusion events facilitate membrane fusion has remained largely elusive. Here, we report that Prm1p forms covalently linked homodimers. Covalent Prm1p dimer formation occurs via intermolecular disulfide bonds of two cysteines, Cys-120 and Cys-545. PRM1 mutants in which these cysteines have been substituted are fusion defective. These PRM1 mutants are normally expressed, retain homotypic interaction and can traffic to the fusion zone. Because prm1-C120S and prm1-C545S mutants can form covalent dimers when coexpressed with wild-type PRM1, an intermolecular C120-C545 disulfide linkage is inferred. Cys-120 is adjacent to a highly conserved hydrophobic domain. Mutation of a charged residue within this hydrophobic domain abrogates formation of covalent dimers, trafficking to the fusion zone, and fusion-promoting activity. The importance of intermolecular disulfide bonding informs models regarding the mechanism of Prm1-mediated cell-cell fusion.

  19. COVALENTLY ATTACHED MULTILAYER ULTRA-THIN FILMS FROM DIAZORESIN AND CALIXARENES

    Institute of Scientific and Technical Information of China (English)

    Zhao-hui Yang; Wei-xiao Cao

    2003-01-01

    A kind of photosensitive ultra-thin film was fabricated from diazoresin (DR) and various calixarenes by using the self-assembly technique. Under UV irradiation both the ionic- and hydrogen bonds between the layers of the film will convert into covalent bonds. As a result, the stability of the film toward polar solvents increases dramatically.

  20. Molecular-dynamics simulation of crystalline 18-crown-6: thermal shortening of covalent bonds

    NARCIS (Netherlands)

    van Eerden, J.; Harkema, Sybolt; Feil, D.

    1990-01-01

    Molecular-dynamics simulations of crystalline 18-crown-6 have been performed in a study of the apparent thermal shortening of covalent bonds observed in crystal structures. At 100 K, a shortening of 0.006 _+ 0.001 A for C----C and C----O bonds was obtained. This result was found to be independent of

  1. A simple approach for immobilization of gold nanoparticles on graphene oxide sheets by covalent bonding

    NARCIS (Netherlands)

    Pham, Tuan Anh; Choi, Byung Choon; Lim, Kwon Taek; Jeong, Yeon Tae

    2011-01-01

    Amino - functionalized gold nanoparticles with a diameter of around 5 nm were immobilized onto the surface of graphene oxide sheets (GOS) by covalent bonding through a simple amidation reaction. Pristine graphite was firstly oxidized and exfoliated to obtain GOS, which further were acylated with

  2. 共价键的离子化%Ionization of Covalent Bond

    Institute of Scientific and Technical Information of China (English)

    王稼国; 荆西平

    2017-01-01

    本文用化学键理论分析和推导了共价键离子化的几种方式,包括金属和非金属单质中共价键的诱导离子化、化合物中共价键的降温和自诱导离子化以及含氢化合物和金属化合物的诱导离子化.从能量角度分析了离子化趋势的规律性,并且讨论了共价键的离子化的一些重要应用.%Several ionization patterns of covalent bond,including induced-ionization of covalent bond in metals and nonmetals,induced-ionization of covalent bond in hydrogen compounds and metal compounds,lowering temperature and self-induced ionization of compound,and so on,were dedueed and analyzed by using chemical bond theory.The trend of ionization was also analyzed on energy changing and several important applications of the ionization of covalent bond were discussed.

  3. Ultrafast cooling by covalently bonded graphene-carbon nanotube hybrid immersed in water

    DEFF Research Database (Denmark)

    Chen, Jie; Walther, Jens Honore; Koumoutsakos, Petros

    2016-01-01

    , we demonstrate, through transient heat-dissipation simulations, that a covalently bonded graphene-carbon nanotube (G-CNT) hybrid immersed in water is a promising solution for the ultrafast cooling of such high-temperature and high heat-flux surfaces. The G-CNT hybrid offers a unique platform...

  4. Nano-Sized Zero Valent Iron and Covalent Organic Polymer Composites for Azo Dye Remediation

    DEFF Research Database (Denmark)

    Mines, Paul D.; Byun, Jeehye; Hwang, Yuhoon

    2014-01-01

    . In this study, the effect of various covalent organic polymers (COPs) as effective supporting materials for nZVI for optimal pollutant degradation was assessed. These COPs demonstrate promising results for the ability to adsorb and remove carbon dioxide, yielding the notion that they are capable of groundwater...... in chlorinated organics, heavy metals, and various other groundwater contaminants....

  5. Catalyst recycling via specific non-covalent adsorption on modified silicas

    NARCIS (Netherlands)

    Kluwer, A.M.; Simons, C.; Knijnenburg, Q.; van der Vlugt, J.I.; de Bruin, B.; Reek, J.N.H.

    2013-01-01

    This article describes a new strategy for the recycling of a homogeneous hydroformylation catalyst, by selective adsorption of the catalyst to tailor-made supports after a batchwise reaction. The separation of the catalyst from the product mixture is based on selective non-covalent supramolecular

  6. Covalent binding of nitrogen mustards to the cysteine-34 residue in human serum albumin

    NARCIS (Netherlands)

    Noort, D.; Hulst, A.G.; Jansen, R.

    2002-01-01

    Covalent binding of various clinically important nitrogen mustards to the cysteine-34 residue of human serum albumin, in vitro and in vivo, is demonstrated. A rapid method for detection of these adducts is presented, based on liquid chromatography-tandem mass spectrometry analysis of the adducted

  7. Nature and consequences of non-covalent interactions between flavonoids and macronutrients in foods.

    Science.gov (United States)

    Bordenave, Nicolas; Hamaker, Bruce R; Ferruzzi, Mario G

    2014-01-01

    Many of the potential health benefits of flavonoids have been associated with their specific chemical and biological properties including their ability to interact and bind non-covalently to macronutrients in foods. While flavonoid-protein interactions and binding have been the subject of intensive study, significantly less is understood about non-covalent interactions with carbohydrates and lipids. These interactions with macronutrients are likely to impact both the flavonoid properties in foods, such as their radical scavenging activity, and the food or beverage matrix itself, including their taste, texture and other sensorial properties. Overall, non-covalent binding of flavonoids with macronutrients is primarily driven by van der Waals interactions. From the flavonoid perspective, these interactions are modulated by characteristics such as degree of polymerization, molecular flexibility, number of external hydroxyl groups, or number of terminal galloyl groups. From the macronutrient standpoint, electrostatic and ionic interactions are generally predominant with carbohydrates, while hydrophobic interactions are generally predominant with lipids and mainly limited to interactions with flavonols. All of these interactions are involved in flavonoid-protein interactions. While primarily associated with undesirable characteristics in foods and beverages, such as astringency, negative impact on macronutrient digestibility and hazing, more recent efforts have attempted to leverage these interactions to develop controlled delivery systems or strategies to enhance flavonoids bioavailability. This paper aims at reviewing the fundamental bases for non-covalent interactions, their occurrence in food and beverage systems and their impact on the physico-chemical, organoleptic and some nutritional properties of food.

  8. Improved Performance of Pseudomonas fluorescens lipase by covalent immobilization onto Amberzyme

    NARCIS (Netherlands)

    Aslan, Yakup; Handayani, Nurrahmi; Stavila, Erythrina; Loos, Katja

    2013-01-01

    Objective: In this study, the conditions of covalent immobilization of Pseudomonas fluorescens lipase onto an oxirane-activated support (Amberzyme) were optimized to obtain a high activity yield. Furthermore, the operational and storage stabilities of immobilized lipase were tested. Methods: Optimum

  9. Inorganic Materials as Supports for Covalent Enzyme Immobilization: Methods and Mechanisms

    Directory of Open Access Journals (Sweden)

    Paolo Zucca

    2014-09-01

    Full Text Available Several inorganic materials are potentially suitable for enzymatic covalent immobilization, by means of several different techniques. Such materials must meet stringent criteria to be suitable as solid matrices: complete insolubility in water, reasonable mechanical strength and chemical resistance under the operational conditions, the capability to form manageable particles with high surface area, reactivity towards derivatizing/functionalizing agents. Non-specific protein adsorption should be always considered when planning covalent immobilization on inorganic solids. A huge mass of experimental work has shown that silica, silicates, borosilicates and aluminosilicates, alumina, titania, and other oxides, are the materials of choice when attempting enzyme immobilizations on inorganic supports. More recently, some forms of elemental carbon, silicon, and certain metals have been also proposed for certain applications. With regard to the derivatization/functionalization techniques, the use of organosilanes through silanization is undoubtedly the most studied and the most applied, although inorganic bridge formation and acylation with selected acyl halides have been deeply studied. In the present article, the most common inorganic supports for covalent immobilization of the enzymes are reviewed, with particular focus on their advantages and disadvantages in terms of enzyme loadings, operational stability, undesired adsorption, and costs. Mechanisms and methods for covalent immobilization are also discussed, focusing on the most widespread activating approaches (such as glutaraldehyde, cyanogen bromide, divinylsulfone, carbodiimides, carbonyldiimidazole, sulfonyl chlorides, chlorocarbonates, N-hydroxysuccinimides.

  10. A Cost-Effective Physical Modeling Exercise to Develop Students' Understanding of Covalent Bonding

    Science.gov (United States)

    Turner, Kristy L.

    2016-01-01

    Chemical bonding is one of the basic concepts in chemistry, and the topic of covalent bonding forms an important core of knowledge for the high school chemistry student. For many teachers it is a challenging concept to teach, not least because it relies mainly on traditional instruction and written work. Similarly, many students find the topic…

  11. Covalently Cross-Linked Sulfone Polybenzimidazole Membranes with Poly(Vinylbenzyl Chloride) for Fuel Cell Applications

    DEFF Research Database (Denmark)

    Yang, Jingshuai; Aili, David; Li, Qingfeng

    2013-01-01

    Covalently cross-linked polymer membranes were fabricated from poly(aryl sulfone benzimidazole) (SO(2) PBI) and poly(vinylbenzyl chloride) (PVBCl) as electrolytes for high-temperature proton-exchange-membrane fuel cells. The cross-linking imparted organo insolubility and chemical stability against...

  12. Reversible posterior leukoencephalopathy syndrome

    International Nuclear Information System (INIS)

    Lee, Eun Ja; Yu, Won Jong; Ahn, Kook Jin; Jung, So Lyung; Lee, Yeon Soo; Kim, Ji Chang; Kang, Si Won; Song, Chang Joon; Song, Soon-Young; Koo, Ja Hong; Kim, Man Deuk

    2001-01-01

    To review reversible posterior leukoencephalopathy syndrome. We reviewed 22 patients (M:F=3:19; age, 17-46 years) with the characteristic clinical and imaging features of reversible posterior leukoencephalopathy syndrome. All underwent brain MRI, and in three cases both CT and MRI were performed. In one, MRA was obtained, and in eleven, follow-up MR images were obtained. We evaluated the causes of this syndrome, its clinical manifestations, and MR findings including the locations of lesions, the presence or absence of contrast enhancement, and the changes seen at follow-up MRI. Of the 22 patients, 13 had eclampsia (six during pregnancy and seven during puerperium). Four were receiving immunosuppressive therapy (three, cyclosporine ; one, FK 506). Four suffered renal failure and one had complicated migraine. The clinical manifestations included headache (n=12), visual disturbance (n=13), seizure (n=15), focal neurologic sign (n=3), and altered mental status (n=2). Fifteen patients had hypertension and the others normotension. MRI revealed that lesions were bilateral (n=20) or unilateral (n=2). In all patients the lesion was found in the cortical and subcortical areas of the parieto-occipital lobes ; other locations were the basal ganglia (n=9), posterior temporal lobe (n=8), frontal lobe (n=5), cerebellum (n=5), pons (n=2), and thalamus (n=1). All lesions were of high signal intensity on T2-weighted images, and of iso to low intensity on T1-weighted images. One was combined with acute hematoma in the left basal ganglia. In eight of 11 patients who underwent postcontrast T1-weighted MRI, there was no definite enhancement ; in one, enhancement was mild, and in tow, patchy. CT studies showed low attenuation, and MRA revealed mild vasospasm. The symptoms of all patients improved. Follow-up MRI in nine of 11 patients depicted complete resolution of the lesions ; in two, small infarctions remained but the extent of the lesions had decreased. Reversible posterior

  13. Reversible posterior leukoencephalopathy syndrome

    Energy Technology Data Exchange (ETDEWEB)

    Lee, Eun Ja; Yu, Won Jong; Ahn, Kook Jin; Jung, So Lyung; Lee, Yeon Soo; Kim, Ji Chang; Kang, Si Won [The Catholic Univ. of Korea, Taejon (Korea, Republic of); Song, Chang Joon [Chungnam National Univ. School of Medicine, Cheonju (Korea, Republic of); Song, Soon-Young; Koo, Ja Hong [Kwandong Univ. College of Medicine, Myungji Hospital, Seoul (Korea, Republic of); Kim, Man Deuk [College of Medicine Pochon CHA Univ., Seoul (Korea, Republic of)

    2001-10-01

    To review reversible posterior leukoencephalopathy syndrome. We reviewed 22 patients (M:F=3:19; age, 17-46 years) with the characteristic clinical and imaging features of reversible posterior leukoencephalopathy syndrome. All underwent brain MRI, and in three cases both CT and MRI were performed. In one, MRA was obtained, and in eleven, follow-up MR images were obtained. We evaluated the causes of this syndrome, its clinical manifestations, and MR findings including the locations of lesions, the presence or absence of contrast enhancement, and the changes seen at follow-up MRI. Of the 22 patients, 13 had eclampsia (six during pregnancy and seven during puerperium). Four were receiving immunosuppressive therapy (three, cyclosporine ; one, FK 506). Four suffered renal failure and one had complicated migraine. The clinical manifestations included headache (n=12), visual disturbance (n=13), seizure (n=15), focal neurologic sign (n=3), and altered mental status (n=2). Fifteen patients had hypertension and the others normotension. MRI revealed that lesions were bilateral (n=20) or unilateral (n=2). In all patients the lesion was found in the cortical and subcortical areas of the parieto-occipital lobes ; other locations were the basal ganglia (n=9), posterior temporal lobe (n=8), frontal lobe (n=5), cerebellum (n=5), pons (n=2), and thalamus (n=1). All lesions were of high signal intensity on T2-weighted images, and of iso to low intensity on T1-weighted images. One was combined with acute hematoma in the left basal ganglia. In eight of 11 patients who underwent postcontrast T1-weighted MRI, there was no definite enhancement ; in one, enhancement was mild, and in tow, patchy. CT studies showed low attenuation, and MRA revealed mild vasospasm. The symptoms of all patients improved. Follow-up MRI in nine of 11 patients depicted complete resolution of the lesions ; in two, small infarctions remained but the extent of the lesions had decreased. Reversible posterior

  14. Reverse osmosis application studies

    International Nuclear Information System (INIS)

    Golomb, A.

    1982-02-01

    To assess the feasibility of applying reverse osmosis (RO) and ultrafiltration (UF) for effective treatment of process and waste streams from operations at Ontario Hydro's thermal and nuclear stations, an extensive literature survey has been carried out. It is concluded that RO is not at present economic for pretreatment of Great Lakes water prior to ion exchange demineralization for boiler makeup. Using both conventional and novel commercial membrane modules, RO pilot studies are recommended for treatment of boiler cleaning wastes, fly ash leachates, and flue gas desulphurization scrubber discharges for removal of heavy metals. Volume reduction and decontamination of nuclear station low-level active liquid waste streams by RO/UF also appear promising. Research programmes are proposed

  15. Reverse photoacoustic standoff spectroscopy

    Science.gov (United States)

    Van Neste, Charles W [Kingston, TN; Senesac, Lawrence R [Knoxville, TN; Thundat, Thomas G [Knoxville, TN

    2011-04-12

    A system and method are disclosed for generating a reversed photoacoustic spectrum at a greater distance. A source may emit a beam to a target and a detector measures signals generated as a result of the beam being emitted on the target. By emitting a chopped/pulsed light beam to the target, it may be possible to determine the target's optical absorbance by monitoring the intensity of light collected at the detector at different wavelengths. As the wavelength of light is changed, the target may absorb or reject each optical frequency. Rejection may increase the intensity at the sensing element and absorption may decrease the intensity. Accordingly, an identifying spectrum of the target may be made with the intensity variation of the detector as a function of illuminating wavelength.

  16. Reverse Osmosis Optimization

    Energy Technology Data Exchange (ETDEWEB)

    McMordie Stoughton, Kate; Duan, Xiaoli; Wendel, Emily M.

    2013-08-26

    This technology evaluation was prepared by Pacific Northwest National Laboratory on behalf of the U.S. Department of Energy’s Federal Energy Management Program (FEMP). ¬The technology evaluation assesses techniques for optimizing reverse osmosis (RO) systems to increase RO system performance and water efficiency. This evaluation provides a general description of RO systems, the influence of RO systems on water use, and key areas where RO systems can be optimized to reduce water and energy consumption. The evaluation is intended to help facility managers at Federal sites understand the basic concepts of the RO process and system optimization options, enabling them to make informed decisions during the system design process for either new projects or recommissioning of existing equipment. This evaluation is focused on commercial-sized RO systems generally treating more than 80 gallons per hour.¬

  17. Reverse Osmosis Optimization

    Energy Technology Data Exchange (ETDEWEB)

    None

    2013-08-01

    This technology evaluation was prepared by Pacific Northwest National Laboratory on behalf of the U.S. Department of Energy’s Federal Energy Management Program (FEMP). The technology evaluation assesses techniques for optimizing reverse osmosis (RO) systems to increase RO system performance and water efficiency. This evaluation provides a general description of RO systems, the influence of RO systems on water use, and key areas where RO systems can be optimized to reduce water and energy consumption. The evaluation is intended to help facility managers at Federal sites understand the basic concepts of the RO process and system optimization options, enabling them to make informed decisions during the system design process for either new projects or recommissioning of existing equipment. This evaluation is focused on commercial-sized RO systems generally treating more than 80 gallons per hour.

  18. Sex Reversal in Amphibians.

    Science.gov (United States)

    Flament, Stéphane

    2016-01-01

    Amphibians have been widely used to study developmental biology due to the fact that embryo development takes place independently of the maternal organism and that observations and experimental approaches are easy. Some amphibians like Xenopus became model organisms in this field. In the first part of this article, the differentiation of the gonads in amphibians and the mechanisms governing this process are reviewed. In the second part, the state of the art about sex reversal, which can be induced by steroid hormones in general and by temperature in some species, is presented. Also information about pollutants found in the environment that could interfere with the development of the amphibian reproductive apparatus or with their reproductive physiology is given. Such compounds could play a part in the amphibian decline, since in the wild, many amphibians are endangered species. © 2016 S. Karger AG, Basel.

  19. Production of recombinant cholesterol oxidase containing covalently bound FAD in Escherichia coli

    Directory of Open Access Journals (Sweden)

    Molla Gianluca

    2010-04-01

    Full Text Available Abstract Background Cholesterol oxidase is an alcohol dehydrogenase/oxidase flavoprotein that catalyzes the dehydrogenation of C(3-OH of cholesterol. It has two major biotechnological applications, i.e. in the determination of serum (and food cholesterol levels and as biocatalyst providing valuable intermediates for industrial steroid drug production. Cholesterol oxidases of type I are those containing the FAD cofactor tightly but not covalently bound to the protein moiety, whereas type II members contain covalently bound FAD. This is the first report on the over-expression in Escherichia coli of type II cholesterol oxidase from Brevibacterium sterolicum (BCO. Results Design of the plasmid construct encoding the mature BCO, optimization of medium composition and identification of the best cultivation/induction conditions for growing and expressing the active protein in recombinant E. coli cells, concurred to achieve a valuable improvement: BCO volumetric productivity was increased from ~500 up to ~25000 U/L and its crude extract specific activity from 0.5 up to 7.0 U/mg protein. Interestingly, under optimal expression conditions, nearly 55% of the soluble recombinant BCO is produced as covalently FAD bound form, whereas the protein containing non-covalently bound FAD is preferentially accumulated in insoluble inclusion bodies. Conclusions Comparison of our results with those published on non-covalent (type I COs expressed in recombinant form (either in E. coli or Streptomyces spp., shows that the fully active type II BCO can be produced in E. coli at valuable expression levels. The improved over-production of the FAD-bound cholesterol oxidase will support its development as a novel biotool to be exploited in biotechnological applications.

  20. Stage-specific histone modification profiles reveal global transitions in the Xenopus embryonic epigenome.

    Directory of Open Access Journals (Sweden)

    Tobias D Schneider

    Full Text Available Vertebrate embryos are derived from a transitory pool of pluripotent cells. By the process of embryonic induction, these precursor cells are assigned to specific fates and differentiation programs. Histone post-translational modifications are thought to play a key role in the establishment and maintenance of stable gene expression patterns underlying these processes. While on gene level histone modifications are known to change during differentiation, very little is known about the quantitative fluctuations in bulk histone modifications during development. To investigate this issue we analysed histones isolated from four different developmental stages of Xenopus laevis by mass spectrometry. In toto, we quantified 59 modification states on core histones H3 and H4 from blastula to tadpole stages. During this developmental period, we observed in general an increase in the unmodified states, and a shift from histone modifications associated with transcriptional activity to transcriptionally repressive histone marks. We also compared these naturally occurring patterns with the histone modifications of murine ES cells, detecting large differences in the methylation patterns of histone H3 lysines 27 and 36 between pluripotent ES cells and pluripotent cells from Xenopus blastulae. By combining all detected modification transitions we could cluster their patterns according to their embryonic origin, defining specific histone modification profiles (HMPs for each developmental stage. To our knowledge, this data set represents the first compendium of covalent histone modifications and their quantitative flux during normogenesis in a vertebrate model organism. The HMPs indicate a stepwise maturation of the embryonic epigenome, which may be causal to the progressing restriction of cellular potency during development.

  1. Electron beam modification of vanadium dioxide oscillators

    Energy Technology Data Exchange (ETDEWEB)

    Belyaev, Maksim; Velichko, Andrey; Putrolaynen, Vadim; Perminov, Valentin; Pergament, Alexander [Petrozavodsk State University, Petrozavodsk (Russian Federation)

    2017-03-15

    The paper presents the results of a study of electron-beam modification (EBM) of VO{sub 2}-switch I-V curve threshold parameters and the self-oscillation frequency of a circuit containing such a switching device. EBM in vacuum is reversible and the parameters are restored when exposed to air at pressure of 150 Pa. At EBM with a dose of 3 C cm{sup -2}, the voltages of switching-on (V{sub th}) and off (V{sub h}), as well as the OFF-state resistance R{sub off}, decrease down to 50% of the initial values, and the oscillation frequency increases by 30% at a dose of 0.7 C cm{sup -2}. Features of physics of EBM of an oscillator are outlined considering the contribution of the metal and semiconductor phases of the switching channel. Controlled modification allows EBM forming of switches with preset parameters. Also, it might be used in artificial oscillatory neural networks for pattern recognition based on frequency shift keying. (copyright 2017 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  2. Silane surface modification for improved bioadhesion of esophageal stents

    Science.gov (United States)

    Karakoy, Mert; Gultepe, Evin; Pandey, Shivendra; Khashab, Mouen A.; Gracias, David H.

    2014-08-01

    Stent migration occurs in 10-40% of patients who undergo placement of esophageal stents, with higher migration rates seen in those treated for benign esophageal disorders. This remains a major drawback of esophageal stent therapy. In this paper, we propose a new surface modification method to increase the adhesion between self-expandable metallic stents (SEMS) and tissue while preserving their removability. Taking advantage of the well-known affinity between epoxide and amine terminated silane coupling agents with amine and carboxyl groups that are abundant in proteins and related molecules in the human body; we modified the surfaces of silicone coated esophageal SEMS with these adhesive self-assembled monolayers (SAMs). We utilized vapor phase silanization to modify the surfaces of different substrates including PDMS strips and SEMS, and measured the force required to slide these substrates on a tissue piece. Our results suggest that surface modification of esophageal SEMS via covalent attachment of protein-binding coupling agents improves adhesion to tissue and could offer a solution to reduce SEMS migration while preserving their removability.

  3. 49 CFR 230.89 - Reverse gear.

    Science.gov (United States)

    2010-10-01

    ... 49 Transportation 4 2010-10-01 2010-10-01 false Reverse gear. 230.89 Section 230.89 Transportation... Reversing Gear § 230.89 Reverse gear. (a) General provisions. Reverse gear, reverse levers, and quadrants... quadrant. Proper counterbalance shall be provided for the valve gear. (b) Air-operated power reverse gear...

  4. Genetic modification and genetic determinism

    Directory of Open Access Journals (Sweden)

    Vorhaus Daniel B

    2006-06-01

    Full Text Available Abstract In this article we examine four objections to the genetic modification of human beings: the freedom argument, the giftedness argument, the authenticity argument, and the uniqueness argument. We then demonstrate that each of these arguments against genetic modification assumes a strong version of genetic determinism. Since these strong deterministic assumptions are false, the arguments against genetic modification, which assume and depend upon these assumptions, are therefore unsound. Serious discussion of the morality of genetic modification, and the development of sound science policy, should be driven by arguments that address the actual consequences of genetic modification for individuals and society, not by ones propped up by false or misleading biological assumptions.

  5. Introduction of a covalent histidine-heme linkage in a hemoglobin: a promising tool for heme protein engineering.

    Science.gov (United States)

    Rice, Selena L; Preimesberger, Matthew R; Johnson, Eric A; Lecomte, Juliette T J

    2014-12-01

    The hemoglobins of the cyanobacteria Synechococcus and Synechocystis (GlbNs) are capable of spontaneous and irreversible attachment of the b heme to the protein matrix. The reaction, which saturates the heme 2-vinyl by addition of a histidine residue, is reproduced in vitro by preparing the recombinant apoprotein, adding ferric heme, and reducing the iron to the ferrous state. Spontaneous covalent attachment of the heme is potentially useful for protein engineering purposes. Thus, to explore whether the histidine-heme linkage can serve in such applications, we attempted to introduce it in a test protein. We selected as our target the heme domain of Chlamydomonas eugametos LI637 (CtrHb), a eukaryotic globin that exhibits less than 50% sequence identity with the cyanobacterial GlbNs. We chose two positions, 75 in the FG corner and 111 in the H helix, to situate a histidine near a vinyl group. We characterized the proteins with gel electrophoresis, absorbance spectroscopy, and NMR analysis. Both T111H and L75H CtrHbs reacted upon reduction of the ferric starting material containing cyanide as the distal ligand to the iron. With L75H CtrHb, nearly complete (>90%) crosslinking was observed to the 4-vinyl as expected from the X-ray structure of wild-type CtrHb. Reaction of T111H CtrHb also occurred at the 4-vinyl, in a 60% yield indicating a preference for the flipped heme orientation in the starting material. The work suggests that the His-heme modification will be applicable to the design of proteins with a non-dissociable heme group. Copyright © 2014 Elsevier Inc. All rights reserved.

  6. Chloramphenicol Biosynthesis: The Structure of CmlS, a Flavin-Dependent Halogenase Shwing a Covalent Flavin-Aspartate Bond

    International Nuclear Information System (INIS)

    Podzelinska, K.; Latimer, R.; Bhattacharya, A.; Vining, L.; Zechel, D.; Jia, Z.

    2010-01-01

    Chloramphenicol is a halogenated natural product bearing an unusual dichloroacetyl moiety that is critical for its antibiotic activity. The operon for chloramphenicol biosynthesis in Streptomyces venezuelae encodes the chloramphenicol halogenase CmlS, which belongs to the large and diverse family of flavin-dependent halogenases (FDH's). CmlS was previously shown to be essential for the formation of the dichloroacetyl group. Here we report the X-ray crystal structure of CmlS determined at 2.2 (angstrom) resolution, revealing a flavin monooxygenase domain shared by all FDHs, but also a unique 'winged-helix' C-terminal domain that creates a T-shaped tunnel leading to the halogenation active site. Intriguingly, the C-terminal tail of this domain blocks access to the halogenation active site, suggesting a structurally dynamic role during catalysis. The halogenation active site is notably nonpolar and shares nearly identical residues with Chondromyces crocatus tyrosyl halogenase (CndH), including the conserved Lys (K71) that forms the reactive chloramine intermediate. The exception is Y350, which could be used to stabilize enolate formation during substrate halogenation. The strictly conserved residue E44, located near the isoalloxazine ring of the bound flavin adenine dinucleotide (FAD) cofactor, is optimally positioned to function as a remote general acid, through a water-mediated proton relay, which could accelerate the reaction of the chloramine intermediate during substrate halogenation, or the oxidation of chloride by the FAD(C4α)-OOH intermediate. Strikingly, the 8α carbon of the FAD cofactor is observed to be covalently attached to D277 of CmlS, a residue that is highly conserved in the FDH family. In addition to representing a new type of flavin modification, this has intriguing implications for the mechanism of FDHs. Based on the crystal structure and in analogy to known halogenases, we propose a reaction mechanism for CmlS.

  7. Theoretical study of molecular hydrogen and spiltover hydrogen storage on two-dimensional covalent-organic frameworks

    International Nuclear Information System (INIS)

    Liu Xiu-Ying; He Jie; Yu Jing-Xin; Fan Zhi-Qin; Li Zheng-Xin

    2014-01-01

    Molecular hydrogen and spiltover hydrogen storages on five two-dimensional (2D) covalent-organic frameworks (COFs) (PPy-COF, TP-COF, BTP-COF, COF-18 Å, and HHTP-DPB COF) are investigated using the grand canonical Monte Carlo (GCMC) simulations and the density functional theory (DFT), respectively. The GCMC simulated results show that HHTP-DPB COF has the best performance for hydrogen storage, followed by BTP-COF, TP-COF, COF-18 Å, and PPy-COF. However, their adsorption amounts at room temperature are all too low to meet the uptake target set by US Department of Energy (US-DOE) and enable practical applications. The effects of pore size, surface area, and isosteric heat of hydrogen on adsorption amount are considered, which indicate that these three factors are all the important factors for determining the H 2 adsorption amount. The chemisorptions of spiltover hydrogen atoms on these five COFs represented by the cluster models are investigated using the DFT method. The saturation cluster models are constructed by considering all possible adsorption sites for these cluster models. The average binding energy of a hydrogen atom and the saturation hydrogen storage density are calculated. The large average binding energy indicates that the spillover process may proceed smoothly and reversibly. The saturation hydrogen storage density is much larger than the physisorption uptake of H 2 molecules at 298 K and 100 bar (1 bar = 10 5 Pa), and is close to or exceeds the 2010 US-DOE target of 6 wt% for hydrogen storage. This suggests that the hydrogen storage capacities of these COFs by spillover may be significantly enhanced. Thus 2D COFs studied in this paper are suitable hydrogen storage media by spillover

  8. In vitro synthesis and purification of PhIP-deoxyguanosine and PhIP-DNA oligomer covalent complexes

    Energy Technology Data Exchange (ETDEWEB)

    Freeman, J.

    1994-12-01

    2-Amino-1-methyl-6-phenylimidazo[4,5-b]pyridine (PhIP) is a heterocyclic amine compound formed when meats are cooked at high temperatures. PhIP damages DNA by forming covalent complexes with DNA carcinogen. In an effort to understand how the binding of PhIP to DNA may cause cancer, it is important to characterize the structures of PhIP-damaged DNA molecules. Our HPLC data support fluorescence and {sup 32}P Post-labeling studies which indicate the formation of several species of 2{prime}deoxyguanosine-(dG) or oligodeoxynucleotide-PhIP adducts. The reaction of PhIP with dG resulted in a reddish precipitate that was likely the major adduct, N-(deoxyguanosin-8-yl)-PhIP (dG-C8-PhIP) adduct, with a more polar adduct fraction remaining in the supernatant. Reversed-phase HPLC analysis of the adducts in the supernatant revealed the existence of species of much shorter retention times than the dG-C8-PhIP adduct, confirming that these species are more polar than dG-C8-PhIP. At least four adducts were formed in the reaction of PhIP with DNA oligomer. HPLC analysis of the PhIP-DNA oligomer supernatant after butanol extractions revealed four unresolved peaks which spectra had maximum wavelengths between 340 and 360 nm. Though adduct peaks were not completely resolved, there was {approximately}3 minutes interval between the DNA oligomer peak and the adduct peaks. Furthermore, fluorescence emission data of the DNA oligomer-PhIP adduct solution show heterogeneous binding. The more polar PhIP adducts were fraction-collected and their structures will be solved by nuclear magnetic resonance or x-ray crystallography.

  9. Field reversal experiments (FRX)

    International Nuclear Information System (INIS)

    Linford, R.K.; Armstrong, W.T.; Platts, D.A.; Sherwood, E.G.

    1978-01-01

    The equilibrium, confinement, and stability properties of the reversed-field configuration (RFC) are being studied in two theta-pinch facilities. The RFC is an elongated toroidal plasma confined in a purely poloidal field geometry. The open field lines of the linear theta pinch support the closed-field RFC much like the vertical field centers the toroidal plasma in a tokamak. Depending on stability and confinement properties, the RFC might be used to greatly reduce the axial losses in linear fusion devices such as mirrors, theta pinches, and liners. The FRX systems produce RFC's with a major radius R = 2-6 cm, minor radius a approximately 2 cm, and a total length l approximately 35 cm. The observed temperatures are T/sub e/ approximately 100 eV and T/sub i/ = 150-350 eV with a peak density n approximately 2 x 10 15 cm -3 . After the plasma reaches equilibrium, the RFC remains stable for up to 30 μs followed by the rapid growth of the rotational m = 2 instability, which terminates the confinement. During the stable equilibrium, the particle and energy confinement times are more than 10 times longer than in an open-field system. The behavior of the m = 2 mode qualitatively agrees with the theoretically predicted instability for rotational velocities exceeding some critical value

  10. Field reversal experiments (FRX)

    International Nuclear Information System (INIS)

    Linford, R.K.; Armstrong, W.T.; Platts, D.A.; Sherwood, E.G.

    1979-01-01

    The equilibrium, confinement, and stability properties of the reversed-field configuration (RFC) are being studied in two theta-pinch facilities. The RFC is an elongated toroidal plasma confined in a purely poloidal field geometry. The open field lines of the linear theta pinch support the closed-field RFC much like the vertical field centres the toroidal plasma in a tokamak. Depending on stability and confinement properties, the RFC might be used to greatly reduce the axial losses in linear fusion devices such as mirrors, theta pinches, and liners. The FRX systems produce RFCs with a major radius R=2-6cm, a minor radius a approximately 2cm, and a total length l approximately 35cm. The observed temperatures are Tsub(e) approximately 100eV and Tsub(i)=150-350eV with a peak density n approximately 2x10 15 cm -3 . After the plasma has reached equilibrium, the RFC remains stable for up to 30μs, followed by the rapid growth of the rotational m=2 instability, which terminates the confinement. During the stable equilibrium, the particle and energy confinement times are more than 10 times longer than in an open-field system. The behaviour of the m=2 mode agrees qualitatively with the theoretically predicted instability for rotational velocities exceeding some critical value. (author)

  11. The effect of substrate modification on microbial growth on surfaces

    International Nuclear Information System (INIS)

    Brown, Angela Ann

    1998-01-01

    The principle aim of the program was to produce a novel, non-leaching antimicrobial surface for commercial development and future use in the liquid food packaging industry. Antimicrobial surfaces which exist presently have been produced to combat the growth of prokaryotic organisms and usually function as slow release systems. A system which could inhibit eukaryotic growth without contaminating the surrounding 'environment' with the inhibitor was considered of great commercial importance. The remit of this study was concerned with creating a surface which could control the growth of eukaryotic organisms found in fruit juice with particular interest in the yeast, Saccharomyces cerevisiae. Putative antimicrobial surfaces were created by the chemical modification of the test substrate polymers; nylon and ethylvinyl alcohol (EVOH). Surfaces were chemically modified by the covalent coupling of antimicrobial agents known to be active against the yeast Saccharomyces cerevisiae as ascertained by the screening process determining the minimum inhibitory concentration (MIC) values of agents in the desired test medium. During the study it was found that a number of surfaces did appear to inhibit yeast growth in fruit juice, however on further investigation the apparent inhibitory effect was discovered to be the result of un-bound material free in the test medium. On removing the possibility of any un-bound material present on the test surface, by a series of surface washings, the inhibitory effect on yeast growth was eliminated. Of the agents tested only one appeared to have an inhibitory effect which could be attributed to a true antimicrobial surface effect, Amical 48. As there is little known about this agent in the literature, its affect on yeast growth was examined and in particular a proposal for the mode of action on yeast is discussed, providing a plausible explanation for the inhibitory effect observed when this agent is covalently immobilised onto nylon. (author)

  12. Towards a reversible functional language

    DEFF Research Database (Denmark)

    Yokoyama, Tetsuo; Axelsen, Holger Bock; Glück, Robert

    2012-01-01

    /equality operator also simplifies inverse computation and program inversion. We discuss the advantages of a reversible functional language using example programs, including run-length encoding. Program inversion is seen to be as lightweight as for imperative reversible languages and realized by recursive descent...

  13. Reverse engineering of RFID devices

    NARCIS (Netherlands)

    Bokslag, W.

    2015-01-01

    This paper discusses the relevance and potential impact of both RFID and reverse engineering of RFID technology, followed by a discussion of common protocols and internals of RFID technology. The focus of the paper is on providing an overview of the different approaches to reverse engineering RFID

  14. How decision reversibility affects motivation

    NARCIS (Netherlands)

    Bullens, L.; van Harreveld, F.; Förster, J.; Higgins, T.E.

    2014-01-01

    The present research examined how decision reversibility can affect motivation. On the basis of extant findings, it was suggested that 1 way it could affect motivation would be to strengthen different regulatory foci, with reversible decision making, compared to irreversible decision making,

  15. Enzymatic reactions in reversed micelles

    NARCIS (Netherlands)

    Hilhorst, M.H.

    1984-01-01

    It has been recognised that enzymes in reversed micelles have potential for application in chemical synthesis. Before these expectations will be realised many problems must be overcome. This thesis deals with some of them.
    In Chapter 1 the present knowledge about reversed micelles and

  16. Reverse genetics of avian metapneumoviruses

    Science.gov (United States)

    An overview of avian metapneumovirus (aMPV) infection in turkeys and development of a reverse genetics system for aMPV subgroup C (aMPV-C) virus will be presented. By using reverse genetics technology, we generated recombinant aMPV-C viruses containing a different length of glycoprotein (G) gene or...

  17. Chemical modification of glass surface with a monolayer of nonchromophoric and chromophoric methacrylate terpolymer

    Energy Technology Data Exchange (ETDEWEB)

    Janik, Ryszard [Department of Polymer Engineering and Technology, Wroclaw University of Technology, 50-370 Wroclaw (Poland); Kucharski, Stanislaw, E-mail: stanislaw.kucharski@pwr.wroc.pl [Department of Polymer Engineering and Technology, Wroclaw University of Technology, 50-370 Wroclaw (Poland); Sobolewska, Anna [Institute of Physical and Theoretical Chemistry, Wroclaw University of Technology, 50-370 Wroclaw (Poland); Barille, Regis [Institut des Sciences et Techniques Moleculaires d' Angers ' Moltech Anjou' , CNRS UMR 6200, 49045 Angers (France)

    2010-11-15

    The methacrylate terpolymers, a nonchromophoric and chromophoric one, containing 2-hydroxyethyl groups were reacted with 3-isocyanatopropyltriethoxysilane to obtain reactive polymers able to form covalent bonding with -SiOH groups of the glass surface via triethoxysilane group condensation. Chemical modification of the Corning 2949 glass plates treated in this way resulted in increase of wetting angle from 11{sup o} to ca. 70-73{sup o}. Determination of ellipsometric parameters revealed low value of the substrate refractive index as compared with that of bulk Corning 2949 glass suggesting roughness of the surface. The AFM image of the bare glass surface and that modified with terpolymer monolayer confirmed this phenomenon. Modification of the glass with the terpolymer monolayer made it possible to create the substrate surface well suited for deposition of familiar chromophore film by spin-coating. The chromophore polymer film deposited onto the modified glass surface was found to be resistant to come unstuck in aqueous solution.

  18. Discovery of a Chemical Modification by Citric Acid in a Recombinant Monoclonal Antibody

    Science.gov (United States)

    2015-01-01

    Recombinant therapeutic monoclonal antibodies exhibit a high degree of heterogeneity that can arise from various post-translational modifications. The formulation for a protein product is to maintain a specific pH and to minimize further modifications. Generally Recognized as Safe (GRAS), citric acid is commonly used for formulation to maintain a pH at a range between 3 and 6 and is generally considered chemically inert. However, as we reported herein, citric acid covalently modified a recombinant monoclonal antibody (IgG1) in a phosphate/citrate-buffered formulation at pH 5.2 and led to the formation of so-called “acidic species” that showed mass increases of 174 and 156 Da, respectively. Peptide mapping revealed that the modification occurred at the N-terminus of the light chain. Three additional antibodies also showed the same modification but displayed different susceptibilities of the N-termini of the light chain, heavy chain, or both. Thus, ostensibly unreactive excipients under certain conditions may increase heterogeneity and acidic species in formulated recombinant monoclonal antibodies. By analogy, other molecules (e.g., succinic acid) with two or more carboxylic acid groups and capable of forming an anhydride may exhibit similar reactivities. Altogether, our findings again reminded us that it is prudent to consider formulations as a potential source for chemical modifications and product heterogeneity. PMID:25136741

  19. What do reversible programs compute?

    DEFF Research Database (Denmark)

    Axelsen, Holger Bock; Glück, Robert

    2011-01-01

    Reversible computing is the study of computation models that exhibit both forward and backward determinism. Understanding the fundamental properties of such models is not only relevant for reversible programming, but has also been found important in other fields, e.g., bidirectional model...... transformation, program transformations such as inversion, and general static prediction of program properties. Historically, work on reversible computing has focussed on reversible simulations of irreversible computations. Here, we take the viewpoint that the property of reversibility itself should...... are not strictly classically universal, but that they support another notion of universality; we call this RTM-universality. Thus, even though the RTMs are sub-universal in the classical sense, they are powerful enough as to include a self-interpreter. Lifting this to other computation models, we propose r...

  20. Fundamentals of reversible flowchart languages

    DEFF Research Database (Denmark)

    Yokoyama, Tetsuo; Axelsen, Holger Bock; Glück, Robert

    2016-01-01

    Abstract This paper presents the fundamentals of reversible flowcharts. They are intended to naturally represent the structure and control flow of reversible (imperative) programming languages in a simple computation model, in the same way classical flowcharts do for conventional languages......, structured reversible flowcharts are as expressive as unstructured ones, as shown by a reversible version of the classic Structured Program Theorem. We illustrate how reversible flowcharts can be concretized with two example programming languages, complete with syntax and semantics: a low-level unstructured...... language and a high-level structured language. We introduce concrete tools such as program inverters and translators for both languages, which follow the structure suggested by the flowchart model. To further illustrate the different concepts and tools brought together in this paper, we present two major...

  1. Covalently attached multilayer assemblies of diazo-resins and binuclear cobalt phthalocyanines

    International Nuclear Information System (INIS)

    Li Xiaofang; Zhao Shuang; Yang Min; Sun Changqing; Guo, Liping

    2005-01-01

    By using the ionic self-assembly technique, ordered multilayer thin films composed of diazo-resin (DAR) as polycation and water-soluble binuclear cobalt phthalocyaninehexasulfonate (Bi-CoPc) as polyanion were alternately fabricated on quartz, CaF 2 and glassy carbon electrodes (GCEs). Upon ultraviolet irradiation, the adjacent interface of the multilayer films reacted to form a covalently cross-linking structure. The obtained thin films were characterized by ultraviolet (UV)-vis, Fourier transform infrared spectrometer (FTIR), X-ray diffraction (XRD), atomic force microscope (AFM), surface photovoltage spectra (SPS), and cyclic voltammetry. The results show that the uniform, highly stable and ordered multilayer thin films were formed. The linkage nature between the adjacent interface of the multilayer films converts from ionic to covalent, and, as a result, the stability of the multilayer thin films dramatically improved. The multilayer thin films on GCEs also exhibited excellent electrochemical behavior

  2. Covalently attached multilayer assemblies of diazo-resins and binuclear cobalt phthalocyanines

    Energy Technology Data Exchange (ETDEWEB)

    Li Xiaofang [Key Lab of Supramolecular Structure and Materials, College of Chemistry, Jilin University, Changchun 130023 (China); Zhao Shuang [Key Lab of Supramolecular Structure and Materials, College of Chemistry, Jilin University, Changchun 130023 (China); Yang Min [Key Lab of Supramolecular Structure and Materials, College of Chemistry, Jilin University, Changchun 130023 (China); Sun Changqing [Key Lab of Supramolecular Structure and Materials, College of Chemistry, Jilin University, Changchun 130023 (China)]. E-mail: sunchq@mail.jlu.edu.cn; Guo, Liping [Department of Chemistry, Northeast Normal University, Changchun 130024 (China)

    2005-05-01

    By using the ionic self-assembly technique, ordered multilayer thin films composed of diazo-resin (DAR) as polycation and water-soluble binuclear cobalt phthalocyaninehexasulfonate (Bi-CoPc) as polyanion were alternately fabricated on quartz, CaF{sub 2} and glassy carbon electrodes (GCEs). Upon ultraviolet irradiation, the adjacent interface of the multilayer films reacted to form a covalently cross-linking structure. The obtained thin films were characterized by ultraviolet (UV)-vis, Fourier transform infrared spectrometer (FTIR), X-ray diffraction (XRD), atomic force microscope (AFM), surface photovoltage spectra (SPS), and cyclic voltammetry. The results show that the uniform, highly stable and ordered multilayer thin films were formed. The linkage nature between the adjacent interface of the multilayer films converts from ionic to covalent, and, as a result, the stability of the multilayer thin films dramatically improved. The multilayer thin films on GCEs also exhibited excellent electrochemical behavior.

  3. Covalent immobilization of lipase from Candida rugosa on Eupergit®

    Directory of Open Access Journals (Sweden)

    Bezbradica Dejan I.

    2005-01-01

    Full Text Available An approach is presented for the stable covalent immobilization of Upase from Candida rugosa on Eupergit® with a high retention of hydrolytic activity. It comprises covalent bonding via lipase carbohydrate moiety previously modified by periodate oxidation, allowing a reduction in the involvement of the enzyme functional groups that are probably important in the catalytic mechanism. The hydrolytic activities of the lipase immobilized on Eupergif1 by two conventional methods (via oxirane group and via glutaralde-hyde and with periodate method were compared. Results of lipase assays suggest that periodate method is superior for lipase immobilization on Eupergit® among methods applied in this study with respect to both, yield of immobilization and hydrolytic activity of the immobilized enzyme.

  4. Combining the Physical Adsorption Approach and the Covalent Attachment Method to Prepare a Bifunctional Bioreactor

    Directory of Open Access Journals (Sweden)

    Zhi Wang

    2012-09-01

    Full Text Available Aminopropyl-functionalized SBA-15 mesoporous silica was used as a support to adsorb myoglobin. Then, in order to avoid the leakage of adsorbed myoglobin, lysozyme was covalently tethered to the internal and external surface of the mesoporous silica with glutaraldehyde as the coupling agent. The property of amino-functionalized mesoporous silica was characterized by N2 adsorption-desorption and thermogravimetric (TG analysis. The feature of the silica-based matrix before and after myoglobin adsorption was identified by fourier transform infrared (FTIR and UV/VIS measurement. With o-dianisidine and H2O2 as the substrate, the peroxidase activity of adsorbed myoglobin was determined. With Micrococus lysodeilicus as the substrate, the antibacterial activity of covalently tethered lysozyme was measured. Results demonstrated that the final product not only presented peroxidase activity of the myoglobin but yielded antibacterial activity of the lysozyme.

  5. Tribology study of reduced graphene oxide sheets on silicon substrate synthesized via covalent assembly.

    Science.gov (United States)

    Ou, Junfei; Wang, Jinqing; Liu, Sheng; Mu, Bo; Ren, Junfang; Wang, Honggang; Yang, Shengrong

    2010-10-19

    Reduced graphene oxide (RGO) sheets were covalently assembled onto silicon wafers via a multistep route based on the chemical adsorption and thermal reduction of graphene oxide (GO). The formation and microstructure of RGO were analyzed by X-ray photoelectron spectroscopy (XPS), attenuated total reflectance Fourier transform infrared (ATR-FTIR) spectroscopy, Raman spectroscopy, and water contact angle (WCA) measurements. Characterization by atomic force microscopy (AFM) was performed to evaluate the morphology and microtribological behaviors of the samples. Macrotribological performance was tested on a ball-on-plate tribometer. Results show that the assembled RGO possesses good friction reduction and antiwear ability, properties ascribed to its intrinsic structure, that is, the covalent bonding to the substrate and self-lubricating property of RGO.

  6. Three-dimensional metal-intercalated covalent organic frameworks for near-ambient energy storage

    Science.gov (United States)

    Gao, Fei; Ding, Zijing; Meng, Sheng

    2013-01-01

    A new form of nanoporous material, metal intercalated covalent organic framework (MCOF) is proposed and its energy storage property revealed. Employing density functional and thermodynamical analysis, we find that stable, chemically active, porous materials could form by stacking covalent organic framework (COF) layers with metals as a gluing agent. Metal acts as active sites, while its aggregation is suppressed by a binding energy significantly larger than the corresponding cohesive energy of bulk metals. Two important parameters, metal binding and metal-metal separation, are tuned by selecting suitable building blocks and linkers when constructing COF layers. Systematic searches among a variety of elements and organic molecules identify Ca-intercalated COF with diphenylethyne units as optimal material for H2 storage, reaching a striking gravimetric density ~ 5 wt% at near-ambient conditions (300 K, 20 bar), in comparison to < 0.1 wt% for bare COF-1 under the same condition. PMID:23698018

  7. Gold nanoparticles covalently assembled onto vesicle structures as possible biosensing platform

    Directory of Open Access Journals (Sweden)

    M. Fátima Barroso

    2016-05-01

    Full Text Available In this contribution a strategy is shown to covalently immobilize gold nanoparticles (AuNPs onto vesicle bilayers with the aim of using this nanomaterial as platform for the future design of immunosensors. A novel methodology for the self-assembly of AuNPs onto large unilamellar vesicle structures is described. The vesicles were formed with 1,2-dioleoyl-sn-glycero-3-phosphocholine (DOPC and 1-undecanethiol (SH. After, the AuNPs photochemically synthesized in pure glycerol were mixed and anchored onto SH–DOPC vesicles. The data provided by voltammetry, spectrometry and microscopy techniques indicated that the AuNPs were successfully covalently anchored onto the vesicle bilayer and decorated vesicles exhibit a spherical shape with a size of 190 ± 10 nm. The developed procedure is easy, rapid and reproducible to start designing a possible immunosensor by using environmentally friendly procedures.

  8. Self-Assembled Polystyrene Beads for Templated Covalent Functionalization of Graphitic Substrates Using Diazonium Chemistry.

    Science.gov (United States)

    Van Gorp, Hans; Walke, Peter; Bragança, Ana M; Greenwood, John; Ivasenko, Oleksandr; Hirsch, Brandon E; De Feyter, Steven

    2018-04-11

    A network of self-assembled polystyrene beads was employed as a lithographic mask during covalent functionalization reactions on graphitic surfaces to create nanocorrals for confined molecular self-assembly studies. The beads were initially assembled into hexagonal arrays at the air-liquid interface and then transferred to the substrate surface. Subsequent electrochemical grafting reactions involving aryl diazonium molecules created covalently bound molecular units that were localized in the void space between the nanospheres. Removal of the bead template exposed hexagonally arranged circular nanocorrals separated by regions of chemisorbed molecules. Small molecule self-assembly was then investigated inside the resultant nanocorrals using scanning tunneling microscopy to highlight localized confinement effects. Overall, this work illustrates the utility of self-assembly principles to transcend length scale gaps in the development of hierarchically patterned molecular materials.

  9. Flavin-N5 Covalent Intermediate in a Nonredox Dehalogenation Reaction Catalyzed by an Atypical Flavoenzyme.

    Science.gov (United States)

    Dai, Yumin; Kizjakina, Karina; Campbell, Ashley C; Korasick, David A; Tanner, John J; Sobrado, Pablo

    2018-01-04

    The flavin-dependent enzyme 2-haloacrylate hydratase (2-HAH) catalyzes the conversion of 2-chloroacrylate, a major component in the manufacture of acrylic polymers, to pyruvate. The enzyme was expressed in Escherichia coli, purified, and characterized. 2-HAH was shown to be monomeric in solution and contained a non-covalent, yet tightly bound, flavin adenine dinucleotide (FAD). Although the catalyzed reaction was redox-neutral, 2-HAH was active only in the reduced state. A covalent flavin-substrate intermediate, consistent with the flavin-acrylate iminium ion, was trapped with cyanoborohydride and characterized by mass spectrometry. Small-angle X-ray scattering was consistent with 2-HAH belonging to the succinate dehydrogenase/fumarate reductase family of flavoproteins. These studies establish 2-HAH as a novel noncanonical flavoenzyme. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  10. Carbon dioxide capture using covalent organic frameworks (COFs) type material-a theoretical investigation.

    Science.gov (United States)

    Dash, Bibek

    2018-04-26

    The present work deals with a density functional theory (DFT) study of porous organic framework materials containing - groups for CO 2 capture. In this study, first principle calculations were performed for CO 2 adsorption using N-containing covalent organic framework (COFs) models. Ab initio and DFT-based methods were used to characterize the N-containing porous model system based on their interaction energies upon complexing with CO 2 and nitrogen gas. Binding energies (BEs) of CO 2 and N 2 molecules with the polymer framework were calculated with DFT methods. Hybrid B3LYP and second order MP2 methods combined with of Pople 6-31G(d,p) and correlation consistent basis sets cc-pVDZ, cc-pVTZ and aug-ccVDZ were used to calculate BEs. The effect of linker groups in the designed covalent organic framework model system on the CO 2 and N 2 interactions was studied using quantum calculations.

  11. Crystal structure of the covalent intermediate of amylosucrase from Neisseria polysaccharea

    DEFF Research Database (Denmark)

    Jensen, Malene H; Mirza, Osman Asghar; Albenne, Cecile

    2004-01-01

    The alpha-retaining amylosucrase from the glycoside hydrolase family 13 performs a transfer reaction of a glucosyl moiety from sucrose to an acceptor molecule. Amylosucrase has previously been shown to be able to use alpha-D-glucopyranosyl fluoride as a substrate, which suggested that it could also...... the first covalent intermediate of an alpha-retaining glycoside hydrolase where the glucosyl moiety is identical to the expected biologically relevant entity. Comparison to other enzymes with anticipated glucosylic covalent intermediates suggests that this structure is a representative model...... for such intermediates. Analysis of the active site shows how oligosaccharide binding disrupts the putative nucleophilic water binding site found in the hydrolases of the GH family 13. This reveals important parts of the structural background for the shift in function from hydrolase to transglycosidase seen...

  12. Potent haloperidol derivatives covalently binding to the dopamine D2 receptor.

    Science.gov (United States)

    Schwalbe, Tobias; Kaindl, Jonas; Hübner, Harald; Gmeiner, Peter

    2017-10-01

    The dopamine D 2 receptor (D 2 R) is a common drug target for the treatment of a variety of neurological disorders including schizophrenia. Structure based design of subtype selective D 2 R antagonists requires high resolution crystal structures of the receptor and pharmacological tools promoting a better understanding of the protein-ligand interactions. Recently, we reported the development of a chemically activated dopamine derivative (FAUC150) designed to covalently bind the L94C mutant of the dopamine D 2 receptor. Using FAUC150 as a template, we elaborated the design and synthesis of irreversible analogs of the potent antipsychotic drug haloperidol forming covalent D 2 R-ligand complexes. The disulfide- and Michael acceptor-functionalized compounds showed significant receptor affinity and an irreversible binding profile in radioligand depletion experiments. Copyright © 2017 Elsevier Ltd. All rights reserved.

  13. Second-Generation Non-Covalent NAAA Inhibitors are Protective in a Model of Multiple Sclerosis.

    Science.gov (United States)

    Migliore, Marco; Pontis, Silvia; Fuentes de Arriba, Angel Luis; Realini, Natalia; Torrente, Esther; Armirotti, Andrea; Romeo, Elisa; Di Martino, Simona; Russo, Debora; Pizzirani, Daniela; Summa, Maria; Lanfranco, Massimiliano; Ottonello, Giuliana; Busquet, Perrine; Jung, Kwang-Mook; Garcia-Guzman, Miguel; Heim, Roger; Scarpelli, Rita; Piomelli, Daniele

    2016-09-05

    Palmitoylethanolamide (PEA) and oleoylethanolamide (OEA) are endogenous lipid mediators that suppress inflammation. Their actions are terminated by the intracellular cysteine amidase, N-acylethanolamine acid amidase (NAAA). Even though NAAA may offer a new target for anti-inflammatory therapy, the lipid-like structures and reactive warheads of current NAAA inhibitors limit the use of these agents as oral drugs. A series of novel benzothiazole-piperazine derivatives that inhibit NAAA in a potent and selective manner by a non-covalent mechanism are described. A prototype member of this class (8) displays high oral bioavailability, access to the central nervous system (CNS), and strong activity in a mouse model of multiple sclerosis (MS). This compound exemplifies a second generation of non-covalent NAAA inhibitors that may be useful in the treatment of MS and other chronic CNS disorders. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  14. Layer-by-Layer Self-Assembled Graphene Multilayer Films via Covalent Bonds for Supercapacitor Electrodes

    Directory of Open Access Journals (Sweden)

    Xianbin Liu

    2015-05-01

    Full Text Available To maximize the utilization of its single-atom thin nature, a facile scheme to fabricate graphene multilayer films via a layer-by-layer self-assembled process was presented. The structure of multilayer films was constructed by covalently bonding graphene oxide (GO using p-phenylenediamine (PPD as a covalent cross-linking agent. The assembly process was confirmed to be repeatable and the structure was stable. With the π-π conjugated structure and a large number of spaces in the framework, the graphene multi‐ layer films exhibited excellent electrochemical perform‐ ance. The uniform ultrathin electrode exhibited a capacitance of 41.71 μF/cm2 at a discharge current of 0.1 μA/cm2, and displayed excellent stability of 88.9 % after 1000 charge-discharge cycles.

  15. Graphene and Carbon-Nanotube Nanohybrids Covalently Functionalized by Porphyrins and Phthalocyanines for Optoelectronic Properties.

    Science.gov (United States)

    Wang, Aijian; Ye, Jun; Humphrey, Mark G; Zhang, Chi

    2018-04-01

    In recent years, there has been a rapid growth in studies of the optoelectronic properties of graphene, carbon nanotubes (CNTs), and their derivatives. The chemical functionalization of graphene and CNTs is a key requirement for the development of this field, but it remains a significant challenge. The focus here is on recent advances in constructing nanohybrids of graphene or CNTs covalently linked to porphyrins or phthalocyanines, as well as their application in nonlinear optics. Following a summary of the syntheses of nanohybrids constructed from graphene or CNTs and porphyrins or phthalocyanines, explicit intraconjugate electronic interactions between photoexcited porphyrins/phthalocyanines and graphene/CNTs are introduced classified by energy transfer, electron transfer, and charge transfer, and their optoelectronic applications are also highlighted. The major current challenges for the development of covalently linked nanohybrids of porphyrins or phthalocyanines and carbon nanostructures are also presented. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  16. Improved Procedure for Preparation of Covalently Bonded Cellulose Tris-phenylcarbamate Chiral Stationary Phases

    Institute of Scientific and Technical Information of China (English)

    秦峰; 陈小明; 刘月启; 邹汉法; 王俊德

    2005-01-01

    The classical method for preparation of covalently boned cellulose derivative chiral stationary phases (CSP) with diisocyanate as spacer was improved. Diisocyanate was firstly allowed to react with 3-aminopropyltriethoxysilane, and the resulting product was then applied as the spacer reagent to immobilize cellulose derivatives onto silica gel. Influences of the amount and the length of the spacer on the optical resolution ability of the CSP were investigated. Comparing improved procedure to classical diisocyanate method, the cross-linking between the glucose units of the cellulose derivatives was avoided to the most extent. With the improved procedure, regio-nonselective ways could be adooted to prepare covalently bonded CSP, which showed an advantage for the rapid preparation.

  17. Molecular characterization of covalent complexes between tissue transglutaminase and gliadin peptides

    DEFF Research Database (Denmark)

    Fleckenstein, Burkhard; Qiao, Shuo-Wang; Larsen, Martin Røssel

    2004-01-01

    recognized by intestinal T cells from patients. Incubation of TG2 with gliadin peptides also results in the formation of covalent TG2-peptide complexes. Here we report the characterization of complexes between TG2 and two immunodominant gliadin peptides. Two types of covalent complexes were found......; the peptides are either linked via a thioester bond to the active site cysteine of TG2 or via isopeptide bonds to particular lysine residues of the enzyme. We quantified the number of gliadin peptides bound to TG2 under different conditions. After 30 min of incubation of TG2 at 1 microm with an equimolar ratio...... of peptides to TG2, approximately equal amounts of peptides were bound by thioester and isopeptide linkage. At higher peptide to TG2 ratios, more than one peptide was linked to TG2, and isopeptide bond formation dominated. The lysine residues in TG2 that act as acyl acceptors were identified by matrix...

  18. Fast and accurate covalent bond predictions using perturbation theory in chemical space

    Science.gov (United States)

    Chang, Kuang-Yu; von Lilienfeld, Anatole

    I will discuss the predictive accuracy of perturbation theory based estimates of changes in covalent bonding due to linear alchemical interpolations among systems of different chemical composition. We have investigated single, double, and triple bonds occurring in small sets of iso-valence-electronic molecular species with elements drawn from second to fourth rows in the p-block of the periodic table. Numerical evidence suggests that first order estimates of covalent bonding potentials can achieve chemical accuracy (within 1 kcal/mol) if the alchemical interpolation is vertical (fixed geometry) among chemical elements from third and fourth row of the periodic table. When applied to nonbonded systems of molecular dimers or solids such as III-V semiconductors, alanates, alkali halides, and transition metals, similar observations hold, enabling rapid predictions of van der Waals energies, defect energies, band-structures, crystal structures, and lattice constants.

  19. Identification of an estrogen receptor α non covalent ubiquitin-binding surface: role in 17β-estradiol-induced transcriptional activity.

    Science.gov (United States)

    Pesiri, Valeria; La Rosa, Piergiorgio; Stano, Pasquale; Acconcia, Filippo

    2013-06-15

    Ubiquitin (Ub)-binding domains (UBDs) located in Ub receptors decode the ubiquitination signal by non-covalently engaging the Ub modification on their binding partners and transduce the Ub signalling through Ub-based molecular interactions. In this way, inducible protein ubiquitination regulates diverse biological processes. The estrogen receptor alpha (ERα) is a ligand-activated transcription factor that mediates the pleiotropic effects of the sex hormone 17β-estradiol (E2). Fine regulation of E2 pleiotropic actions depends on E2-dependent ERα association with a plethora of binding partners and/or on the E2 modulation of receptor ubiquitination. Indeed, E2-induced ERα polyubiquitination triggers receptor degradation and transcriptional activity, and E2-dependent reduction in ERα monoubiquitination is crucial for E2 signalling. Monoubiquitinated proteins often contain UBDs, but whether non-covalent Ub-ERα binding could occur and play a role in E2-ERα signalling is unknown. Here, we report an Ub-binding surface within the ERα ligand binding domain that directs in vitro the receptor interaction with both ubiquitinated proteins and recombinant Ub chains. Mutational analysis reveals that ERα residues leucine 429 and alanine 430 are involved in Ub binding. Moreover, impairment of ERα association to ubiquitinated species strongly affects E2-induced ERα transcriptional activity. Considering the importance of UBDs in the Ub-based signalling network and the central role of different ERα binding partners in the modulation of E2-dependent effects, our discoveries provide novel insights into ERα activity that could also be relevant for ERα-dependent diseases.

  20. Covalent defects restrict supramolecular self-assembly of homopolypeptides: case study of β2-fibrils of poly-L-glutamic acid.

    Directory of Open Access Journals (Sweden)

    Aleksandra Fulara

    Full Text Available Poly-L-glutamic acid (PLGA often serves as a model in studies on amyloid fibrils and conformational transitions in proteins, and as a precursor for synthetic biomaterials. Aggregation of PLGA chains and formation of amyloid-like fibrils was shown to continue on higher levels of superstructural self-assembly coinciding with the appearance of so-called β2-sheet conformation manifesting in dramatic redshift of infrared amide I' band below 1600 cm(-1. This spectral hallmark has been attributed to network of bifurcated hydrogen bonds coupling C = O and N-D (N-H groups of the main chains to glutamate side chains. However, other authors reported that, under essentially identical conditions, PLGA forms the conventional in terms of infrared characteristics β1-sheet structure (exciton-split amide I' band with peaks at ca. 1616 and 1683 cm(-1. Here we attempt to shed light on this discrepancy by studying the effect of increasing concentration of intentionally induced defects in PLGA on the tendency to form β1/β2-type aggregates using infrared spectroscopy. We have employed carbodiimide-mediated covalent modification of Glu side chains with n-butylamine (NBA, as well as electrostatics-driven inclusion of polylysine chains, as two different ways to trigger structural defects in PLGA. Our study depicts a clear correlation between concentration of defects in PLGA and increasing tendency to depart from the β2-structure toward the one less demanding in terms of chemical uniformity of side chains: β1-structure. The varying predisposition to form β1- or β2-type aggregates assessed by infrared absorption was compared with the degree of morphological order observed in electron microscopy images. Our results are discussed in the context of latent covalent defects in homopolypeptides (especially with side chains capable of hydrogen-bonding that could obscure their actual propensities to adopt different conformations, and limit applications in the field of

  1. Covalent Defects Restrict Supramolecular Self-Assembly of Homopolypeptides: Case Study of β2-Fibrils of Poly-L-Glutamic Acid

    Science.gov (United States)

    Fulara, Aleksandra; Hernik, Agnieszka; Nieznańska, Hanna; Dzwolak, Wojciech

    2014-01-01

    Poly-L-glutamic acid (PLGA) often serves as a model in studies on amyloid fibrils and conformational transitions in proteins, and as a precursor for synthetic biomaterials. Aggregation of PLGA chains and formation of amyloid-like fibrils was shown to continue on higher levels of superstructural self-assembly coinciding with the appearance of so-called β2-sheet conformation manifesting in dramatic redshift of infrared amide I′ band below 1600 cm−1. This spectral hallmark has been attributed to network of bifurcated hydrogen bonds coupling C = O and N-D (N-H) groups of the main chains to glutamate side chains. However, other authors reported that, under essentially identical conditions, PLGA forms the conventional in terms of infrared characteristics β1-sheet structure (exciton-split amide I′ band with peaks at ca. 1616 and 1683 cm−1). Here we attempt to shed light on this discrepancy by studying the effect of increasing concentration of intentionally induced defects in PLGA on the tendency to form β1/β2-type aggregates using infrared spectroscopy. We have employed carbodiimide-mediated covalent modification of Glu side chains with n-butylamine (NBA), as well as electrostatics-driven inclusion of polylysine chains, as two different ways to trigger structural defects in PLGA. Our study depicts a clear correlation between concentration of defects in PLGA and increasing tendency to depart from the β2-structure toward the one less demanding in terms of chemical uniformity of side chains: β1-structure. The varying predisposition to form β1- or β2-type aggregates assessed by infrared absorption was compared with the degree of morphological order observed in electron microscopy images. Our results are discussed in the context of latent covalent defects in homopolypeptides (especially with side chains capable of hydrogen-bonding) that could obscure their actual propensities to adopt different conformations, and limit applications in the field of synthetic

  2. Covalent attachment of aptamer onto nanocomposite as a high performance electrochemical sensing platform: Fabrication of an ultra-sensitive ibuprofen electrochemical aptasensor

    Energy Technology Data Exchange (ETDEWEB)

    Roushani, Mahmoud, E-mail: mahmoudroushani@yahoo.com; Shahdost-fard, Faezeh

    2016-11-01

    In the present study, we report a selective electrochemical aptasensor for the ultrasensitive detection of an anti-inflammatory drug, ibuprofen (IBP). The proposed system was achieved by the modification of a glassy carbon electrode (GCE) with multiwalled carbon nanotubes/ionic liquid/chitosan (MWCNTs/IL/Chit) nanocomposite and the covalent immobilization of the IBP specific aptamer (Apt) onto the modified electrode surface followed by methylene blue (MB) intercalated onto the Apt as the electrochemical redox marker. Upon the incubation of the IBP as a target in the proposed aptasensor, the peak current of MB decreases due to the formation of the Apt-IBP complex and the displacement of MB from the immobilized Apt onto the modified electrode surface. The nanocomposite not only increases the electrode surface area and accelerate the electron transfer kinetics but also it provides a highly stable matrix to enhance the loading amount of the Apt DNA sequence. Through differential pulse voltammetry (DPV) experiments, it was found that the proposed aptasensor could detect the IBP with a linear range (70 pM up to 6 μM) and the detection limit (LOD) as low as 20 pM. The results showed that the aptasensor had good sensitivity, stability, reproducibility, and specificity to detect the IBP. The proposed aptasensor was successfully applied for measuring the IBP concentration in real samples. Based on our experiments we can say that the present method proposes new horizons for the development of other aptasensors for diagnostic application in biosensing. - Highlights: • An electrochemical aptasensor is developed for ultrasensitive detection of IBP. • The aptasensor is made by covalent immobilization of aptamer on a modified GCE. • A nanocomposite as a modifier provides a specific surface with high conductivity. • This nanocomposite leads to a high density of the DNA sequence on the GCE surface. • This method proposes new horizons for development other aptasensors for

  3. Gating mechanism of Kv11.1 (hERG) K+ channels without covalent connection between voltage sensor and pore domains.

    Science.gov (United States)

    de la Peña, Pilar; Domínguez, Pedro; Barros, Francisco

    2018-03-01

    Kv11.1 (hERG, KCNH2) is a voltage-gated potassium channel crucial in setting the cardiac rhythm and the electrical behaviour of several non-cardiac cell types. Voltage-dependent gating of Kv11.1 can be reconstructed from non-covalently linked voltage sensing and pore modules (split channels), challenging classical views of voltage-dependent channel activation based on a S4-S5 linker acting as a rigid mechanical lever to open the gate. Progressive displacement of the split position from the end to the beginning of the S4-S5 linker induces an increasing negative shift in activation voltage dependence, a reduced z g value and a more negative ΔG 0 for current activation, an almost complete abolition of the activation time course sigmoid shape and a slowing of the voltage-dependent deactivation. Channels disconnected at the S4-S5 linker near the S4 helix show a destabilization of the closed state(s). Furthermore, the isochronal ion current mode shift magnitude is clearly reduced in the different splits. Interestingly, the progressive modifications of voltage dependence activation gating by changing the split position are accompanied by a shift in the voltage-dependent availability to a methanethiosulfonate reagent of a Cys introduced at the upper S4 helix. Our data demonstrate for the first time that alterations in the covalent connection between the voltage sensor and the pore domains impact on the structural reorganizations of the voltage sensor domain. Also, they support the hypothesis that the S4-S5 linker integrates signals coming from other cytoplasmic domains that constitute either an important component or a crucial regulator of the gating machinery in Kv11.1 and other KCNH channels.

  4. Covalent attachment of aptamer onto nanocomposite as a high performance electrochemical sensing platform: Fabrication of an ultra-sensitive ibuprofen electrochemical aptasensor

    International Nuclear Information System (INIS)

    Roushani, Mahmoud; Shahdost-fard, Faezeh

    2016-01-01

    In the present study, we report a selective electrochemical aptasensor for the ultrasensitive detection of an anti-inflammatory drug, ibuprofen (IBP). The proposed system was achieved by the modification of a glassy carbon electrode (GCE) with multiwalled carbon nanotubes/ionic liquid/chitosan (MWCNTs/IL/Chit) nanocomposite and the covalent immobilization of the IBP specific aptamer (Apt) onto the modified electrode surface followed by methylene blue (MB) intercalated onto the Apt as the electrochemical redox marker. Upon the incubation of the IBP as a target in the proposed aptasensor, the peak current of MB decreases due to the formation of the Apt-IBP complex and the displacement of MB from the immobilized Apt onto the modified electrode surface. The nanocomposite not only increases the electrode surface area and accelerate the electron transfer kinetics but also it provides a highly stable matrix to enhance the loading amount of the Apt DNA sequence. Through differential pulse voltammetry (DPV) experiments, it was found that the proposed aptasensor could detect the IBP with a linear range (70 pM up to 6 μM) and the detection limit (LOD) as low as 20 pM. The results showed that the aptasensor had good sensitivity, stability, reproducibility, and specificity to detect the IBP. The proposed aptasensor was successfully applied for measuring the IBP concentration in real samples. Based on our experiments we can say that the present method proposes new horizons for the development of other aptasensors for diagnostic application in biosensing. - Highlights: • An electrochemical aptasensor is developed for ultrasensitive detection of IBP. • The aptasensor is made by covalent immobilization of aptamer on a modified GCE. • A nanocomposite as a modifier provides a specific surface with high conductivity. • This nanocomposite leads to a high density of the DNA sequence on the GCE surface. • This method proposes new horizons for development other aptasensors for

  5. An efficient immunodetection method for histone modifications in plants.

    Science.gov (United States)

    Nic-Can, Geovanny; Hernández-Castellano, Sara; Kú-González, Angela; Loyola-Vargas, Víctor M; De-la-Peña, Clelia

    2013-12-16

    Epigenetic mechanisms can be highly dynamic, but the cross-talk among them and with the genome is still poorly understood. Many of these mechanisms work at different places in the cell and at different times of organism development. Covalent histone modifications are one of the most complex and studied epigenetic mechanisms involved in cellular reprogramming and development in plants. Therefore, the knowledge of the spatial distribution of histone methylation in different tissues is important to understand their behavior on specific cells. Based on the importance of epigenetic marks for biology, we present a simplified, inexpensive and efficient protocol for in situ immunolocalization on different tissues such as flowers, buds, callus, somatic embryo and meristematic tissue from several plants of agronomical and biological importance. Here, we fully describe all the steps to perform the localization of histone modifications. Using this method, we were able to visualize the distribution of H3K4me3 and H3K9me2 without loss of histological integrity of tissues from several plants, including Agave tequilana, Capsicum chinense, Coffea canephora and Cedrela odorata, as well as Arabidopsis thaliana. There are many protocols to study chromatin modifications; however, most of them are expensive, difficult and require sophisticated equipment. Here, we provide an efficient protocol for in situ localization of histone methylation that dispenses with the use of expensive and sensitive enzymes. The present method can be used to investigate the cellular distribution and localization of a wide array of proteins, which could help to clarify the biological role that they play at specific times and places in different tissues of various plant species.

  6. Photoreactivation reverses ultraviolet radition induced premutagenic lesions leading to frameshift mutations in Escherichia coli

    International Nuclear Information System (INIS)

    Yamamoto, Kazuo

    1985-01-01

    The effect of photoreactivation of the ultraviolet radiation induced reversion of a trpE9777 frameshift mutation was studied in a uvr A6 derivative of Escherichia coli K12. Two different photoreactivation treatments were used, one providing a single flash of photoreactivating light and another providing 10 min of light from fluorescent lamps. The reversion frequency of the trpE9777 frameshift mutation was strongly reduced when subsueqently exposed to visible light. The dose modification factor (the ratio of equally effective doses), for cells challenged with single-flash photoreactivation, for survival and induction of reversion to Trp + was 3.6 and 3.4, respectively. UV induction of RecA protein synthesis was not reversed by a single flash of photoreactivation. The dose modification factor for 10 min of fluorescent lamp photoreactivation for survival and for induction of reversion to Trp + was 6.5 and 6.3, respectively. The dose modification factor for 10 min of photoreactivation for induction of RecA protein was 1.7-2.5. Photoreactivation decreased the reversion of trpE9777 and increased survival to the same extent. We concluded that cyclobutyl pyrimidine dimers are the premutagenic lesions of UV mutagenesis of the trpE9777 allele in a uvr A6 background. (orig.)

  7. A carrier for non-covalent delivery of functional beta-galactosidase and antibodies against amyloid plaques and IgM to the brain.

    Directory of Open Access Journals (Sweden)

    Gobinda Sarkar

    Full Text Available BACKGROUND: Therapeutic intervention of numerous brain-associated disorders currently remains unrealized due to serious limitations imposed by the blood-brain-barrier (BBB. The BBB generally allows transport of small molecules, typically <600 daltons with high octanol/water partition coefficients, but denies passage to most larger molecules. However, some receptors present on the BBB allow passage of cognate proteins to the brain. Utilizing such receptor-ligand systems, several investigators have developed methods for delivering proteins to the brain, a critical requirement of which involves covalent linking of the target protein to a carrier entity. Such covalent modifications involve extensive preparative and post-preparative chemistry that poses daunting limitations in the context of delivery to any organ. Here, we report creation of a 36-amino acid peptide transporter, which can transport a protein to the brain after routine intravenous injection of the transporter-protein mixture. No covalent linkage of the protein with the transporter is necessary. APPROACH: A peptide transporter comprising sixteen lysine residues and 20 amino acids corresponding to the LDLR-binding domain of apolipoprotein E (ApoE was synthesized. Transport of beta-galactosidase, IgG, IgM, and antibodies against amyloid plques to the brain upon iv injection of the protein-transporter mixture was evaluated through staining for enzyme activity or micro single photon emission tomography (micro-SPECT or immunostaining. Effect of the transporter on the integrity of the BBB was also investigated. PRINCIPAL FINDINGS: The transporter enabled delivery to the mouse brain of functional beta-galactosidase, human IgG and IgM, and two antibodies that labeled brain-associated amyloid beta plaques in a mouse model of Alzheimer's disease. SIGNIFICANCE: The results suggest the transporter is able to transport most or all proteins to the brain without the need for chemically linking the

  8. Fabrication and characterization of all-covalent nanocomposite functionalized screen-printed voltammetric sensors

    International Nuclear Information System (INIS)

    Jasmin, Jean-Philippe; Cannizzo, Caroline; Dumas, Eddy; Chaussé, Annie

    2014-01-01

    Highlights: • Screen printed electrodes were covalently functionalized by gold nanoparticles. • The covalent grafting of AuNPs was achieved via diazonium salt chemistry. • Two grafting methods and two types of AuNPs were compared. • Carboxylate ligands were grafted on these nanostructured electrodes. • Good preliminary responses towards lead analysis were obtained by SW-ASV. - Abstract: We report in this paper an all-covalent method to obtain highly nanostructured carbon screen printed electrodes (SPEs) bearing gold nanoparticles (AuNPs) functionalized by complexing groups using diazonium salts chemistry. SPEs were first modified with 4-aminophenyl functions (SPE-Ph-NH 2 ). The amino moieties were then converted into diazonium salts (SPE-Ph-N 2 + Cl − ). These reactive SPEs were then used to immobilize AuNPs by electrochemical or spontaneous method. The spontaneous method proved to be a more efficient grafting approach. Two types of AuNPs suspensions were compared: AuNPs obtained via the well-known Turkevich method, citrate-stabilized and having a diameter of about 20 nm, and AuNPs obtained by the method recently described by Eah et al., stabilizer-free with an average diameter of 4 nm. We show that the size of the Au-NPs, their concentration and their surface properties are key parameters that affect the electrochemical properties of the final nanostructured SPEs. The covalent grafting of 4-carboxyphenyl ligands through diazonium chemistry, able to complex metallic cations, at the surface of SPE-Ph-AuNPs allowed their use for the detection of Pb(II). Electrochemical Impedance Spectroscopy, Cyclic Voltammetry, Scanning Electron Microscopy, Rutherford Backscattering and X-ray Photoelectron Spectroscopy were used to characterize these nanostructured materials

  9. Designing Porphyrinic Covalent Organic Frameworks for the Photodynamic Inactivation of Bacteria

    Czech Academy of Sciences Publication Activity Database

    Hynek, Jan; Zelenka, J.; Rathouský, Jiří; Kubát, Pavel; Ruml, T.; Demel, Jan; Lang, Kamil

    2018-01-01

    Roč. 10, č. 10 (2018), s. 8527-8535 ISSN 1944-8244 R&D Projects: GA ČR(CZ) GA16-15020S Institutional support: RVO:61388980 ; RVO:61388955 Keywords : antibacterial coating * biofilm * covalent organic framework * photodynamic * porphyrin * singlet oxygen Subject RIV: CA - Inorganic Chemistry; CF - Physical ; Theoretical Chemistry (UFCH-W) OBOR OECD: Inorganic and nuclear chemistry; Physical chemistry (UFCH-W) Impact factor: 7.504, year: 2016

  10. Nanomolar hydrogen peroxide detection using horseradish peroxidase covalently linked to undoped nanocrystalline diamond surfaces

    Czech Academy of Sciences Publication Activity Database

    Wang, Q.; Kromka, Alexander; Houdková, Jana; Babchenko, Oleg; Rezek, Bohuslav; Li, M.; Boukherroub, R.; Szunerits, S.

    2012-01-01

    Roč. 28, č. 1 (2012), s. 587-592 ISSN 0743-7463 R&D Projects: GA AV ČR KAN400100701; GA AV ČR(CZ) IAAX00100902 Institutional research plan: CEZ:AV0Z10100521 Keywords : intrinsic diamond * large area growth * optical biosensor * covalent * XPS Subject RIV: BM - Solid Matter Physics ; Magnetism Impact factor: 4.187, year: 2012

  11. Synthesis and characterization of covalent diphenylalanine nanotube-folic acid conjugates

    DEFF Research Database (Denmark)

    León, John Jairo Castillo; Rindzevicius, Tomas; Wu, Kaiyu

    2014-01-01

    Herein, we describe the synthesis and characterization of a covalent nanoscale assembly formed between diphenylalanine micro/nanotubes (PNT) and folic acid (FA). The conjugate was obtained via chemical functionalization through coupling of amine groups of PNTs and carboxylic groups of FA. The sur...... for applications in the detection and diagnosis of cancer or tropical diseases such as leishmaniasis and as a carrier nanosystem delivering drugs to malignant tumors that overexpress folate receptors....

  12. Iron Intercalation in Covalent-Organic Frameworks: A Promising Approach for Semiconductors

    OpenAIRE

    Pakhira, Srimanta; Lucht, Kevin P.; Mendoza-Cortes, Jose L.

    2017-01-01

    Covalent-organic frameworks (COFs) are intriguing platforms for designing functional molecular materials. Here, we present a computational study based on van der Waals dispersion-corrected hybrid density functional theory (DFT-D) to design boroxine-linked and triazine-linked COFs intercalated with Fe. Keeping the original $P-6m2$ symmetry of the pristine COF (COF-Fe-0), we have computationally designed seven new COFs by intercalating Fe atoms between two organic layers. The equilibrium struct...

  13. Description of Non-Covalent Interactions in SCC-DFTB Methods

    Czech Academy of Sciences Publication Activity Database

    Miriyala, Vijay Madhav; Řezáč, Jan

    2017-01-01

    Roč. 38, č. 10 (2017), s. 688-697 ISSN 0192-8651 R&D Projects: GA ČR(CZ) GJ16-11321Y Institutional support: RVO:61388963 Keywords : density functional tight binding * DFTB3 * non- covalent interactions * dispersion correction * hydrogen bonding correction Subject RIV: CF - Physical ; Theoretical Chemistry OBOR OECD: Physical chemistry Impact factor: 3.229, year: 2016

  14. Anisotropic Covalency Contributions to Superexchange Pathways in Type One Copper Active Sites

    Science.gov (United States)

    2015-01-01

    Type one (T1) Cu sites deliver electrons to catalytic Cu active sites: the mononuclear type two (T2) Cu site in nitrite reductases (NiRs) and the trinuclear Cu cluster in the multicopper oxidases (MCOs). The T1 Cu and the remote catalytic sites are connected via a Cys-His intramolecular electron-transfer (ET) bridge, which contains two potential ET pathways: P1 through the protein backbone and P2 through the H-bond between the Cys and the His. The high covalency of the T1 Cu–S(Cys) bond is shown here to activate the T1 Cu site for hole superexchange via occupied valence orbitals of the bridge. This covalency-activated electronic coupling (HDA) facilitates long-range ET through both pathways. These pathways can be selectively activated depending on the geometric and electronic structure of the T1 Cu site and thus the anisotropic covalency of the T1 Cu–S(Cys) bond. In NiRs, blue (π-type) T1 sites utilize P1 and green (σ-type) T1 sites utilize P2, with P2 being more efficient. Comparing the MCOs to NiRs, the second-sphere environment changes the conformation of the Cys-His pathway, which selectively activates HDA for superexchange by blue π sites for efficient turnover in catalysis. These studies show that a given protein bridge, here Cys-His, provides different superexchange pathways and electronic couplings depending on the anisotropic covalencies of the donor and acceptor metal sites. PMID:25310460

  15. The use of Wannier function in the calculations of band structure of covalent crystals

    International Nuclear Information System (INIS)

    Lu Dong; Yang Guang

    1985-10-01

    A variational procedure has been used to build up Wannier functions to study the energy bands of diamond, silicon and α-tin. For the case of silicon the Wannier function, density of charge and band structure are calculated self-consistently and a simple method in a non-self-consistent way has been used to compute the band structure of diamond, silicon and α-tin. The method seems to be effective to describe the electronic properties of covalent crystals. (author)

  16. Inulin hydrolysis by inulinase immobilized covalently on magnetic nanoparticles prepared with wheat gluten hydrolysates

    OpenAIRE

    Homa Torabizadeh; Asieh Mahmoudi

    2018-01-01

    Inulinase can produce a high amount of fructose syrup from inulin in a one-step enzymatic process. Inulinase from Aspergillus niger was immobilized covalently on Fe3O4 magnetic nanoparticles functionalized with wheat gluten hydrolysates (WGHs). Wheat gluten was enzymatically hydrolyzed by two endopeptidases Alcalase and Neutrase and related nanoparticles were prepared by desolvation method. Magnetite nanoparticles were coated with WGHs nanoparticles and then inulinase was immobilized onto it ...

  17. The Geomagnetic Field During a Reversal

    Science.gov (United States)

    Heirtzler, James R.

    2003-01-01

    By modifying the IGRF it is possible to learn what may happen to the geomagnetic field during a geomagnetic reversal. If the entire IGRF reverses then the declination and inclination only reverse when the field strength is zero. If only the dipole component of the IGRF reverses a large geomagnetic field remains when the dipole component is zero and he direction of the field at the end of the reversal is not exactly reversed from the directions at the beginning of the reversal.

  18. Microwave plasma induced surface modification of diamond-like carbon films

    Science.gov (United States)

    Rao Polaki, Shyamala; Kumar, Niranjan; Gopala Krishna, Nanda; Madapu, Kishore; Kamruddin, Mohamed; Dash, Sitaram; Tyagi, Ashok Kumar

    2017-12-01

    Tailoring the surface of diamond-like carbon (DLC) film is technically relevant for altering the physical and chemical properties, desirable for useful applications. A physically smooth and sp3 dominated DLC film with tetrahedral coordination was prepared by plasma-enhanced chemical vapor deposition technique. The surface of the DLC film was exposed to hydrogen, oxygen and nitrogen plasma for physical and chemical modifications. The surface modification was based on the concept of adsorption-desorption of plasma species and surface entities of films. Energetic chemical species of microwave plasma are adsorbed, leading to desorbtion of the surface carbon atoms due to energy and momentum exchange. The interaction of such reactive species with DLC films enhanced the roughness, surface defects and dangling bonds of carbon atoms. Adsorbed hydrogen, oxygen and nitrogen formed a covalent network while saturating the dangling carbon bonds around the tetrahedral sp3 valency. The modified surface chemical affinity depends upon the charge carriers and electron covalency of the adsorbed atoms. The contact angle of chemically reconstructed surface increases when a water droplet interacts either through hydrogen or van dear Waals bonding. These weak interactions influenced the wetting property of the DLC surface to a great extent.

  19. Alignment of non-covalent interactions at protein-protein interfaces.

    Directory of Open Access Journals (Sweden)

    Hongbo Zhu

    Full Text Available BACKGROUND: The study and comparison of protein-protein interfaces is essential for the understanding of the mechanisms of interaction between proteins. While there are many methods for comparing protein structures and protein binding sites, so far no methods have been reported for comparing the geometry of non-covalent interactions occurring at protein-protein interfaces. METHODOLOGY/PRINCIPAL FINDINGS: Here we present a method for aligning non-covalent interactions between different protein-protein interfaces. The method aligns the vector representations of van der Waals interactions and hydrogen bonds based on their geometry. The method has been applied to a dataset which comprises a variety of protein-protein interfaces. The alignments are consistent to a large extent with the results obtained using two other complementary approaches. In addition, we apply the method to three examples of protein mimicry. The method successfully aligns respective interfaces and allows for recognizing conserved interface regions. CONCLUSIONS/SIGNIFICANCE: The Galinter method has been validated in the comparison of interfaces in which homologous subunits are involved, including cases of mimicry. The method is also applicable to comparing interfaces involving non-peptidic compounds. Galinter assists users in identifying local interface regions with similar patterns of non-covalent interactions. This is particularly relevant to the investigation of the molecular basis of interaction mimicry.

  20. Diazonium-derived aryl films on gold nanoparticles: evidence for a carbon-gold covalent bond.

    Science.gov (United States)

    Laurentius, Lars; Stoyanov, Stanislav R; Gusarov, Sergey; Kovalenko, Andriy; Du, Rongbing; Lopinski, Gregory P; McDermott, Mark T

    2011-05-24

    Tailoring the surface chemistry of metallic nanoparticles is generally a key step for their use in a wide range of applications. There are few examples of organic films covalently bound to metal nanoparticles. We demonstrate here that aryl films are formed on gold nanoparticles from the spontaneous reduction of diazonium salts. The structure and the bonding of the film is probed with surface-enhanced Raman scattering (SERS). Extinction spectroscopy and SERS show that a nitrobenzene film forms on gold nanoparticles from the corresponding diazonium salt. Comparison of the SERS spectrum with spectra computed from density functional theory models reveals a band characteristic of a Au-C stretch. The observation of this stretch is direct evidence of a covalent bond. A similar band is observed in high-resolution electron energy loss spectra of nitrobenzene layers on planar gold. The bonding of these types of films through a covalent interaction on gold is consistent with their enhanced stability observed in other studies. These findings provide motivation for the use of diazonium-derived films on gold and other metals in applications where high stability and/or strong adsorbate-substrate coupling are required.

  1. Fabrication of molecular hybrid films of gold nanoparticle and polythiophene by covalent assembly

    Energy Technology Data Exchange (ETDEWEB)

    Sundaramurthy, Jayaraman, E-mail: jsu2@np.edu.sg [Department of Chemical & Biomolecular Engineering, National University of Singapore, Block E5, 4 Engineering Drive 4, 117576 (Singapore); Environmental & Water Technology Centre of Innovation, Ngee Ann Polytechnic, 599489 (Singapore); Dharmarajan, Rajarathnam [CERAR, University of South Australia, Mawson Lakes, SA 5095 (Australia); Srinivasan, M.P., E-mail: chesmp@nus.edu.sg [Department of Chemical & Biomolecular Engineering, National University of Singapore, Block E5, 4 Engineering Drive 4, 117576 (Singapore)

    2015-08-31

    This work demonstrates the fabrication of molecular hybrid films comprising gold nanoparticles (AuNPs) incorporated in covalently assembled, substituted polythiophene (poly(3-(2-bromoethoxy)ethoxymethylthiophene-2,5-diyl (PBrEEMT))) films by different surface chemistry routes. AuNPs are incorporated in the immobilized polythiophene matrix due to its affinity for amine and sulfur. The amount of AuNPs present depends on the nature of the incorporation, the extent of film coverage and interaction of thiophene and amine groups. PBrEEMT films functionalized with amine rich polyallylamine immobilize greater numbers of AuNPs due to more extensive gold–amine interactions. Covalent binding between AuNP and PBrEEMT films was accomplished by using pre-functionalised AuNPs (4-aminothiophenol functionalized AuNPs). Atomic force microscopy, field emission scanning electron microscopy and X-ray photoelectron spectroscopy were used to study the morphology and chemical constituents of assembled films. These approaches will pave the way for developing facile methods for nanoparticle incorporation and will also facilitate direct interaction of nanoparticles with the conducting polymer matrix and enhance the electrical properties of the films. - Highlights: • Covalent molecular assembly enabled the fabrication of molecular hybrid films. • Monomeric and polymeric species were employed as intermediate linkers. • Adopted approaches facilitated the direct interaction of gold nanoparticle in films. • The amount of nanoparticle incorporation depended on the extent of film coverage.

  2. Rehealable, fully recyclable, and malleable electronic skin enabled by dynamic covalent thermoset nanocomposite.

    Science.gov (United States)

    Zou, Zhanan; Zhu, Chengpu; Li, Yan; Lei, Xingfeng; Zhang, Wei; Xiao, Jianliang

    2018-02-01

    Electronic skin (e-skin) mimicking functionalities and mechanical properties of natural skin can find broad applications. We report the first dynamic covalent thermoset-based e-skin, which is connected through robust covalent bonds, rendering the resulting devices good chemical and thermal stability at service condition. By doping the dynamic covalent thermoset with conductive silver nanoparticles, we demonstrate a robust yet rehealable, fully recyclable, and malleable e-skin. Tactile, temperature, flow, and humidity sensing capabilities are realized. The e-skin can be rehealed when it is damaged and can be fully recycled at room temperature, which has rarely, if at all, been demonstrated for e-skin. After rehealing or recycling, the e-skin regains mechanical and electrical properties comparable to the original e-skin. In addition, malleability enables the e-skin to permanently conform to complex, curved surfaces without introducing excessive interfacial stresses. These properties of the e-skin yield an economical and eco-friendly technology that can find broad applications in robotics, prosthetics, health care, and human-computer interface.

  3. Pulmonary toxicity of trichloroethylene in mice. Covalent binding and morphological manifestations

    International Nuclear Information System (INIS)

    Forkert, P.G.; Birch, D.W.

    1989-01-01

    We examined the time course of trichloroethylene (TCE)-induced pulmonary injury and focused on morphological changes and covalent binding of [ 14 C]TCE soon after administration of a single dose of TCE (2000 mg/kg) to CD-1 male mice. At 1 hr after chemical treatment, Clara cells of the bronchiolar epithelium exhibited necrotic changes involving the mitochondria and endoplasmic reticulum. Dilatation of the endoplasmic reticulum became more severe at 2 hr after TCE administration and, by 4 hr, distended cisternae coalesced to form small vacuoles within the cytoplasmic matrix of the Clara cell. The severity of cellular damage increased progressively between 8 and 12 hr and, by 24 hr, the majority of Clara cells within an airway were severely vacuolated. Covalent binding of [ 14 C]TCE to lung macromolecules was evident at 1 hr, peaked at 4 hr, declined thereafter, and reached a plateau between 12 and 24 hr. Peak binding (142.6 +/- 31.8 nmol/g of wet weight) represented approximately 20% of [ 14 C]TCE distributed to the lung. Although the levels of binding in the liver were at all times greater than those in the lung, liver injury was relatively insignificant. The results demonstrate a positive correlation between the onset of Clara cell injury and the formation of reactive metabolites, as assessed by covalent binding of [ 14 C]TCE

  4. Covalent bonding of chloroanilines to humic constituents: Pathways, kinetics, and stability

    International Nuclear Information System (INIS)

    Kong, Deyang; Xia, Qing; Liu, Guoqiang; Huang, Qingguo; Lu, Junhe

    2013-01-01

    Covalent coupling to natural humic constituents comprises an important transformation pathway for anilinic pollutants in the environment. We systematically investigated the reactions of chlorine substituted anilines with catechol and syringic acid in horseradish peroxidase (HRP) catalyzed systems. It was demonstrated that although nucleophilic addition was the mechanism of covalent bonding to both catechol and syringic acid, chloroanilines coupled to the 2 humic constituents via slightly different pathways. 1,4-addition and 1,2-addition are involved to catechol and syringic acid, respectively. 1,4-addition showed empirical 2nd order kinetics and this pathway seemed to be more permanent than 1,2-addition. Stability experiments demonstrated that cross-coupling products with syringic acid could be easily released in acidic conditions. However, cross-coupling with catechol was relatively stable at similar conditions. Thus, the environmental behavior and bioavailability of the coupling products should be carefully assessed. -- Highlights: •Chloroanilines covalently coupled to humic constituents in HRP catalyzed processes, which facilitated their transformation. •MS technique was employed to analyze the coupling products and therefore elucidate the reaction pathways. •Chloroanilines couple to catechol and syringic acid via 1,4- and 1,2-nucleophilic addition pathways, respectively. •Cross-coupling products formed via 1,4-nucleophilic addition pathway were more stable than those via 1,2-addition pathway. -- Bound residues of chloroanilines formed via 1,2- and 1,4-nucleophilic addition pathways showed different stability

  5. Encapsulation and covalent binding of molecular payload in enzymatically activated micellar nanocarriers.

    Science.gov (United States)

    Rosenbaum, Ido; Harnoy, Assaf J; Tirosh, Einat; Buzhor, Marina; Segal, Merav; Frid, Liat; Shaharabani, Rona; Avinery, Ram; Beck, Roy; Amir, Roey J

    2015-02-18

    The high selectivity and often-observed overexpression of specific disease-associated enzymes make them extremely attractive for triggering the release of hydrophobic drug or probe molecules from stimuli-responsive micellar nanocarriers. Here we utilized highly modular amphiphilic polymeric hybrids, composed of a linear hydrophilic polyethylene glycol (PEG) and an esterase-responsive hydrophobic dendron, to prepare and study two diverse strategies for loading of enzyme-responsive micelles. In the first type of micelles, hydrophobic coumarin-derived dyes were encapsulated noncovalently inside the hydrophobic core of the micelle, which was composed of lipophilic enzyme-responsive dendrons. In the second type of micellar nanocarrier the hydrophobic molecular cargo was covalently linked to the end-groups of the dendron through enzyme-cleavable bonds. These amphiphilic hybrids self-assembled into micellar nanocarriers with their cargo covalently encapsulated within the hydrophobic core. Both types of micelles were highly responsive toward the activating enzyme and released their molecular cargo upon enzymatic stimulus. Importantly, while faster release was observed with noncovalent encapsulation, higher loading capacity and slower release rate were achieved with covalent encapsulation. Our results clearly indicate the great potential of enzyme-responsive micellar delivery platforms due to the ability to tune their payload capacities and release rates by adjusting the loading strategy.

  6. Covalent bond force profile and cleavage in a single polymer chain

    Science.gov (United States)

    Garnier, Lionel; Gauthier-Manuel, Bernard; van der Vegte, Eric W.; Snijders, Jaap; Hadziioannou, Georges

    2000-08-01

    We present here the measurement of the single-polymer entropic elasticity and the single covalent bond force profile, probed with two types of atomic force microscopes (AFM) on a synthetic polymer molecule: polymethacrylic acid in water. The conventional AFM allowed us to distinguish two types of interactions present in this system when doing force spectroscopic measurements: the first interaction is associated with adsorption sites of the polymer chains onto a bare gold surface, the second interaction is directly correlated to the rupture process of a single covalent bond. All these bridging interactions allowed us to stretch the single polymer chain and to determine the various factors playing a role in the elasticity of these molecules. To obtain a closer insight into the bond rupture process, we moved to a force sensor stable in position when measuring attractive forces. By optimizing the polymer length so as to fulfill the elastic stability conditions, we were able for the first time to map out the entire force profile associated with the cleavage of a single covalent bond. Experimental data coupled with molecular quantum mechanical calculations strongly suggest that the breaking bond is located at one end of the polymer chain.

  7. Construction of a Hierarchical Architecture of Covalent Organic Frameworks via a Postsynthetic Approach.

    Science.gov (United States)

    Zhang, Gen; Tsujimoto, Masahiko; Packwood, Daniel; Duong, Nghia Tuan; Nishiyama, Yusuke; Kadota, Kentaro; Kitagawa, Susumu; Horike, Satoshi

    2018-02-21

    Covalent organic frameworks (COFs) represent an emerging class of crystalline porous materials that are constructed by the assembly of organic building blocks linked via covalent bonds. Several strategies have been developed for the construction of new COF structures; however, a facile approach to fabricate hierarchical COF architectures with controlled domain structures remains a significant challenge, and has not yet been achieved. In this study, a dynamic covalent chemistry (DCC)-based postsynthetic approach was employed at the solid-liquid interface to construct such structures. Two-dimensional imine-bonded COFs having different aromatic groups were prepared, and a homogeneously mixed-linker structure and a heterogeneously core-shell hollow structure were fabricated by controlling the reactivity of the postsynthetic reactions. Solid-state nuclear magnetic resonance (NMR) spectroscopy and transmission electron microscopy (TEM) confirmed the structures. COFs prepared by a postsynthetic approach exhibit several functional advantages compared with their parent phases. Their Brunauer-Emmett-Teller (BET) surface areas are 2-fold greater than those of their parent phases because of the higher crystallinity. In addition, the hydrophilicity of the material and the stepwise adsorption isotherms of H 2 O vapor in the hierarchical frameworks were precisely controlled, which was feasible because of the distribution of various domains of the two COFs by controlling the postsynthetic reaction. The approach opens new routes for constructing COF architectures with functionalities that are not possible in a single phase.

  8. Covalent Bonding of Pyrrolobenzodiazepines (PBDs) to Terminal Guanine Residues within Duplex and Hairpin DNA Fragments

    Science.gov (United States)

    Mantaj, Julia; Jackson, Paul J. M.; Karu, Kersti; Rahman, Khondaker M.; Thurston, David E.

    2016-01-01

    Pyrrolobenzodiazepines (PBDs) are covalent-binding DNA-interactive agents with growing importance as payloads in Antibody Drug Conjugates (ADCs). Until now, PBDs were thought to covalently bond to C2-NH2 groups of guanines in the DNA-minor groove across a three-base-pair recognition sequence. Using HPLC/MS methodology with designed hairpin and duplex oligonucleotides, we have now demonstrated that the PBD Dimer SJG-136 and the C8-conjugated PBD Monomer GWL-78 can covalently bond to a terminal guanine of DNA, with the PBD skeleton spanning only two base pairs. Control experiments with the non-C8-conjugated anthramycin along with molecular dynamics simulations suggest that the C8-substituent of a PBD Monomer, or one-half of a PBD Dimer, may provide stability for the adduct. This observation highlights the importance of PBD C8-substituents, and also suggests that PBDs may bind to terminal guanines within stretches of DNA in cells, thus representing a potentially novel mechanism of action at the end of DNA strand breaks. PMID:27055050

  9. Non-covalent interaction between polyubiquitin and GTP cyclohydrolase 1 dictates its degradation.

    Directory of Open Access Journals (Sweden)

    Yu Zhao

    Full Text Available GTP cyclohydrolase 1 (GTPCH1 is the rate-limiting enzyme in the de novo synthesis of tetrahydrobiopterin (BH4. GTPCH1 protein degradation has been reported in animal models of several diseases, including diabetes mellitus and hypertension. However, the molecular mechanisms by which GTPCH1 is degraded remain uncharacterized. Here we report a novel non-covalent interaction between polyubiquitin and GTPCH1 in vitro and in vivo. The non-covalent binding of GTPCH1 to polyubiquitin via an ubiquitin-binding domain (UBD results in ubiquitination and degradation. Ectopic expression of ubiquitin in cultured cells accelerated GTPCH1 degradation. In cultured cells and in vitro assays, Lys48-linked ubiquitin chains, but not Lys63-linked chains, interacted with GTPCH1 and targeted it for degradation. Consistently, proteasome inhibition attenuated GTPCH1 degradation. Finally, direct mutagenesis of an isoleucine (Ile131 in the hydrophobic patch of the GTPCH1 UBD affected its ubiquitin binding and the enzyme stability. Taken together, we conclude that GTPCH1 non-covalently interacts with polyubiquitin via an ubiquitin-binding domain. The polyubiquitin binding directs GTPCH1 ubiquitination and proteasome degradation.

  10. Establishment of modified reversible regional cerebral ischemic models

    International Nuclear Information System (INIS)

    Ji Xunming; Ling Feng; Zhao Xiqing; Xuan Yun; Wang Yueqin; Ling Xiaolan; Chang Hongjun; Zhang Zhiping

    2005-01-01

    Objective: Modifying the method of establishing reversible middle cerebral ischemic models in rats for improvement of the stability and rate of success, so as to raise the reliability of cerebral ischemic study. Methods: Sixty male Wistar rats were randomly divided into two groups, modified and control groups, 30 rats in each group. The method of silicone- tipping on one end of the nylon suture was used to modify the establishment of embolus, and tip-heating method was used to establish the traditional embolus with all the other steps of the procedure just the same. The Zea Longa 5 scoring scale was used to estimate the neurological deficiency while TTC staining method was used to measure and calculate the volume of cerebral infarction. The percentage of successful models with 3-4 grade scorings and the coefficient of the variations of cerebral infarct volume were used to estimate the stability of the models. Results: The rate of success of establishment models in the modification group was significantly higher in comparing with the traditional group (93% vs 60%, χ 2 =9.32, P=0.002). The percentage of model establishment with 3-4 grade neurological scores in modification group was higher than that in the traditional group 96.4% vs 61.2%, χ 2 =9.51, P=0.002). The cerebral infarct volume in modification group and traditional group were (4.1450±0.5019) cm 3 and (3.8435 ± 0.8164) cm 3 , and the coefficients of variation were 12.01% and 21.24% respectively, which indicated that the stability of models was significantly higher in modification group than in the traditional one. Conclusions: The rates of success and stability of the models for reversible focal cerebral ischemia made by the modification method were significantly improved, with decreasing the cost of model creation and increasing the accuracy of study of ischemic cerebral vascular disease. (authors)

  11. Mass Spectrometric Characterization of Circulating Covalent Protein Adducts Derived from a Drug Acyl Glucuronide Metabolite: Multiple Albumin Adductions in Diclofenac Patients

    Science.gov (United States)

    Hammond, Thomas G.; Meng, Xiaoli; Jenkins, Rosalind E.; Maggs, James L.; Castelazo, Anahi Santoyo; Regan, Sophie L.; Bennett, Stuart N. L.; Earnshaw, Caroline J.; Aithal, Guruprasad P.; Pande, Ira; Kenna, J. Gerry; Stachulski, Andrew V.; Park, B. Kevin

    2014-01-01

    Covalent protein modifications by electrophilic acyl glucuronide (AG) metabolites are hypothetical causes of hypersensitivity reactions associated with certain carboxylate drugs. The complex rearrangements and reactivities of drug AG have been defined in great detail, and protein adducts of carboxylate drugs, such as diclofenac, have been found in liver and plasma of experimental animals and humans. However, in the absence of definitive molecular characterization, and specifically, identification of signature glycation conjugates retaining the glucuronyl and carboxyl residues, it cannot be assumed any of these adducts is derived uniquely or even fractionally from AG metabolites. We have therefore undertaken targeted mass spectrometric analyses of human serum albumin (HSA) isolated from diclofenac patients to characterize drug-derived structures and, thereby, for the first time, have deconstructed conclusively the pathways of adduct formation from a drug AG and its isomeric rearrangement products in vivo. These analyses were informed by a thorough understanding of the reactions of HSA with diclofenac AG in vitro. HSA from six patients without drug-related hypersensitivities had either a single drug-derived adduct or one of five combinations of 2–8 adducts from among seven diclofenac N-acylations and three AG glycations on seven of the protein’s 59 lysines. Only acylations were found in every patient. We present evidence that HSA modifications by diclofenac in vivo are complicated and variable, that at least a fraction of these modifications are derived from the drug’s AG metabolite, and that albumin adduction is not inevitably a causation of hypersensitivity to carboxylate drugs or a coincidental association. PMID:24902585

  12. Structural dynamic modifications via models

    Indian Academy of Sciences (India)

    The study shows that as many as half of the matrix ... the dynamicist's analytical modelling skill which would appear both in the numerator as. Figure 2. ..... Brandon J A 1990 Strategies for structural dynamic modification (New York: John Wiley).

  13. Modifications to Replacement Costs System

    International Nuclear Information System (INIS)

    Godec, M.

    1989-01-01

    The purpose of this memorandum is to document the improvements and modifications made to the Replacement Costs of Crude Oil (REPCO) Supply Analysis System. While some of this work was performed under our previous support contract to DOE/ASFE, we are presenting all modifications and improvements are presented here for completeness. The memo primarily documents revisions made to the Lower-48 Onshore Model. Revisions and modifications made to other components and models in the REPCO system which are documented elsewhere are only highlighted in this memo. Generally, the modifications made to the Lower-48 Onshore Model reflect changes that have occurred in domestic drilling, oil field costs, and reserves since 1982, the date of the most recent available data used for the original Replacement Costs report, published in 1985

  14. Reversible photoluminescence in spiropyran-modified porous silicon

    International Nuclear Information System (INIS)

    Lee, Chen-Yu; Hu, Chih-Hsuan; Cheng, Sheng-Lin; Chu, Chih-Chien; Hsiao, Vincent K.S.

    2015-01-01

    Spiropyran-modified porous silicon (spiro-PS) was used for the first time as an organic–inorganic hybrid material by using reversible photoluminescence (PL). Before spiropyran modification, the peak wavelength from PS was approximately 600 nm. Subsequent spiropyran modification strongly quenched the PL intensity, from 15,000 to 2000 counts. However, under UV light irradiation, the PL intensity from spiro-PS was increased gradually to 20,000 counts because of the photoinduced ring opening from a colorless spiropyran (SP-form) to a colored merocyanine (MC-form). Furthermore, the resulting peak wavelength of the PL of an MC–PS sample red-shifted from 600 to 650 nm, and the PL intensity was higher than that of unmodified PS. Because the fluorescence emission band (500–700 nm) of PS substantially overlapped the absorption band (500–700 nm) of the MC-form of spiropyran, the energy transfer from the PS (donor) to the open-ring-state MC-form (acceptor) occurs efficiently. The intensity of the PL from spiro-PS can be reversibly modulated using a heat stimulus. The current demonstrations have potential in reversible solid-state lighting or data storage applications. - Highlights: • Spiropyran-modified porous silicon (spiro-PS) was used for the first time as an organic–inorganic hybrid material with reversible photoluminescence (PL). • UV light irradiation make PL intensity from spiro-PS increased due to the photo-induced ring opening process. • The energy transfer from the PS (donor) to the open-ring state of spiropyran (acceptor) was to be efficient due to the fluorescence emission band of PS substantially overlapped with the absorption band of the ring-opened spiro. • The intensity of the PL from spiro-PS can be reversibly modulated using a heat stimulus

  15. Three-Dimensionally Functionalized Reverse Phase Glycoprotein Array for Cancer Biomarker Discovery and Validation.

    Science.gov (United States)

    Pan, Li; Aguilar, Hillary Andaluz; Wang, Linna; Iliuk, Anton; Tao, W Andy

    2016-11-30

    Glycoproteins have vast structural diversity that plays an important role in many biological processes and have great potential as disease biomarkers. Here, we report a novel functionalized reverse phase protein array (RPPA), termed polymer-based reverse phase glycoprotein array (polyGPA), to capture and profile glycoproteomes specifically, and validate glycoproteins. Nitrocellulose membrane functionalized with globular hydroxyaminodendrimers was used to covalently capture preoxidized glycans on glycoproteins from complex protein samples such as biofluids. The captured glycoproteins were subsequently detected using the same validated antibodies as in RPPA. We demonstrated the outstanding specificity, sensitivity, and quantitative capabilities of polyGPA by capturing and detecting purified as well as endogenous α-1-acid glycoprotein (AGP) in human plasma. We further applied quantitative N-glycoproteomics and the strategy to validate a panel of glycoproteins identified as potential biomarkers for bladder cancer by analyzing urine glycoproteins from bladder cancer patients or matched healthy individuals.

  16. Standard approach to plant modifications

    International Nuclear Information System (INIS)

    Mecredy, R.C.

    1988-01-01

    Organizational and management approaches to the design, installation, and turnover of nuclear plant modifications have changed dramatically in the last 10 to 15 yr. In response to these changes, organizational and individual responsibilities have been defined and management systems have been established at Rochester Gas and Electric (RG and E) Corporation to ensure that high-quality plant modifications are installed in a timely manner that satisfies user needs at minimal cost

  17. How decision reversibility affects motivation.

    Science.gov (United States)

    Bullens, Lottie; van Harreveld, Frenk; Förster, Jens; Higgins, Tory E

    2014-04-01

    The present research examined how decision reversibility can affect motivation. On the basis of extant findings, it was suggested that 1 way it could affect motivation would be to strengthen different regulatory foci, with reversible decision making, compared to irreversible decision making, strengthening prevention-related motivation relatively more than promotion-related motivation. If so, then decision reversibility should have effects associated with the relative differences between prevention and promotion motivation. In 5 studies, we manipulated the reversibility of a decision and used different indicators of regulatory focus motivation to test these predictions. Specifically, Study 1 tested for differences in participants' preference for approach versus avoidance strategies toward a desired end state. In Study 2, we used speed and accuracy performance as indicators of participants' regulatory motivation, and in Study 3, we measured global versus local reaction time performance. In Study 4, we approached the research question in a different way, making use of the value-from-fit hypothesis (Higgins, 2000, 2002). We tested whether a fit between chronic regulatory focus and focus induced by the reversibility of the decision increased participants' subjective positive feelings about the decision outcome. Finally, in Study 5, we tested whether regulatory motivation, induced by decision reversibility, also influenced participants' preference in specific product features. The results generally support our hypothesis showing that, compared to irreversible decisions, reversible decisions strengthen a prevention focus more than a promotion focus. Implications for research on decision making are discussed.

  18. Supercritical fluid reverse micelle separation

    Science.gov (United States)

    Fulton, J.L.; Smith, R.D.

    1993-11-30

    A method of separating solute material from a polar fluid in a first polar fluid phase is provided. The method comprises combining a polar fluid, a second fluid that is a gas at standard temperature and pressure and has a critical density, and a surfactant. The solute material is dissolved in the polar fluid to define the first polar fluid phase. The combined polar and second fluids, surfactant, and solute material dissolved in the polar fluid is maintained under near critical or supercritical temperature and pressure conditions such that the density of the second fluid exceeds the critical density thereof. In this way, a reverse micelle system defining a reverse micelle solvent is formed which comprises a continuous phase in the second fluid and a plurality of reverse micelles dispersed in the continuous phase. The solute material is dissolved in the polar fluid and is in chemical equilibrium with the reverse micelles. The first polar fluid phase and the continuous phase are immiscible. The reverse micelles each comprise a dynamic aggregate of surfactant molecules surrounding a core of the polar fluid. The reverse micelle solvent has a polar fluid-to-surfactant molar ratio W, which can vary over a range having a maximum ratio W[sub o] that determines the maximum size of the reverse micelles. The maximum ratio W[sub o] of the reverse micelle solvent is then varied, and the solute material from the first polar fluid phase is transported into the reverse micelles in the continuous phase at an extraction efficiency determined by the critical or supercritical conditions. 27 figures.

  19. Facile synthesis of triazine-triphenylamine-based microporous covalent polymer adsorbent for flue gas CO2 capture

    KAUST Repository

    Das, Swapan Kumar; Wang, Xinbo; Lai, Zhiping

    2017-01-01

    The sustainable capture and sequestration of CO2 from flue gas emission is an important and unavoidable challenge to control greenhouse gas release and climate change. In this report, we describe a triazine-triphenylamine-based microporous covalent

  20. 4fn-15d centroid shift in lanthanides and relation with anion polarizability, covalency, and cation electronegativity

    International Nuclear Information System (INIS)

    Dorenbos, P.; Andriessen, J.; Eijk, C.W.E. van

    2003-01-01

    Data collected on the centroid shift of the 5d-configuration of Ce 3+ in oxide and fluoride compounds were recently analyzed with a model involving the correlated motion between 5d-electron and ligand electrons. The correlation effects are proportional to the polarizability of the anion ligands and it leads, like covalency, to lowering of the 5d-orbital energies. By means of ab initio Hartree-Fock-LCAO calculations including configuration interaction the contribution from covalency and correlated motion to the centroid shift are determined separately for Ce 3+ in various compounds. It will be shown that in fluoride compounds, covalency provides an insignificant contribution. In oxides, polarizability appears to be of comparable importance as covalency