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Sample records for factor complex formation

  1. Factors Leading to the Formation of Arc Cloud Complexes.

    DTIC Science & Technology

    1985-12-01

    I. M2i .16 MICROCnWY O TEST CHART NATIONAL BUREAU 0F STANDARDS-1963-A ils. ... TEXAS A&M UNIVERSITY DEPARTMENT OF R AOL mMETEOROLOGY FACTORS LEADING...PERFORMING ORGANIZATION NAME AND ADDRESS 10. PROGRAM ELEMENT, PROJECT, TASKAFIT STUDENT AT: AREA & WORK UNIT NUMBERS Texas A&M Univ II. CONTROLLING...to an ACC. /0 FACTORS LEADING TO THE FORMATION OF ARC CLOUD COMPLEXES A Thesis by MARK JOHN WELSHINGER Submitted to the Graduate College of Texas A&M

  2. Factors leading to the formation of arc cloud complexes

    NASA Technical Reports Server (NTRS)

    Welshinger, Mark John; Brundidge, Kenneth C.

    1987-01-01

    A total of 12 mesoscale convective systems (MCSs) were investigated. The duration of the gust front, produced by each MCS, was used to classify the MCSs. Category 1 MCSs were defined as ones that produced a gust front and the gust front lasted for more than 6 h. There were 7 category 1 MCSs in the sample. Category 2 MCSs were defined as ones that produced a gust front and the gust front lasted for 6 h or less. There were 4 category 2 MCSs. The MCS of Case 12 was not categorized because the precipitation characteristics were similar to a squall line, rather than an MCS. All of the category 1 MCSs produced arc cloud complexes (ACCs), while only one of the category 2 MCSs produced an ACC. To determine if there were any differences in the characteristics between the MCSs of the two categories, composite analyses were accomplished. The analyses showed that there were significant differences in the characteristics of category 1 and 2 MCSs. Category 1 MCSs, on average, had higher thunderstorm heights, greater precipitation intensities, colder cloud top temperatures and produced larger magnitudes of surface divergence than category 2 MCSs.

  3. SEPALLATA3: the 'glue' for MADS box transcription factor complex formation

    PubMed Central

    Immink, Richard GH; Tonaco, Isabella AN; de Folter, Stefan; Shchennikova, Anna; van Dijk, Aalt DJ; Busscher-Lange, Jacqueline; Borst, Jan W; Angenent, Gerco C

    2009-01-01

    Background Plant MADS box proteins play important roles in a plethora of developmental processes. In order to regulate specific sets of target genes, MADS box proteins dimerize and are thought to assemble into multimeric complexes. In this study a large-scale yeast three-hybrid screen is utilized to provide insight into the higher-order complex formation capacity of the Arabidopsis MADS box family. SEPALLATA3 (SEP3) has been shown to mediate complex formation and, therefore, special attention is paid to this factor in this study. Results In total, 106 multimeric complexes were identified; in more than half of these at least one SEP protein was present. Besides the known complexes involved in determining floral organ identity, various complexes consisting of combinations of proteins known to play a role in floral organ identity specification, and flowering time determination were discovered. The capacity to form this latter type of complex suggests that homeotic factors play essential roles in down-regulation of the MADS box genes involved in floral timing in the flower via negative auto-regulatory loops. Furthermore, various novel complexes were identified that may be important for the direct regulation of the floral transition process. A subsequent detailed analysis of the APETALA3, PISTILLATA, and SEP3 proteins in living plant cells suggests the formation of a multimeric complex in vivo. Conclusions Overall, these results provide strong indications that higher-order complex formation is a general and essential molecular mechanism for plant MADS box protein functioning and attribute a pivotal role to the SEP3 'glue' protein in mediating multimerization. PMID:19243611

  4. Complex formation with nucleic acids and aptamers alters the antigenic properties of platelet factor 4

    PubMed Central

    Jaax, Miriam E.; Krauel, Krystin; Marschall, Thomas; Brandt, Sven; Gansler, Julia; Fürll, Birgitt; Appel, Bettina; Fischer, Silvia; Block, Stephan; Helm, Christiane A.; Müller, Sabine; Preissner, Klaus T.

    2013-01-01

    The tight electrostatic binding of the chemokine platelet factor 4 (PF4) to polyanions induces heparin-induced thrombocytopenia, a prothrombotic adverse drug reaction caused by immunoglobulin G directed against PF4/polyanion complexes. This study demonstrates that nucleic acids, including aptamers, also bind to PF4 and enhance PF4 binding to platelets. Systematic assessment of RNA and DNA constructs, as well as 4 aptamers of different lengths and secondary structures, revealed that increasing length and double-stranded segments of nucleic acids augment complex formation with PF4, while single nucleotides or single-stranded polyA or polyC constructs do not. Aptamers were shown by circular dichroism spectroscopy to induce structural changes in PF4 that resemble those induced by heparin. Moreover, heparin-induced anti-human–PF4/heparin antibodies cross-reacted with human PF4/nucleic acid and PF4/aptamer complexes, as shown by an enzyme immunoassay and a functional platelet activation assay. Finally, administration of PF4/44mer–DNA protein C aptamer complexes in mice induced anti–PF4/aptamer antibodies, which cross-reacted with murine PF4/heparin complexes. These data indicate that the formation of anti-PF4/heparin antibodies in postoperative patients may be augmented by PF4/nucleic acid complexes. Moreover, administration of therapeutic aptamers has the potential to induce anti-PF4/polyanion antibodies and a prothrombotic diathesis. PMID:23673861

  5. Analysis of functional domains of the host cell factor involved in VP16 complex formation.

    PubMed

    Hughes, T A; La Boissière, S; O'Hare, P

    1999-06-04

    We present biochemical analyses of the regions of the host cell factor (HCF) involved in VP16 complex formation and in the association between the N- and C-terminal domains of HCF itself. We show that the kelch repeat region of HCF (residues 1-380) is sufficient for VP16 complex formation, but that residues C-terminal to the repeats (positions 381-450) interfere with this activity. However, these latter residues are required for the interaction between the N- and C-terminal regions of HCF. The extreme C-terminal region of HCF, corresponding to an area of strong conservation with a Caenorhabditis elegans homologue, is sufficient for interaction with the N-terminal region. These results are discussed with respect to possible differences in the roles of HCF in VP16 activity versus its normal cellular function.

  6. Crystal Structure of Human Factor VIII: Implications for the Formation of the Factor IXa-Factor VIIIa Complex

    SciTech Connect

    Ngo, J.C.; Huang, M.; Roth, D.A.; Furie, B.C.; Furie, B.

    2008-06-03

    Factor VIII is a procofactor that plays a critical role in blood coagulation, and is missing or defective in hemophilia A. We determined the X-ray crystal structure of B domain-deleted human factor VIII. This protein is composed of five globular domains and contains one Ca{sup 2+} and two Cu{sup 2+} ions. The three homologous A domains form a triangular heterotrimer where the A1 and A3 domains serve as the base and interact with the C2 and C1 domains, respectively. The structurally homologous C1 and C2 domains reveal membrane binding features. Based on biochemical studies, a model of the factor IXa-factor VIIIa complex was constructed by in silico docking. Factor IXa wraps across the side of factor VIII, and an extended interface spans the factor VIII heavy and light chains. This model provides insight into the activation of factor VIII and the interaction of factor VIIIa with factor IXa on the membrane surface.

  7. Crystal Structure of Human Factor VIII: Implications for the Formation of the Factor IXa-Factor VIIIa Complex

    SciTech Connect

    Chi Ki Ngo,J.; Huang, M.; Roth, D.; Furie, B.; Furie, B.

    2008-01-01

    Factor VIII is a procofactor that plays a critical role in blood coagulation, and is missing or defective in hemophilia A. We determined the X-ray crystal structure of B domain-deleted human factor VIII. This protein is composed of five globular domains and contains one Ca(2+) and two Cu(2+) ions. The three homologous A domains form a triangular heterotrimer where the A1 and A3 domains serve as the base and interact with the C2 and C1 domains, respectively. The structurally homologous C1 and C2 domains reveal membrane binding features. Based on biochemical studies, a model of the factor IXa-factor VIIIa complex was constructed by in silico docking. Factor IXa wraps across the side of factor VIII, and an extended interface spans the factor VIII heavy and light chains. This model provides insight into the activation of factor VIII and the interaction of factor VIIIa with factor IXa on the membrane surface.

  8. Bacillus subtilis δ Factor Functions as a Transcriptional Regulator by Facilitating the Open Complex Formation.

    PubMed

    Prajapati, Ranjit Kumar; Sengupta, Shreya; Rudra, Paulami; Mukhopadhyay, Jayanta

    2016-01-15

    Most bacterial RNA polymerases (RNAP) contain five conserved subunits, viz. 2α, β, β', and ω. However, in many Gram-positive bacteria, especially in fermicutes, RNAP is associated with an additional factor, called δ. For over three decades since its identification, it had been thought that δ functioned as a subunit of RNAP to enhance the level of transcripts by recycling RNAP. In support of the previous observations, we also find that δ is involved in recycling of RNAP by releasing the RNA from the ternary complex. We further show that δ binds to RNA and is able to recycle RNAP when the length of the nascent RNA reaches a critical length. However, in this work we decipher a new function of δ. Performing biochemical and mutational analysis, we show that Bacillus subtilis δ binds to DNA immediately upstream of the promoter element at A-rich sequences on the abrB and rrnB1 promoters and facilitates open complex formation. As a result, δ facilitates RNAP to initiate transcription in the second scale, compared with minute scale in the absence of δ. Using transcription assay, we show that δ-mediated recycling of RNAP cannot be the sole reason for the enhancement of transcript yield. Our observation that δ does not bind to RNAP holo enzyme but is required to bind to DNA upstream of the -35 promoter element for transcription activation suggests that δ functions as a transcriptional regulator.

  9. Insights into complement convertase formation based on the structure of the factor B-cobra venom factor complex.

    PubMed

    Janssen, Bert J C; Gomes, Lucio; Koning, Roman I; Svergun, Dmitri I; Koster, Abraham J; Fritzinger, David C; Vogel, Carl-Wilhelm; Gros, Piet

    2009-08-19

    Immune protection by the complement system critically depends on assembly of C3 convertases on the surface of pathogens and altered host cells. These short-lived protease complexes are formed through pro-convertases, which for the alternative pathway consist of the complement component C3b and the pro-enzyme factor B (FB). Here, we present the crystal structure at 2.2-A resolution, small-angle X-ray scattering and electron microscopy (EM) data of the pro-convertase formed by human FB and cobra venom factor (CVF), a potent homologue of C3b that generates more stable convertases. FB is loaded onto CVF through its pro-peptide Ba segment by specific contacts, which explain the specificity for the homologous C3b over the native C3 and inactive products iC3b and C3c. The protease segment Bb binds the carboxy terminus of CVF through the metal-ion dependent adhesion site of the Von Willebrand factor A-type domain. A possible dynamic equilibrium between a 'loading' and 'activation' state of the pro-convertase may explain the observed difference between the crystal structure of CVFB and the EM structure of C3bB. These insights into formation of convertases provide a basis for further development of complement therapeutics.

  10. Bacterial formate hydrogenlyase complex

    PubMed Central

    McDowall, Jennifer S.; Murphy, Bonnie J.; Haumann, Michael; Palmer, Tracy; Armstrong, Fraser A.; Sargent, Frank

    2014-01-01

    Under anaerobic conditions, Escherichia coli can carry out a mixed-acid fermentation that ultimately produces molecular hydrogen. The enzyme directly responsible for hydrogen production is the membrane-bound formate hydrogenlyase (FHL) complex, which links formate oxidation to proton reduction and has evolutionary links to Complex I, the NADH:quinone oxidoreductase. Although the genetics, maturation, and some biochemistry of FHL are understood, the protein complex has never been isolated in an intact form to allow biochemical analysis. In this work, genetic tools are reported that allow the facile isolation of FHL in a single chromatographic step. The core complex is shown to comprise HycE (a [NiFe] hydrogenase component termed Hyd-3), FdhF (the molybdenum-dependent formate dehydrogenase-H), and three iron-sulfur proteins: HycB, HycF, and HycG. A proportion of this core complex remains associated with HycC and HycD, which are polytopic integral membrane proteins believed to anchor the core complex to the cytoplasmic side of the membrane. As isolated, the FHL complex retains formate hydrogenlyase activity in vitro. Protein film electrochemistry experiments on Hyd-3 demonstrate that it has a unique ability among [NiFe] hydrogenases to catalyze production of H2 even at high partial pressures of H2. Understanding and harnessing the activity of the FHL complex is critical to advancing future biohydrogen research efforts. PMID:25157147

  11. Some factors affecting precipitation and complex formation of an IgG cryoglobulin

    PubMed Central

    Hansson, Ulla-Britt; Lindström, Folke D.

    1973-01-01

    A patient with a monoclonal IgG kappa cryoglobulin presented with the purpura-arthralgia syndrome but showed no evidence of plasma cell myeloma. Cold exposure provoked hypocomplementaemia and increased urinary histamine excretion. A papular lesion provoked by cold exposure showed a vasculitis type lesion on biopsy. The cryoglobulin had a higher sedimentation rate, twice as many sulphydryl groups and a markedly lower content of sialic acid, than the non-cryo IgG from the same patient. On cryoprecipitation the monoclonal cryoglobulin preferentially interacted with autologous non-cryo IgG forming intermediate type, 9S IgG–11S IgG complexes. This was thought to depend in part on rheumatoid factor activity of the cryoglobulin. The effect on cryoprecipitation of various low molecular weight substances was studied. PMID:4199093

  12. Complexity of formation in holography

    NASA Astrophysics Data System (ADS)

    Chapman, Shira; Marrochio, Hugo; Myers, Robert C.

    2017-01-01

    It was recently conjectured that the quantum complexity of a holographic boundary state can be computed by evaluating the gravitational action on a bulk region known as the Wheeler-DeWitt patch. We apply this complexity=action duality to evaluate the `complexity of formation' [1, 2], i.e. the additional complexity arising in preparing the entangled thermofield double state with two copies of the boundary CFT compared to preparing the individual vacuum states of the two copies. We find that for boundary dimensions d > 2, the difference in the complexities grows linearly with the thermal entropy at high temperatures. For the special case d = 2, the complexity of formation is a fixed constant, independent of the temperature. We compare these results to those found using the complexity=volume duality.

  13. A Rac/Cdc42 exchange factor complex promotes formation of lateral filopodia and blood vessel lumen morphogenesis

    PubMed Central

    Abraham, Sabu; Scarcia, Margherita; Bagshaw, Richard D.; McMahon, Kathryn; Grant, Gary; Harvey, Tracey; Yeo, Maggie; Esteves, Filomena O.G.; Thygesen, Helene H.; Jones, Pamela F.; Speirs, Valerie; Hanby, Andrew M.; Selby, Peter J.; Lorger, Mihaela; Dear, T. Neil; Pawson, Tony; Marshall, Christopher J.; Mavria, Georgia

    2015-01-01

    During angiogenesis, Rho-GTPases influence endothelial cell migration and cell–cell adhesion; however it is not known whether they control formation of vessel lumens, which are essential for blood flow. Here, using an organotypic system that recapitulates distinct stages of VEGF-dependent angiogenesis, we show that lumen formation requires early cytoskeletal remodelling and lateral cell–cell contacts, mediated through the RAC1 guanine nucleotide exchange factor (GEF) DOCK4 (dedicator of cytokinesis 4). DOCK4 signalling is necessary for lateral filopodial protrusions and tubule remodelling prior to lumen formation, whereas proximal, tip filopodia persist in the absence of DOCK4. VEGF-dependent Rac activation via DOCK4 is necessary for CDC42 activation to signal filopodia formation and depends on the activation of RHOG through the RHOG GEF, SGEF. VEGF promotes interaction of DOCK4 with the CDC42 GEF DOCK9. These studies identify a novel Rho-family GTPase activation cascade for the formation of endothelial cell filopodial protrusions necessary for tubule remodelling, thereby influencing subsequent stages of lumen morphogenesis. PMID:26129894

  14. A Rac/Cdc42 exchange factor complex promotes formation of lateral filopodia and blood vessel lumen morphogenesis.

    PubMed

    Abraham, Sabu; Scarcia, Margherita; Bagshaw, Richard D; McMahon, Kathryn; Grant, Gary; Harvey, Tracey; Yeo, Maggie; Esteves, Filomena O G; Thygesen, Helene H; Jones, Pamela F; Speirs, Valerie; Hanby, Andrew M; Selby, Peter J; Lorger, Mihaela; Dear, T Neil; Pawson, Tony; Marshall, Christopher J; Mavria, Georgia

    2015-07-01

    During angiogenesis, Rho-GTPases influence endothelial cell migration and cell-cell adhesion; however it is not known whether they control formation of vessel lumens, which are essential for blood flow. Here, using an organotypic system that recapitulates distinct stages of VEGF-dependent angiogenesis, we show that lumen formation requires early cytoskeletal remodelling and lateral cell-cell contacts, mediated through the RAC1 guanine nucleotide exchange factor (GEF) DOCK4 (dedicator of cytokinesis 4). DOCK4 signalling is necessary for lateral filopodial protrusions and tubule remodelling prior to lumen formation, whereas proximal, tip filopodia persist in the absence of DOCK4. VEGF-dependent Rac activation via DOCK4 is necessary for CDC42 activation to signal filopodia formation and depends on the activation of RHOG through the RHOG GEF, SGEF. VEGF promotes interaction of DOCK4 with the CDC42 GEF DOCK9. These studies identify a novel Rho-family GTPase activation cascade for the formation of endothelial cell filopodial protrusions necessary for tubule remodelling, thereby influencing subsequent stages of lumen morphogenesis.

  15. TMED10 Protein Interferes with Transforming Growth Factor (TGF)-β Signaling by Disrupting TGF-β Receptor Complex Formation.

    PubMed

    Nakano, Naoko; Tsuchiya, Yuki; Kako, Kenro; Umezaki, Kenryu; Sano, Keigo; Ikeno, Souichi; Otsuka, Eri; Shigeta, Masashi; Nakagawa, Ai; Sakata, Nobuo; Itoh, Fumiko; Nakano, Yota; Iemura, Shun-Ichiro; van Dinther, Maarten; Natsume, Tohru; Ten Dijke, Peter; Itoh, Susumu

    2017-03-10

    The intensity and duration of TGF-β signaling determine the cellular biological response. How this is negatively regulated is not well understood. Here, we identified a novel negative regulator of TGF-β signaling, transmembrane p24-trafficking protein 10 (TMED10). TMED10 disrupts the complex formation between TGF-β type I (also termed ALK5) and type II receptors (TβRII). Misexpression studies revealed that TMED10 attenuated TGF-β-mediated signaling. A 20-amino acid-long region from Thr(91) to Glu(110) within the extracellular region of TMED10 was found to be crucial for TMED10 interaction with both ALK5 and TβRII. Synthetic peptides corresponding to this region inhibit both TGF-β-induced Smad2 phosphorylation and Smad-dependent transcriptional reporter activity. In a xenograft cancer model, where previously TGF-β was shown to elicit tumor-promoting effects, gain-of-function and loss-of-function studies for TMED10 revealed a decrease and increase in the tumor size, respectively. Thus, we determined herein that TMED10 expression levels are the key determinant for efficiency of TGF-β receptor complex formation and signaling.

  16. Analysis of small latent transforming growth factor-beta complex formation and dissociation by surface plasmon resonance. Absence of direct interaction with thrombospondins.

    PubMed

    Bailly, S; Brand, C; Chambaz, E M; Feige, J J

    1997-06-27

    Transforming growth factor-beta (TGFbeta) is a pluripotent regulator of cell growth and differentiation. The growth factor is expressed as a latent complex that must be converted to an active form before interacting with its ubiquitous high affinity receptors. This conversion involves the release of the mature TGFbeta through disruption of the noncovalent interactions with its propeptide or latency associated protein (LAP). Complex formation or dissociation between LAP and TGFbeta plays a very important role in TGFbeta biological activity at different steps. To further characterize the kinetic parameters of this interaction, we have employed surface plasmon resonance biosensor methodology. Using this technique, we observed real time association of LAP with mature TGFbeta1. The complex formation showed an equilibrium Kd around 3-7 nM. Furthermore, we observed dissociation of the complex in the presence of extreme pH, chaotropic agents, or plasmin, confirming their effects on TGFbeta activation. The same approach was used to examine whether latent TGFbeta1 could interact with thrombospondins, previously described as activators of latent TGFbeta. Using this method, we could not detect any direct interaction of thrombospondins with either LAP alone, TGFbeta1 alone, or the small latent TGFbeta1 complex. This suggests that activation of latent TGFbeta1 complex by thrombospondins is through an indirect mechanism.

  17. Factors stimulating bone formation.

    PubMed

    Lind, M; Bünger, C

    2001-10-01

    The aim of this review is to describe major approaches for stimulating bone healing and to review other factors affecting bone healing. Spinal bone fusion after surgery is a demanding process requiring optimal conditions for clinical success. Bone formation and healing can be enhanced through various methods. Experimental studies have revealed an array of stimulative measures. These include biochemical stimulation by use of hormones and growth factors, physical stimulation through mechanical and electromagnetic measures, and bone grafting by use of bone tissue or bone substitutes. Newer biological techniques such as stem cell transplantation and gene therapy can also be used to stimulate bone healing. Apart from bone transplantation, clinical experience with the many stimulation modalities is limited. Possible areas for clinical use of these novel methods are discussed.

  18. Traumatic Brain Injury Impairs Soluble N-Ethylmaleimide-Sensitive Factor Attachment Protein Receptor Complex Formation and Alters Synaptic Vesicle Distribution in the Hippocampus

    PubMed Central

    Carlson, Shaun W.; Yan, Hong; Ma, Michelle; Li, Youming; Henchir, Jeremy

    2016-01-01

    Abstract Traumatic brain injury (TBI) impairs neuronal function and can culminate in lasting cognitive impairment. While impaired neurotransmitter release has been well established after experimental TBI, little is understood about the mechanisms underlying this consequence. In the synapse, vesicular docking and neurotransmitter release requires the formation of the soluble N-ethylmaleimide-sensitive factor attachment protein receptor (SNARE) complex. Impairments in vesicle docking, and alterations in SNARE complex formation are associated with impaired neurotransmitter release. We hypothesized that TBI reduces SNARE complex formation and disrupts synaptic vesicle distribution in the hippocampus. To examine the effect of TBI on the SNARE complex, rats were subjected to controlled cortical impact (CCI) or sham injury, and the brains were assessed at 6 h, 1 d, one week, two weeks, or four weeks post-injury. Immunoblotting of hippocampal homogenates revealed significantly reduced SNARE complex formation at one week and two weeks post-injury. To assess synaptic vesicles distribution, rats received CCI or sham injury and the brains were processed for transmission electron microscopy at one week post-injury. Synapses in the hippocampus were imaged at 100k magnification, and vesicle distribution was assessed in pre-synaptic terminals at the active zone. CCI resulted in a significant reduction in vesicle number within 150 nm of the active zone. These findings provide the first evidence of TBI-induced impairments in synaptic vesicle docking, and suggest that reductions in the pool of readily releasable vesicles and impaired SNARE complex formation are two novel mechanisms contributing to impaired neurotransmission after TBI. PMID:25923735

  19. Endogenous factors enhance HIV infection of tissue naive CD4 T cells by stimulating high molecular mass APOBEC3G complex formation.

    PubMed

    Kreisberg, Jason F; Yonemoto, Wes; Greene, Warner C

    2006-04-17

    Human immunodeficiency virus (HIV) can infect resting CD4 T cells residing in lymphoid tissues but not those circulating in peripheral blood. The molecular mechanisms producing this difference remain unknown. We explored the potential role of the tissue microenvironment and its influence on the action of the antiviral factor APOBEC3G (A3G) in regulating permissivity to HIV infection. We found that endogenous IL-2 and -15 play a key role in rendering resident naive CD4 T cells susceptible to HIV infection. Infection of memory CD4 T cells also requires endogenous soluble factors, but not IL-2 or -15. A3G is found in a high molecular mass complex in HIV infection-permissive, tissue-resident naive CD4 T cells but resides in a low molecular mass form in nonpermissive, blood-derived naive CD4 T cells. Upon treatment with endogenous soluble factors, these cells become permissive for HIV infection, as low molecular mass A3G is induced to assemble into high molecular mass complexes. These findings suggest that in lymphoid tissues, endogenous soluble factors, likely including IL-2 and -15 and others, stimulate the formation of high molecular mass A3G complexes in tissue-resident naive CD4 T cells, thereby relieving the potent postentry restriction block for HIV infection conferred by low molecular mass A3G.

  20. Transcription factor complex formation and chromatin fine structure alterations at the murine c-fms (CSF-1 receptor) locus during maturation of myeloid precursor cells

    PubMed Central

    Tagoh, Hiromi; Himes, Roy; Clarke, Deborah; Leenen, Pieter J.M.; Riggs, Arthur D.; Hume, David; Bonifer, Constanze

    2002-01-01

    Expression of the gene for the macrophage colony stimulating factor receptor (CSF-1R), c-fms, has been viewed as a hallmark of the commitment of multipotent precursor cells to macrophages. Lineage-restricted expression of the gene is controlled by conserved elements in the proximal promoter and within the first intron. To investigate the developmental regulation of c-fms at the level of chromatin structure, we developed an in vitro system to examine the maturation of multipotent myeloid precursor cells into mature macrophages. The dynamics of chromatin fine structure alterations and transcription factor occupancy at the c-fms promoter and intronic enhancer was examined by in vivo DMS and UV-footprinting. We show that the c-fms gene is already transcribed at low levels in early myeloid precursors on which no CSF-1R surface expression can be detected. At this stage of myelopoiesis, the formation of transcription factor complexes on the promoter was complete. By contrast, occupancy of the enhancer was acutely regulated during macrophage differentiation. Our data show that cell-intrinsic differentiation decisions at the c-fms locus precede the appearance of c-fms on the cell surface. They also suggest that complex lineage-specific enhancers such as the c-fms intronic enhancer regulate local chromatin structure through the coordinated assembly and disassembly of distinct transcription factor complexes. PMID:12101129

  1. The interaction surface of a bacterial transcription elongation factor required for complex formation with an antiterminator during transcription antitermination.

    PubMed

    Mishra, Saurabh; Mohan, Shalini; Godavarthi, Sapna; Sen, Ranjan

    2013-09-27

    The bacterial transcription elongation factor, NusA, functions as an antiterminator when it is bound to the lambdoid phage derived antiterminator protein, N. The mode of N-NusA interaction is unknown, knowledge of which is essential to understand the antitermination process. It was reported earlier that in the absence of the transcription elongation complex (EC), N interacts with the C-terminal AR1 domain of NusA. However, the functional significance of this interaction is obscure. Here we identified mutations in NusA N terminus (NTD) specifically defective for N-mediated antitermination. These are located at a convex surface of the NusA-NTD, situated opposite its concave RNA polymerase (RNAP) binding surface. These NusA mutants disrupt the N-nut site interactions on the nascent RNA emerging out of a stalled EC. In the N/NusA-modified EC, a Cys-53 (S53C) from the convex surface of the NusA-NTD forms a specific disulfide (S-S) bridge with a Cys-39 (S39C) of the NusA binding region of the N protein. We conclude that when bound to the EC, the N interaction surface of NusA shifts from the AR1 domain to its NTD domain. This occurred due to a massive away-movement of the adjacent AR2 domain of NusA upon binding to the EC. We propose that the close proximity of this altered N-interaction site of NusA to its RNAP binding surface, enables N to influence the NusA-RNAP interaction during transcription antitermination that in turn facilitates the conversion of NusA into an antiterminator.

  2. The B cell coactivator Bob1 shows DNA sequence-dependent complex formation with Oct-1/Oct-2 factors, leading to differential promoter activation.

    PubMed

    Gstaiger, M; Georgiev, O; van Leeuwen, H; van der Vliet, P; Schaffner, W

    1996-06-03

    We have shown previously that both octamer binding transcription factors, namely the ubiquitous Oct-1 and the B cell-specific Oct-2A protein, can be enhanced in transcriptional activity by their association with the B cell-specific coactivator protein Bob1, also called OBF-1 or OCA-B. Here we study the structural requirements for ternary complex formation of DNA-Oct-Bob1 and coactivation function of Bob1. In analogy to DNA-bound transcription factors, Bob1 has a modular structure that includes an interaction domain (amino acids 1-65) and a C-terminal domain (amino acids 65-256), both important for transcriptional activation. A mutational analysis has resolved a region of seven amino acids (amino acids 26-32) in the N-terminus of Bob1 that are important for contacting the DNA binding POU domain of Oct-1 or Oct-2. In contrast to the viral coactivator VP16 (vmw65), which interacts with Oct-1 via the POU homeosubdomain, Bob1 association with Oct factors requires residues located in the POU-specific subdomain. Because the same residues are also involved in DNA recognition, we surmised that this association would affect the DNA binding specificity of the Oct-Bob1 complex compared with free Oct factors. While Oct-1 or Oct-2 bind to a large variety of octamer sequences, Bob1 ternary complex formation is indeed highly selective and occurs only in a subset of these sequences, leading to the differential coactivation of octamer-containing promoters. The results uncover a new level in selectivity that furthers our understanding in the regulation of cell type-specific gene expression.

  3. Transcriptional activation of human CYP17 in H295R adrenocortical cells depends on complex formation among p54(nrb)/NonO, protein-associated splicing factor, and SF-1, a complex that also participates in repression of transcription.

    PubMed

    Sewer, Marion B; Nguyen, Viet Q; Huang, Ching-Jung; Tucker, Philip W; Kagawa, Norio; Waterman, Michael R

    2002-04-01

    The first 57 bp upstream of the transcription initiation site of the human CYP17 (hCYP17) gene are essential for both basal and cAMP-dependent transcription. EMSA carried out by incubating H295R adrenocortical cell nuclear extracts with radiolabeled -57/-38 probe from the hCYP17 promoter showed the formation of three DNA-protein complexes. The fastest complex contained steroidogenic factor (SF-1) and p54(nrb)/NonO, the intermediate complex contained p54(nrb)/NonO and polypyrimidine tract-binding protein-associated splicing factor (PSF), and the slowest complex contained an SF-1/PSF/p54(nrb)/NonO complex. (Bu)(2)cAMP treatment resulted in a cAMP-inducible increase in the binding intensity of only the upper complex and also activated hCYP17 gene transcription. SF-1 coimmunoprecipitated with p54(nrb)/NonO, indicating direct interaction between these proteins. Functional assays revealed that PSF represses basal transcription. Further, the repression of hCYP17 promoter-reporter construct luciferase activity resulted from PSF interacting with the corepressor mSin3A. Trichostatin A attenuated the inhibition of basal transcription, suggesting that a histone deacetylase interacts with the SF-1/PSF/p54(nrb)/NonO/mSin3A complex. Our studies lend support to the idea that the balance between transcriptional activation and repression is essential in the control of adrenocortical steroid hormone biosynthesis.

  4. Statistical Factors in Complexation Reactions.

    ERIC Educational Resources Information Center

    Chung, Chung-Sun

    1985-01-01

    Four cases which illustrate statistical factors in complexation reactions (where two of the reactants are monodentate ligands) are presented. Included are tables showing statistical factors for the reactions of: (1) square-planar complexes; (2) tetrahedral complexes; and (3) octahedral complexes. (JN)

  5. Roles of factor Va heavy and light chains in protein and lipid rearrangements associated with the formation of a bovine factor Va-membrane complex.

    PubMed Central

    Koppaka, V; Talbot, W F; Zhai, X; Lentz, B R

    1997-01-01

    Factor Va is an essential protein cofactor of the enzyme factor Xa, which activates prothrombin to thrombin during blood coagulation. Peptides with an apparent Mr of approximately 94,000 (heavy chain; HC) and approximately 74,000 or 72,000 (light chain; LC) interact in the presence of Ca2+ to form active Va. The two forms of Va-LC differ in their carboxyl-terminal C2 domain. Using Va reconstituted with either LC form, we examined the effects of the two LC species on membrane binding and on the activity of membrane-bound Va. We found that 1) Va composed of the 72,000 LC bound only slightly more tightly to membranes composed of a mixture of neutral and acidic lipids, the Kd being reduced by a factor of approximately 3 at 5 mM and by a factor of 6 at 2 mM Ca2+. 2) The two forms of Va seemed to undergo different conformational changes when bound to a membrane. 3) The activity of bovine Va varied somewhat with LC species, the difference being greatest at limiting Xa concentration. We have also addressed the role of the two Va peptides in membrane lipid rearrangements and binding: 1) Va binding increased lateral packing density in mixed neutral/acidic lipid membranes. In the solid phase, Va-HC had no effect, whereas Va-LC and whole Va had similar but small effects. In the fluid phase, Va-HC and whole Va both altered membrane packing, with Va-HC having the largest effect. 2) Va-HC bound reversibly and in a Ca2+-independent fashion to membranes composed of neutral phospholipid (Kd, approximately 0.3 microM; stoichiometry approximately 91). High ionic strength had little effect on binding. 3) The substantial effect of Va on packing within neutral phospholipid membranes was mimicked by Va-HC. 4) Based on measurements of membrane phase behavior, binding of Va or its peptide components did not induce thermodynamically discernible lateral membrane domains. These results suggest that the membrane association of factor Va is a complex process involving both chains of Va, changes

  6. Pattern Formation and Complexity Emergence

    NASA Astrophysics Data System (ADS)

    Berezin, Alexander A.

    2001-03-01

    Success of nonlinear modelling of pattern formation and self-organization encourages speculations on informational and number theoretical foundations of complexity emergence. Pythagorean "unreasonable effectiveness of integers" in natural processes is perhaps extrapolatable even to universal emergence "out-of-nothing" (Leibniz, Wheeler). Because rational numbers (R = M/N) are everywhere dense on real axis, any digital string (hence any "book" from "Library of Babel" of J.L.Borges) is "recorded" infinitely many times in arbitrary many rationals. Furthermore, within any arbitrary small interval there are infinitely many Rs for which (either or both) integers (Ms and Ns) "carry" any given string of any given length. Because any iterational process (such as generation of fractal features of Mandelbrot Set) is arbitrary closely approximatable with rational numbers, the infinite pattern of integers expresses itself in generation of complexity of the world, as well as in emergence of the world itself. This "tunnelling" from Platonic World ("Platonia" of J.Barbour) to a real (physical) world is modern recast of Leibniz's motto ("for deriving all from nothing there suffices a single principle").

  7. Spray formation with complex fluids

    NASA Astrophysics Data System (ADS)

    Lustig, S.; Rosen, M.

    2011-05-01

    Droplet formation through Faraday excitation has been tested in the low driving frequency limit. Kerosene was used to model liquid fuel with the addition of PIB in different proportions. All fluids were characterized in detail. The mechanisms of ejection were investigated to identify the relative influence of viscosity and surface tension. It was also possible to characterize the type of instability leading to the emission drop process.

  8. Mixed real/complex factorization

    SciTech Connect

    Lima, L.T.G. . Dept. of Electrical Engineering); Martines, N.; Pinto, H.J.C.P. . Centro de Pesquisas de Energia Electrica)

    1993-02-01

    This paper describes a mixed real/complex sparse matrix factorization and solution scheme applied to a large matrix problem. Large system eigenanalysis and frequency domain methods will directly benefit from the proposed scheme, which can reduce both memory and CPU time requirements when compared to conventional complex-only solutions. The application in hand is the small signal electromechanical stability analysis of large power systems. The savings obtained are significant considering the CPU intensive nature of these matrix problems.

  9. Complementary quantitative proteomics reveals that transcription factor AP-4 mediates E-box-dependent complex formation for transcriptional repression of HDM2.

    PubMed

    Ku, Wei-Chi; Chiu, Sung-Kay; Chen, Yi-Ju; Huang, Hsin-Hung; Wu, Wen-Guey; Chen, Yu-Ju

    2009-09-01

    Transcription factor activating enhancer-binding protein 4 (AP-4) is a basic helix-loop-helix protein that binds to E-box elements. AP-4 has received increasing attention for its regulatory role in cell growth and development, including transcriptional repression of the human homolog of murine double minute 2 (HDM2), an important oncoprotein controlling cell growth and survival, by an unknown mechanism. Here we demonstrate that AP-4 binds to an E-box located in the HDM2-P2 promoter and represses HDM2 transcription in a p53-independent manner. Incremental truncations of AP-4 revealed that the C-terminal Gln/Pro-rich domain was essential for transcriptional repression of HDM2. To further delineate the molecular mechanism(s) of AP-4 transcriptional control and its potential implications, we used DNA-affinity purification followed by complementary quantitative proteomics, cICAT and iTRAQ labeling methods, to identify a previously unknown E-box-bound AP-4 protein complex containing 75 putative components. The two labeling methods complementarily quantified differentially AP-4-enriched proteins, including the most significant recruitment of DNA damage response proteins, followed by transcription factors, transcriptional repressors/corepressors, and histone-modifying proteins. Specific interaction of AP-4 with CCCTC binding factor, stimulatory protein 1, and histone deacetylase 1 (an AP-4 corepressor) was validated using AP-4 truncation mutants. Importantly, inclusion of trichostatin A did not alleviate AP-4-mediated repression of HDM2 transcription, suggesting a previously unidentified histone deacetylase-independent repression mechanism. In contrast, the complementary quantitative proteomics study suggested that transcription repression occurs via coordination of AP-4 with other transcription factors, histone methyltransferases, and/or a nucleosome remodeling SWI.SNF complex. In addition to previously known functions of AP-4, our data suggest that AP-4 participates in a

  10. STAR FORMATION ACROSS THE W3 COMPLEX

    SciTech Connect

    Román-Zúñiga, Carlos G.; Ybarra, Jason E.; Tapia, Mauricio; Megías, Guillermo D.; Lada, Elizabeth A.; Alves, Joáo F.

    2015-09-15

    We present a multi-wavelength analysis of the history of star formation in the W3 complex. Using deep, near-infrared ground-based images combined with images obtained with Spitzer and Chandra observatories, we identified and classified young embedded sources. We identified the principal clusters in the complex and determined their structure and extension. We constructed extinction-limited samples for five principal clusters and constructed K-band luminosity functions that we compare with those of artificial clusters with varying ages. This analysis provided mean ages and possible age spreads for the clusters. We found that IC 1795, the centermost cluster of the complex, still hosts a large fraction of young sources with circumstellar disks. This indicates that star formation was active in IC 1795 as recently as 2 Myr ago, simultaneous to the star-forming activity in the flanking embedded clusters, W3-Main and W3(OH). A comparison with carbon monoxide emission maps indicates strong velocity gradients in the gas clumps hosting W3-Main and W3(OH) and shows small receding clumps of gas at IC 1795, suggestive of rapid gas removal (faster than the T Tauri timescale) in the cluster-forming regions. We discuss one possible scenario for the progression of cluster formation in the W3 complex. We propose that early processes of gas collapse in the main structure of the complex could have defined the progression of cluster formation across the complex with relatively small age differences from one group to another. However, triggering effects could act as catalysts for enhanced efficiency of formation at a local level, in agreement with previous studies.

  11. Star Formation Across the W3 Complex

    NASA Astrophysics Data System (ADS)

    Román-Zúñiga, Carlos G.; Ybarra, Jason E.; Megías, Guillermo D.; Tapia, Mauricio; Lada, Elizabeth A.; Alves, Joáo F.

    2015-09-01

    We present a multi-wavelength analysis of the history of star formation in the W3 complex. Using deep, near-infrared ground-based images combined with images obtained with Spitzer and Chandra observatories, we identified and classified young embedded sources. We identified the principal clusters in the complex and determined their structure and extension. We constructed extinction-limited samples for five principal clusters and constructed K-band luminosity functions that we compare with those of artificial clusters with varying ages. This analysis provided mean ages and possible age spreads for the clusters. We found that IC 1795, the centermost cluster of the complex, still hosts a large fraction of young sources with circumstellar disks. This indicates that star formation was active in IC 1795 as recently as 2 Myr ago, simultaneous to the star-forming activity in the flanking embedded clusters, W3-Main and W3(OH). A comparison with carbon monoxide emission maps indicates strong velocity gradients in the gas clumps hosting W3-Main and W3(OH) and shows small receding clumps of gas at IC 1795, suggestive of rapid gas removal (faster than the T Tauri timescale) in the cluster-forming regions. We discuss one possible scenario for the progression of cluster formation in the W3 complex. We propose that early processes of gas collapse in the main structure of the complex could have defined the progression of cluster formation across the complex with relatively small age differences from one group to another. However, triggering effects could act as catalysts for enhanced efficiency of formation at a local level, in agreement with previous studies.

  12. Complex organic molecules and star formation

    NASA Astrophysics Data System (ADS)

    Bacmann, A.; Faure, A.

    2014-12-01

    Star forming regions are characterised by the presence of a wealth of chemical species. For the past two to three decades, ever more complex organic species have been detected in the hot cores of protostars. The evolution of these molecules in the course of the star forming process is still uncertain, but it is likely that they are partially incorporated into protoplanetary disks and then into planetesimals and the small bodies of planetary systems. The complex organic molecules seen in star forming regions are particularly interesting since they probably make up building blocks for prebiotic chemistry. Recently we showed that these species were also present in the cold gas in prestellar cores, which represent the very first stages of star formation. These detections question the models which were until now accepted to account for the presence of complex organic molecules in star forming regions. In this article, we shortly review our current understanding of complex organic molecule formation in the early stages of star formation, in hot and cold cores alike and present new results on the formation of their likely precursor radicals.

  13. Dynamic studies of H-Ras•GTPγS interactions with nucleotide exchange factor Sos reveal a transient ternary complex formation in solution

    PubMed Central

    Vo, Uybach; Vajpai, Navratna; Embrey, Kevin J.; Golovanov, Alexander P.

    2016-01-01

    The cycling between GDP- and GTP- bound forms of the Ras protein is partly regulated by the binding of Sos. The structural/dynamic behavior of the complex formed between activated Sos and Ras at the point of the functional cycle where the nucleotide exchange is completed has not been described to date. Here we show that solution NMR spectra of H-Ras∙GTPγS mixed with a functional fragment of Sos (SosCat) at a 2:1 ratio are consistent with the formation of a rather dynamic assembly. H-Ras∙GTPγS binding was in fast exchange on the NMR timescale and retained a significant degree of molecular tumbling independent of SosCat, while SosCat also tumbled largely independently of H-Ras. Estimates of apparent molecular weight from both NMR data and SEC-MALS revealed that, at most, only one H-Ras∙GTPγS molecule appears stably bound to Sos. The weak transient interaction between Sos and the second H-Ras∙GTPγS may provide a necessary mechanism for complex dissociation upon the completion of the native GDP → GTP exchange reaction, but also explains measurable GTP → GTP exchange activity of Sos routinely observed in in vitro assays that use fluorescently-labelled analogs of GTP. Overall, the data presents the first dynamic snapshot of Ras functional cycle as controlled by Sos. PMID:27412770

  14. Environmental factors that shape biofilm formation.

    PubMed

    Toyofuku, Masanori; Inaba, Tomohiro; Kiyokawa, Tatsunori; Obana, Nozomu; Yawata, Yutaka; Nomura, Nobuhiko

    2015-01-01

    Cells respond to the environment and alter gene expression. Recent studies have revealed the social aspects of bacterial life, such as biofilm formation. Biofilm formation is largely affected by the environment, and the mechanisms by which the gene expression of individual cells affects biofilm development have attracted interest. Environmental factors determine the cell's decision to form or leave a biofilm. In addition, the biofilm structure largely depends on the environment, implying that biofilms are shaped to adapt to local conditions. Second messengers such as cAMP and c-di-GMP are key factors that link environmental factors with gene regulation. Cell-to-cell communication is also an important factor in shaping the biofilm. In this short review, we will introduce the basics of biofilm formation and further discuss environmental factors that shape biofilm formation. Finally, the state-of-the-art tools that allow us investigate biofilms under various conditions are discussed.

  15. Interactive formation control in complex environments.

    PubMed

    Henry, Joseph; Shum, Hubert P H; Komura, Taku

    2014-02-01

    The degrees of freedom of a crowd is much higher than that provided by a standard user input device. Typically, crowd-control systems require multiple passes to design crowd movements by specifying waypoints, and then defining character trajectories and crowd formation. Such multi-pass control would spoil the responsiveness and excitement of real-time control systems. In this paper, we propose a single-pass algorithm to control a crowd in complex environments. We observe that low-level details in crowd movement are related to interactions between characters and the environment, such as diverging/merging at cross points, or climbing over obstacles. Therefore, we simplify the problem by representing the crowd with a deformable mesh, and allow the user, via multitouch input, to specify high-level movements and formations that are important for context delivery. To help prevent congestion, our system dynamically reassigns characters in the formation by employing a mass transport solver to minimize their overall movement. The solver uses a cost function to evaluate the impact from the environment, including obstacles and areas affecting movement speed. Experimental results show realistic crowd movement created with minimal high-level user inputs. Our algorithm is particularly useful for real-time applications including strategy games and interactive animation creation.

  16. Interactive Formation Control in Complex Environments.

    PubMed

    Henry, Joseph; Shum, Hubert P H; Komura, Taku

    2013-08-13

    The degrees of freedom of a crowd is much higher than that provided by a standard user input device. Typically, crowd control systems require multiple passes to design crowd movements by specifying waypoints, and then defining character trajectories and crowd formation. Such multi-pass control would spoil the responsiveness and excitement of real-time control systems. In this paper, we propose a single-pass algorithm to control a crowd in complex environments. We observe that low level details in crowd movement are related to interactions between characters and the environment, such as diverging/merging at cross points, or climbing over obstacles. Therefore, we simplify the problem by representing the crowd with a deformable mesh, and allow the user, via multi-touch input, to specify high level movements and formations that are important for context delivery. To help prevent congestion, our system dynamically reassigns characters in the formation by employing a mass transport solver to minimise their overall movement. The solver uses a cost function to evaluate the impact from the environment, including obstacles and areas affecting movement speed. Experimental results show realistic crowd movement created with minimal high-level user inputs. Our algorithm is particularly useful for real-time applications including strategy games and interactive animation creation.

  17. The Drosophila GAGA factor is required for dosage compensation in males and for the formation of the male-specific-lethal complex chromatin entry site at 12DE.

    PubMed Central

    Greenberg, Anthony J; Yanowitz, Judith L; Schedl, Paul

    2004-01-01

    Drosophila melanogaster males have one X chromosome, while females have two. To compensate for the resulting disparity in X-linked gene expression between the two sexes, most genes from the male X chromosome are hyperactivated by a special dosage compensation system. Dosage compensation is achieved by a complex of at least six proteins and two noncoding RNAs that specifically associate with the male X. A central question is how the X chromosome is recognized. According to a current model, complexes initially assemble at approximately 35 chromatin entry sites on the X and then spread bidirectionally along the chromosome where they occupy hundreds of sites. Here, we report that mutations in Trithorax-like (Trl) lead to the loss of a single chromatin entry site on the X, male lethality, and mislocalization of dosage compensation complexes. PMID:15020425

  18. Subcutaneous administration of insulin-like growth factor (IGF)-II/IGF binding protein-2 complex stimulates bone formation and prevents loss of bone mineral density in a rat model of disuse osteoporosis

    NASA Technical Reports Server (NTRS)

    Conover, Cheryl A.; Johnstone, Edward W.; Turner, Russell T.; Evans, Glenda L.; John Ballard, F. John; Doran, Patrick M.; Khosla, Sundeep

    2002-01-01

    Elevated serum levels of insulin-like growth factor binding protein-2 (IGFBP-2) and a precursor form of IGF-II are associated with marked increases in bone formation and skeletal mass in patients with hepatitis C-associated osteosclerosis. In vitro studies indicate that IGF-II in complex with IGFBP-2 has high affinity for bone matrix and is able to stimulate osteoblast proliferation. The purpose of this study was to determine the ability of the IGF-II/IGFBP-2 complex to increase bone mass in vivo. Osteopenia of the femur was induced by unilateral sciatic neurectomy in rats. At the time of surgery, 14-day osmotic minipumps containing vehicle or 2 microg IGF-II+9 microg IGFBP-2/100g body weight/day were implanted subcutaneously in the neck. Bone mineral density (BMD) measurements were taken the day of surgery and 14 days later using a PIXImus small animal densitometer. Neurectomy of the right hindlimb resulted in a 9% decrease in right femur BMD (P<0.05 vs. baseline). This loss in BMD was completely prevented by treatment with IGF-II/IGFBP-2. On the control limb, there was no loss of BMD over the 14 days and IGF-II/IGFBP-2 treatment resulted in a 9% increase in left femur BMD (P<0.05). Bone histomorphometry indicated increases in endocortical and cancellous bone formation rates and in trabecular thickness. These results demonstrate that short-term administration of the IGF-II/IGFBP-2 complex can prevent loss of BMD associated with disuse osteoporosis and stimulate bone formation in adult rats. Furthermore, they provide proof of concept for a novel anabolic approach to increasing bone mass in humans with osteoporosis.

  19. Identification of neuronal and angiogenic growth factors in an in vitro blood-brain barrier model system: Relevance in barrier integrity and tight junction formation and complexity.

    PubMed

    Freese, Christian; Hanada, Sanshiro; Fallier-Becker, Petra; Kirkpatrick, C James; Unger, Ronald E

    2017-05-01

    We previously demonstrated that the co-cultivation of endothelial cells with neural cells resulted in an improved integrity of the in vitro blood-brain barrier (BBB), and that this model could be useful to evaluate the transport properties of potential central nervous system disease drugs through the microvascular brain endothelial. In this study we have used real-time PCR, fluorescent microscopy, protein arrays and enzyme-linked immunosorbent assays to determine which neural- and endothelial cell-derived factors are produced in the co-culture and improve the integrity of the BBB. In addition, a further improvement of the BBB integrity was achieved by adjusting serum concentrations and growth factors or by the addition of brain pericytes. Under specific conditions expression of angiogenic, angiostatic and neurotrophic factors such as endostatin, pigment epithelium derived factor (PEDF/serpins-F1), tissue inhibitor of metalloproteinases (TIMP-1), and vascular endothelial cell growth factor (VEGF) closely mimicked the in vivo situation. Freeze-fracture analysis of these cultures demonstrated the quality and organization of the endothelial tight junction structures and their association to the two different lipidic leaflets of the membrane. Finally, a multi-cell culture model of the BBB with a transendothelial electrical resistance up to 371 (±15) Ω×cm(2) was developed, which may be useful for preliminary screening of drug transport across the BBB and to evaluate cellular crosstalk of cells involved in the neurovascular unit.

  20. Nanoparticle-protein complexes mimicking corona formation in ocular environment.

    PubMed

    Jo, Dong Hyun; Kim, Jin Hyoung; Son, Jin Gyeong; Dan, Ki Soon; Song, Sang Hoon; Lee, Tae Geol; Kim, Jeong Hun

    2016-12-01

    Nanoparticles adsorb biomolecules to form corona upon entering the biological environment. In this study, tissue-specific corona formation is provided as a way of controlling protein interaction with nanoparticles in vivo. In the vitreous, the composition of the corona was determined by the electrostatic and hydrophobic properties of the associated proteins, regardless of the material (gold and silica) or size (20- and 100-nm diameter) of the nanoparticles. To control protein adsorption, we pre-incubate 20-nm gold nanoparticles with 5 selectively enriched proteins from the corona, formed in the vitreous, to produce nanoparticle-protein complexes. Compared to bare nanoparticles, nanoparticle-protein complexes demonstrate improved binding to vascular endothelial growth factor (VEGF) in the vitreous. Furthermore, nanoparticle-protein complexes retain in vitro anti-angiogenic properties of bare nanoparticles. In particular, priming the nanoparticles (gold and silica) with tissue-specific corona proteins allows nanoparticle-protein complexes to exert better in vivo therapeutic effects by higher binding to VEGF than bare nanoparticles. These results suggest that controlled corona formation that mimics in vivo processes may be useful in the therapeutic use of nanomaterials in local environment.

  1. Factors influencing acrylamide formation in gingerbread.

    PubMed

    Amrein, Thomas M; Schönbächler, Barbara; Escher, Felix; Amadò, Renato

    2005-01-01

    The influence of ingredients, additives, and process conditions on the acrylamide formation in gingerbread was investigated. The sources for reducing sugars and free asparagine were identified and the effect of different baking agents on the acrylamide formation was evaluated. Ammonium hydrogencarbonate strongly enhanced the acrylamide formation, but its N-atom was not incorporated into acrylamide, nor did acrylic acid form acrylamide in gingerbread. Acrylamide concentration and browning intensity increased both with baking time and correlated with each other. The use of sodium hydrogencarbonate as baking agent reduced the acrylamide concentration by more than 60%. Free asparagine was a limiting factor for acrylamide formation, but the acrylamide content could also be lowered by replacing reducing sugars with sucrose or by adding moderate amounts of organic acids. A significant reduction of the acrylamide content in gingerbread can be achieved by using sodium hydrogencarbonate as baking agent, minimizing free asparagine, and avoiding prolonged baking.

  2. Formation of a Ternary Complex for Selenocysteine Biosynthesis in Bacteria*

    PubMed Central

    Silva, Ivan R.; Serrão, Vitor H. B.; Manzine, Livia R.; Faim, Lívia M.; da Silva, Marco T. A.; Makki, Raphaela; Saidemberg, Daniel M.; Cornélio, Marinônio L.; Palma, Mário S.; Thiemann, Otavio H.

    2015-01-01

    The synthesis of selenocysteine-containing proteins (selenoproteins) involves the interaction of selenocysteine synthase (SelA), tRNA (tRNASec), selenophosphate synthetase (SelD, SPS), a specific elongation factor (SelB), and a specific mRNA sequence known as selenocysteine insertion sequence (SECIS). Because selenium compounds are highly toxic in the cellular environment, the association of selenium with proteins throughout its metabolism is essential for cell survival. In this study, we demonstrate the interaction of SPS with the SelA-tRNASec complex, resulting in a 1.3-MDa ternary complex of 27.0 ± 0.5 nm in diameter and 4.02 ± 0.05 nm in height. To assemble the ternary complex, SPS undergoes a conformational change. We demonstrated that the glycine-rich N-terminal region of SPS is crucial for the SelA-tRNASec-SPS interaction and selenoprotein biosynthesis, as revealed by functional complementation experiments. Taken together, our results provide new insights into selenoprotein biosynthesis, demonstrating for the first time the formation of the functional ternary SelA-tRNASec-SPS complex. We propose that this complex is necessary for proper selenocysteine synthesis and may be involved in avoiding the cellular toxicity of selenium compounds. PMID:26378233

  3. On the Formation of "Hypercoordinated" Uranyl Complexes

    SciTech Connect

    Schoendorff, George E.; De Jong, Wibe A.; van Stipdonk, Michael J.; Gibson, John K.; Rios, Daniel; Gordon, Mark S.; Windus, Theresa L.

    2011-09-05

    Recent gas phase experimental studies suggest the presence of hypercoordinated uranyl complexes. Coordination of acetone (Ace) to uranyl to form hypercoordinated species is examined using density functional theory (DFT) with a range of functionals and second order perturbation theory (MP2). Complexes with up to eight acetones were studied. It is shown that no more than six acetones can bind directly to uranium and that the observed uranyl complexes are not hypercoordinated.

  4. Factors involved in the initiation of phage phi 29 DNA replication in vitro: requirement of the gene 2 product for the formation of the protein p3-dAMP complex.

    PubMed Central

    Blanco, L; Garcìa, J A; Peñalva, M A; Salas, M

    1983-01-01

    To study the requirements for the in vitro formation of the protein p3-dAMP complex, the first step in phi29 DNA replication, extracts from B. subtilis infected with phi29 mutants in genes 2, 3, 5, 6 and 17, involved in DNA synthesis, have been used. The formation of the initiation complex is completely dependent on the presence of a functional gene 2 product, in addition to protein p3 and phi29 DNA-protein p3 as template. ATP is also required, although it can be replaced by other nucleotides. The products of genes 5, 6 and 17 do not seem to be needed in the formation of the initiation complex. Inhibitors of the host DNA polymerase III, DNA gyrase or RNA polymerase had no effect on the formation of the protein p3-dAMP complex, suggesting that these proteins are not involved in the initiation of phi29 DNA replication. ddATP or aphidicolin, inhibitors of DNA chain elongation, had also no effect on the formation of the initiation complex. Images PMID:6402761

  5. Defective thrombus formation in mice lacking coagulation factor XII

    PubMed Central

    Renné, Thomas; Pozgajová, Miroslava; Grüner, Sabine; Schuh, Kai; Pauer, Hans-Ulrich; Burfeind, Peter; Gailani, David; Nieswandt, Bernhard

    2005-01-01

    Blood coagulation is thought to be initiated by plasma protease factor VIIa in complex with the membrane protein tissue factor. In contrast, coagulation factor XII (FXII)–mediated fibrin formation is not believed to play an important role for coagulation in vivo. We used FXII-deficient mice to study the contributions of FXII to thrombus formation in vivo. Intravital fluorescence microscopy and blood flow measurements in three distinct arterial beds revealed a severe defect in the formation and stabilization of platelet-rich occlusive thrombi. Although FXII-deficient mice do not experience spontaneous or excessive injury-related bleeding, they are protected against collagen- and epinephrine-induced thromboembolism. Infusion of human FXII into FXII-null mice restored injury-induced thrombus formation. These unexpected findings change the long-standing concept that the FXII-induced intrinsic coagulation pathway is not important for clotting in vivo. The results establish FXII as essential for thrombus formation, and identify FXII as a novel target for antithrombotic therapy. PMID:16009717

  6. Structural determinants for the formation of sulfhemeprotein complexes

    PubMed Central

    Román-Morales, Elddie; Pietri, Ruth; Ramos-Santana, Brenda; Vinogradov, Serge N.; Lewis-Ballester, Ariel; López-Garriga, Juan

    2010-01-01

    Several hemoglobins were explored by UV-Vis and resonance Raman spectroscopy to define sulfheme complex formation. Evaluation of these proteins upon the reaction with H2O2 or O2 in the presence of H2S suggest: (a) the formation of the sulfheme derivate requires a HisE7 residue in the heme distal site with an adequate orientation to form an active ternary complex; (b) that the ternary complex intermediate involves the HisE7, the peroxo or ferryl species, and the H2S molecule. This moiety precedes and triggers the sulfheme formation. PMID:20732304

  7. Changes in protein structure at the interface accompanying complex formation

    PubMed Central

    Chakravarty, Devlina; Janin, Joël; Robert, Charles H.; Chakrabarti, Pinak

    2015-01-01

    Protein interactions are essential in all biological processes. The changes brought about in the structure when a free component forms a complex with another molecule need to be characterized for a proper understanding of molecular recognition as well as for the successful implementation of docking algorithms. Here, unbound (U) and bound (B) forms of protein structures from the Protein–Protein Interaction Affinity Database are compared in order to enumerate the changes that occur at the interface atoms/residues in terms of the solvent-accessible surface area (ASA), secondary structure, temperature factors (B factors) and disorder-to-order transitions. It is found that the interface atoms optimize contacts with the atoms in the partner protein, which leads to an increase in their ASA in the bound interface in the majority (69%) of the proteins when compared with the unbound interface, and this is independent of the root-mean-square deviation between the U and B forms. Changes in secondary structure during the transition indicate a likely extension of helices and strands at the expense of turns and coils. A reduction in flexibility during complex formation is reflected in the decrease in B factors of the interface residues on going from the U form to the B form. There is, however, no distinction in flexibility between the interface and the surface in the monomeric structure, thereby highlighting the potential problem of using B factors for the prediction of binding sites in the unbound form for docking another protein. 16% of the proteins have missing (disordered) residues in the U form which are observed (ordered) in the B form, mostly with an irregular conformation; the data set also shows differences in the composition of interface and non-interface residues in the disordered polypeptide segments as well as differences in their surface burial. PMID:26594372

  8. Changes in protein structure at the interface accompanying complex formation.

    PubMed

    Chakravarty, Devlina; Janin, Joël; Robert, Charles H; Chakrabarti, Pinak

    2015-11-01

    Protein interactions are essential in all biological processes. The changes brought about in the structure when a free component forms a complex with another molecule need to be characterized for a proper understanding of molecular recognition as well as for the successful implementation of docking algorithms. Here, unbound (U) and bound (B) forms of protein structures from the Protein-Protein Interaction Affinity Database are compared in order to enumerate the changes that occur at the interface atoms/residues in terms of the solvent-accessible surface area (ASA), secondary structure, temperature factors (B factors) and disorder-to-order transitions. It is found that the interface atoms optimize contacts with the atoms in the partner protein, which leads to an increase in their ASA in the bound interface in the majority (69%) of the proteins when compared with the unbound interface, and this is independent of the root-mean-square deviation between the U and B forms. Changes in secondary structure during the transition indicate a likely extension of helices and strands at the expense of turns and coils. A reduction in flexibility during complex formation is reflected in the decrease in B factors of the interface residues on going from the U form to the B form. There is, however, no distinction in flexibility between the interface and the surface in the monomeric structure, thereby highlighting the potential problem of using B factors for the prediction of binding sites in the unbound form for docking another protein. 16% of the proteins have missing (disordered) residues in the U form which are observed (ordered) in the B form, mostly with an irregular conformation; the data set also shows differences in the composition of interface and non-interface residues in the disordered polypeptide segments as well as differences in their surface burial.

  9. Direct electronic probing of biological complexes formation

    NASA Astrophysics Data System (ADS)

    Macchia, Eleonora; Magliulo, Maria; Manoli, Kyriaki; Giordano, Francesco; Palazzo, Gerardo; Torsi, Luisa

    2014-10-01

    Functional bio-interlayer organic field - effect transistors (FBI-OFET), embedding streptavidin, avidin and neutravidin as bio-recognition element, have been studied to probe the electronic properties of protein complexes. The threshold voltage control has been achieved modifying the SiO2 gate diaelectric surface by means of the deposition of an interlayer of bio-recognition elements. A threshold voltage shift with respect to the unmodified dielectric surface toward more negative potential values has been found for the three different proteins, in agreement with their isoelectric points. The relative responses in terms of source - drain current, mobility and threshold voltage upon exposure to biotin of the FBI-OFET devices have been compared for the three bio-recognition elements.

  10. Administration of growth hormone (GH), but not insulin-like growth factor-I (IGF-I), by continuous infusion can induce the formation of the 150-kilodalton IGF-binding protein-3 complex in GH-deficient rats.

    PubMed

    Gargosky, S E; Tapanainen, P; Rosenfeld, R G

    1994-05-01

    In the adult circulation, 70-90% of the serum insulin-like growth factors (IGFs) are carried by IGF-binding protein-3 (IGFBP-3), which exists as part of a 150-kilodalton (kDa) ternary complex including IGF and an acid-labile subunit (ALS). We have examined the hormonal regulation and molecular distribution of IGFBP-3 in the circulation of a uniquely GH-deficient (GHD) rat model. For 7 days, GHD rats were given GH by either twice daily injections (1 mg/kg) or continuous infusion (2.4 mg/kg.day) or IGF-I by continuous infusion (1.4 mg/kg.day). Each day, weight and feed and water intake were monitored, and on day 7, liver, kidney, spleen, heart, and lung were weighted, and sera were collected. Serum IGF-I was analyzed by immunoassay, and the molecular distribution of the IGFBPs was determined by neutral size-exclusion chromatography combined with Western ligand blot and Western immunoblot. The GHD rats were 40-60% lighter than their normal littermates, and all organs examined were proportionately smaller. Serum IGF-I and IGFBP-3 levels were less than 10% of those in normal rats. Incubation of serum from GHD rats with [125I]IGF-II showed that radiolabel was incorporated only into a 44-kDa IGFBP region that contained the smaller IGFBPs. IGFBP-3 eluted around 60 kDa. No 150-kDa IGFBP region was detected. The administration of GH or IGF-I to GHD rats resulted in significant increases in weight gained, although food and water intake remained unaltered. Weight gain was observed in all three treatments groups. Both GH treatment regimens significantly increased liver, spleen, and lung weight, whereas IGF-I therapy increased spleen, kidney, and heart. Administration of GH twice daily did not increase serum IGF-I or IGFBP-3 concentrations, and the molecular distribution of IGFBP-3 remained unchanged. In contrast, continuous infusion of GH resulted in 5-fold increases in serum IGF-I and increases in IGFBP-3 levels. Size-exclusion chromatography combined with Western ligand blot

  11. Positronium formation in solid transition metal losartanates complexes

    NASA Astrophysics Data System (ADS)

    de Oliveira, F. C.; Denadai, A. M. L.; Fulgêncio, F.; da Silva, J. G.; Windmöller, D.; Marques-Netto, A.; Machado, J. C.; Magalhães, W. F.

    2013-10-01

    In this Letter, positron annihilation lifetime (PALS) measurements were performed in transition metal losartanates complexes, MT(Los)2, and in potassium losartanate, KLos, in order to built up insights about the positronium formation mechanism in molecular environment. A correlation was obtained between formation probability, I3, and the covalence of complexes, evaluated by molar electrical conductivity in dimethylformamide (DMF). Furthermore, some metallic ion properties, such as reduction potential and pauling electronegativity, were also correlated with I3. These results were analyzed in terms of the spur model and of the recently proposed mechanism, named cybotatic correlated system kinetic mechanism (CCSKM), which involves molecular excited states in positronium formation.

  12. Complex molecule formation around massive young stellar objects.

    PubMed

    Oberg, Karin I; Fayolle, Edith C; Reiter, John B; Cyganowski, Claudia

    2014-01-01

    Interstellar complex organic molecules were first identified in the hot inner regions of massive young stellar objects (MYSOs), but have more recently been found in many colder sources, indicating that complex molecules can form at a range of temperatures. However, individually these observations provide limited constraints on how complex molecules form, and whether the same formation pathways dominate in cold, warm and hot environments. To address these questions, we use spatially resolved observations from the Submillimeter Array of three MYSOs together with mostly unresolved literature data to explore how molecular ratios depend on environmental parameters, especially temperature. Towards the three MYSOs, we find multiple complex organic emission peaks characterized by different molecular compositions and temperatures. In particular, CH3CCH and CH3CN seem to always trace a lukewarm (T = 60 K) and a hot (T > 100 K) complex chemistry, respectively. These spatial trends are consistent with abundance-temperature correlations of four representative complex organics--CH3CCH, CH3CN, CH3OCH3 and CH3CHO--in a large sample of complex molecule hosts mined from the literature. Together, these results indicate a general chemical evolution with temperature, i.e. that new complex molecule formation pathways are activated as a MYSO heats up. This is qualitatively consistent with model predictions. Furthermore, these results suggest that ratios of complex molecules may be developed into a powerful probe of the evolutionary stage of a MYSO, and may provide information about its formation history.

  13. Crystal structures of complexes of NAD{sup +}-dependent formate dehydrogenase from methylotrophic bacterium Pseudomonas sp. 101 with formate

    SciTech Connect

    Filippova, E. V. Polyakov, K. M.; Tikhonova, T. V.; Stekhanova, T. N.; Boiko, K. M.; Sadykhov, I. G.; Tishkov, V. I.; Popov, V. O.; Labru, N.

    2006-07-15

    Formate dehydrogenase (FDH) from the methylotrophic bacterium Pseudomonas sp. 101 catalyzes oxidation of formate to NI{sub 2} with the coupled reduction of nicotinamide adenine dinucleotide (NAD{sup +}). The three-dimensional structures of the apo form (the free enzyme) and the holo form (the ternary FDH-NAD{sup +}-azide complex) of FDH have been established earlier. In the present study, the structures of FDH complexes with formate are solved at 2.19 and 2.28 A resolution by the molecular replacement method and refined to the R factors of 22.3 and 20.5%, respectively. Both crystal structures contain four protein molecules per asymmetric unit. These molecules form two dimers identical to the dimer of the apo form of FDH. Two possible formatebinding sites are found in the active site of the FDH structure. In the complexes the sulfur atom of residue Cys354 exists in the oxidized state.

  14. The significance of ACTH for the process of formation of complex heparin compounds in the blood during immobilization stress

    NASA Technical Reports Server (NTRS)

    Kudryashov, B. A.; Shapiro, F. B.; Lomovskaya, F. B.; Lyapina, L. A.

    1979-01-01

    Adrenocorticotropin (ACTH) was administered to rats at different times following adrenalectomy. Adrenocorticotropin caused a significant increase in the formation of heparin complexes even in the absence of stress factor. When ACTH secretion is blocked, immobilization stress is not accompanied by an increase in the process of complex formation. The effect of ACTH on the formation of heparin complexes was mediated through its stimulation of the adrenal cortex.

  15. Factors Affecting the Formation of 2:1 Host:Guest Inclusion Complexes of 2-[(R-Phenyl)amine]-1,4-naphthalenediones (PAN) in β- and γ-Cyclodextrins.

    PubMed

    Jankowski, Christopher K; Lamouroux, Christine; Jiménez-Estrada, Manuel; Arseneau, Sebastien; Wagner, Brian D

    2016-11-18

    The molecular hosts cyclodextrins form inclusion complexes with a wide variety of guests, resulting in complexes with various host:guest stoichiometries. In the case of a series of 19 1,4-naphthoquinolines as guests with either β- or γ-cyclodextrin studied using electrospray mass spectroscopy, in most cases only 1:1 complexes were observed, with 2:1 host:guest complexes observed in just 6 out of 38 host:guest combinations. It is shown that these higher-order complexes were observed only in the case of small (or no) electronically withdrawing substituents, and were much less likely in the case of the larger γ-cyclodextrin host. The size and electronic properties of the substituents involved shows that both steric and electronic factors must be taken into account in predicting which cyclodextrin host:guest stoichiometries will be stable enough to form (or once formed, be robust enough to be observed in the ESI-MS experiments). It is clear that the prediction of host-guest stoichiometry for a specific host-guest pair is complicated, and involves a subtle interplay of both electronic and steric factors. However, there are definite trends, which can be used to help predict host:guest stoichiometry for a given host-guest pair.

  16. The role of von Willebrand factor in thrombus formation.

    PubMed

    Ruggeri, Zaverio M

    2007-01-01

    Von Willebrand factor (VWF) is a large multimeric glycoprotein produced in endothelial cells and megakaryocytes and present in subendothelial matrix, blood plasma and platelets. VWF mediates adhesion and aggregation of platelets at sites of vascular injury, processes that are critical for both haemostasis and thrombosis. Thrombus formation involves complex events that are influenced by different environmental conditions. Progress in understanding the structure and function of VWF and the mechanisms that underlie its interactions with platelets has led to important insight into the differentiation between normal haemostasis and pathological arterial thrombosis. The conventional view of signalling-induced platelet aggregation has recently been extended to include activation-independent aggregation. A novel mechanism has been demonstrated for initiating thrombus formation under high haemodynamic forces that involves alpha(IIb)beta(3)-independent platelet aggregation at the interface between immobilised and soluble VWF. This VWF-mediated process may be a key determinant of platelet accumulation in stenotic arteries leading to acute thrombotic occlusion.

  17. Virulence factors of the Mycobacterium tuberculosis complex

    PubMed Central

    Forrellad, Marina A.; Klepp, Laura I.; Gioffré, Andrea; Sabio y García, Julia; Morbidoni, Hector R.; Santangelo, María de la Paz; Cataldi, Angel A.; Bigi, Fabiana

    2013-01-01

    The Mycobacterium tuberculosis complex (MTBC) consists of closely related species that cause tuberculosis in both humans and animals. This illness, still today, remains to be one of the leading causes of morbidity and mortality throughout the world. The mycobacteria enter the host by air, and, once in the lungs, are phagocytated by macrophages. This may lead to the rapid elimination of the bacillus or to the triggering of an active tuberculosis infection. A large number of different virulence factors have evolved in MTBC members as a response to the host immune reaction. The aim of this review is to describe the bacterial genes/proteins that are essential for the virulence of MTBC species, and that have been demonstrated in an in vivo model of infection. Knowledge of MTBC virulence factors is essential for the development of new vaccines and drugs to help manage the disease toward an increasingly more tuberculosis-free world. PMID:23076359

  18. Geology of the Biwabik Iron Formation and Duluth Complex

    USGS Publications Warehouse

    Jirsa, M.A.; Miller, J.D.; Morey, G.B.

    2008-01-01

    The Biwabik Iron Formation is a ???1.9 billion year-old sequence of iron-rich sedimentary rocks that was metamorphosed at its eastern-most extent by ???1.1 billion year-old intrusions of the Duluth Complex. The metamorphic recrystallization of iron-formation locally produced iron-rich amphiboles and other fibrous iron-silicate minerals. The presence of these minerals in iron-formation along the eastern part of what is known as the Mesabi Iron Range, and their potential liberation by iron mining has raised environmental health concerns. We describe here the geologic setting and mineralogic composition of the Biwabik Iron Formation in and adjacent to the contact metamorphic aureole of the Duluth Complex. The effects of metamorphism are most pronounced within a few kilometers of the contact, and decrease progressively away from it. The contact aureole has been divided into four metamorphic zones-each characterized by the composition and crystal structure of the metamorphic minerals it contains. The recrystallization of iron-formation to iron-rich amphibole minerals (grunerite and cummingtonite) and iron-pyroxene minerals (hedenbergite and ferrohypersthene) is best developed in zones that are most proximal to the Duluth Complex contact. ?? 2007 Elsevier Inc. All rights reserved.

  19. Geology of the Biwabik Iron Formation and Duluth Complex.

    PubMed

    Jirsa, Mark A; Miller, James D; Morey, G B

    2008-10-01

    The Biwabik Iron Formation is a approximately 1.9 billion year-old sequence of iron-rich sedimentary rocks that was metamorphosed at its eastern-most extent by approximately 1.1 billion year-old intrusions of the Duluth Complex. The metamorphic recrystallization of iron-formation locally produced iron-rich amphiboles and other fibrous iron-silicate minerals. The presence of these minerals in iron-formation along the eastern part of what is known as the Mesabi Iron Range, and their potential liberation by iron mining has raised environmental health concerns. We describe here the geologic setting and mineralogic composition of the Biwabik Iron Formation in and adjacent to the contact metamorphic aureole of the Duluth Complex. The effects of metamorphism are most pronounced within a few kilometers of the contact, and decrease progressively away from it. The contact aureole has been divided into four metamorphic zones-each characterized by the composition and crystal structure of the metamorphic minerals it contains. The recrystallization of iron-formation to iron-rich amphibole minerals (grunerite and cummingtonite) and iron-pyroxene minerals (hedenbergite and ferrohypersthene) is best developed in zones that are most proximal to the Duluth Complex contact.

  20. Thermodynamics and kinetics of aqueous ferric phosphate complex formation

    SciTech Connect

    Wilhelmy, R.B.; Patel, R.C.; Matijevic, E.

    1985-09-25

    The equilibria and kinetics of complexation of iron(III) with phosphoric acid (at pH < 2) were studied at 25 and 50/sup 0/C at ionic strength ..mu.. = 2.5 M by using spectrophotometric and stopped-flow techniques. The results are consistent with the formation of two complexes, FeH/sub 2/PO/sub 4//sup 2 +/ and Fe(H/sub 2/PO/sub 4/)/sub 2//sup +/. The second species could only be detected by the analysis of kinetic data. The equilibrium constants, extinction coefficients, rate constants, and activation parameters for the formation of these complexes are given. A mechanism is proposed to account for the observed hydrogen ion dependency of the apparent forward rate constants. 35 references, 8 figures, 6 tables.

  1. Formation of Complex Molecules via radiative association reactions

    NASA Astrophysics Data System (ADS)

    Acharyya, Kinsuk; Herbst, Eric

    2016-07-01

    The detection of increasing numbers of complex organic molecules in the various phases of star formation plays a key role since they follow the same chemical rules of carbon-based chemistry that are observed in our planet Earth. Many of these molecules are believed to be formed on the surfaces of grains, and can then be released to the gas phase when these grains are heated. This is evident when we observe a rich chemistry in hot core regions. However, recently complex organic molecules have also been observed in cold clouds. Therefore, it is necessary to re-examine various pathways for the formation of these molecules in the gas phase. In this presentation, I will discuss role of radiative association reactions in the formation of complex molecules in the gas phase and at low temperature. We will compare abundance of assorted molecules with and without new radiative association reactions and will show that the abundance of a few complex molecules such as HCOOCH3, CH3OCH3 etc. can go up due to introduction of these reactions, which can help to explain their observed abundances.

  2. Positronium formation studies in crystalline molecular complexes: Triphenylphosphine oxide - Acetanilide

    NASA Astrophysics Data System (ADS)

    Oliveira, F. C.; Denadai, A. M. L.; Guerra, L. D. L.; Fulgêncio, F. H.; Windmöller, D.; Santos, G. C.; Fernandes, N. G.; Yoshida, M. I.; Donnici, C. L.; Magalhães, W. F.; Machado, J. C.

    2013-04-01

    Hydrogen bond formation in the triphenylphosphine oxide (TPPO), acetanilide (ACN) supramolecular heterosynton system, named [TPPO0.5·ACN0.5], has been studied by Positron Annihilation Lifetime Spectroscopy (PALS) and supported by several analytical techniques. In toluene solution, Isothermal Titration Calorimetry (ITC) presented a 1:1 stoichiometry and indicated that the complexation process is driven by entropy, with low enthalpy contribution. X-ray structure determination showed the existence of a three-dimensional network of hydrogen bonds, allowing also the confirmation of the existence of a 1:1 crystalline molecular complex in solid state. The results of thermal analysis (TGA, DTA and DSC) and FTIR spectroscopy showed that the interactions in the complex are relatively weaker than those found in pure precursors, leading to a higher positronium formation probability at [TPPO0.5·ACN0.5]. These weak interactions in the complex enhance the possibility of the n- and π-electrons to interact with positrons and consequently, the probability of positronium formation is higher. Through the present work is shown that PALS is a sensible powerful tool to investigate intermolecular interactions in solid heterosynton supramolecular systems.

  3. Accelerating procelain formation by incorporating a complex additive

    SciTech Connect

    Maslennikova, G.N.; Dubovitskii, S.A.; Moroz, I.K.

    1986-05-01

    The authors studied the influence of a complex additive consisting of oxides of calcium, zinc, and magnesium on the formaton of porcelain. In order to achieve a more uniform distribution of the complex additive in the porcelain body it was incorporated in the form of water soluble salts-nitrates, which ensured comparability of results and excluded the effect of the different types of anions. The study of the main parameters of sintering (porosity, shrinkage, and mechanical strength) for the test bodies showed that they sinter at lower temperatures and attain zero porosity, maximum shrinkage, and mechanical strength. The most typical bodies indentified in this way were investigated by methods of complex differential thermal analysis and x-ray diffraction. Thus, the introduction of complex additives consisting of calcium, zinc, and magnesium oxides contributes to the earlier formation of porcelain. With the reduction of firing temperatures by 100/sup 0/C the authors observe an improvement in the basic properties of porcelain.

  4. Rosette: Understanding Star Formation in Molecular Cloud Complexes

    NASA Astrophysics Data System (ADS)

    Wang, Junfeng

    2010-09-01

    We propose Chandra imaging of three embedded clusters in the Rosette Molecular Cloud (RMC) complex. With complementary existing Spitzer and FLAMINGOS infrared surveys, the Chandra observation is critical for us to: (1) create a complete census of the young stars in the cloud; (2) study the spatial distribution of the young stars in different evolutionary stages within the RMC and the disk frequency in the embedded clusters; (3) construct X-ray Luminosity Function (XLF) and Initial Mass Function (IMF) for the clusters to examine XLF/IMF variations; (4) elucidate star formation history in this complex.

  5. Gel phase formation in dilute triblock copolyelectrolyte complexes

    NASA Astrophysics Data System (ADS)

    Srivastava, Samanvaya; Andreev, Marat; Levi, Adam E.; Goldfeld, David J.; Mao, Jun; Heller, William T.; Prabhu, Vivek M.; de Pablo, Juan J.; Tirrell, Matthew V.

    2017-02-01

    Assembly of oppositely charged triblock copolyelectrolytes into phase-separated gels at low polymer concentrations (<1% by mass) has been observed in scattering experiments and molecular dynamics simulations. Here we show that in contrast to uncharged, amphiphilic block copolymers that form discrete micelles at low concentrations and enter a phase of strongly interacting micelles in a gradual manner with increasing concentration, the formation of a dilute phase of individual micelles is prevented in polyelectrolyte complexation-driven assembly of triblock copolyelectrolytes. Gel phases form and phase separate almost instantaneously on solvation of the copolymers. Furthermore, molecular models of self-assembly demonstrate the presence of oligo-chain aggregates in early stages of copolyelectrolyte assembly, at experimentally unobservable polymer concentrations. Our discoveries contribute to the fundamental understanding of the structure and pathways of complexation-driven assemblies, and raise intriguing prospects for gel formation at extraordinarily low concentrations, with applications in tissue engineering, agriculture, water purification and theranostics.

  6. Gel phase formation in dilute triblock copolyelectrolyte complexes

    PubMed Central

    Srivastava, Samanvaya; Andreev, Marat; Levi, Adam E.; Goldfeld, David J.; Mao, Jun; Heller, William T.; Prabhu, Vivek M.; de Pablo, Juan J.; Tirrell, Matthew V.

    2017-01-01

    Assembly of oppositely charged triblock copolyelectrolytes into phase-separated gels at low polymer concentrations (<1% by mass) has been observed in scattering experiments and molecular dynamics simulations. Here we show that in contrast to uncharged, amphiphilic block copolymers that form discrete micelles at low concentrations and enter a phase of strongly interacting micelles in a gradual manner with increasing concentration, the formation of a dilute phase of individual micelles is prevented in polyelectrolyte complexation-driven assembly of triblock copolyelectrolytes. Gel phases form and phase separate almost instantaneously on solvation of the copolymers. Furthermore, molecular models of self-assembly demonstrate the presence of oligo-chain aggregates in early stages of copolyelectrolyte assembly, at experimentally unobservable polymer concentrations. Our discoveries contribute to the fundamental understanding of the structure and pathways of complexation-driven assemblies, and raise intriguing prospects for gel formation at extraordinarily low concentrations, with applications in tissue engineering, agriculture, water purification and theranostics. PMID:28230046

  7. Demixing-stimulated lane formation in binary complex plasma

    SciTech Connect

    Du, C.-R.; Jiang, K.; Suetterlin, K. R.; Ivlev, A. V.; Morfill, G. E.

    2011-11-29

    Recently lane formation and phase separation have been reported for experiments with binary complex plasmas in the PK3-Plus laboratory onboard the International Space Station (ISS). Positive non-additivity of particle interactions is known to stimulate phase separation (demixing), but its effect on lane formation is unknown. In this work, we used Langevin dynamics (LD) simulation to probe the role of non-additivity interactions on lane formation. The competition between laning and demixing leads to thicker lanes. Analysis based on anisotropic scaling indices reveals a crossover from normal laning mode to a demixing-stimulated laning mode. Extensive numerical simulations enabled us to identify a critical value of the non-additivity parameter {Delta} for the crossover.

  8. The catalytic role of uranyl in formation of polycatechol complexes

    PubMed Central

    2011-01-01

    To better understand the association of contaminant uranium with natural organic matter (NOM) and the fate of uranium in ground water, spectroscopic studies of uranium complexation with catechol were conducted. Catechol provides a model for ubiquitous functional groups present in NOM. Liquid samples were analyzed using Raman, FTIR, and UV-Vis spectroscopy. Catechol was found to polymerize in presence of uranyl ions. Polymerization in presence of uranyl was compared to reactions in the presence of molybdate, another oxyion, and self polymerization of catechol at high pH. The effect of time and dissolved oxygen were also studied. It was found that oxygen was required for self-polymerization at elevated pH. The potential formation of phenoxy radicals as well as quinones was monitored. The benzene ring was found to be intact after polymerization. No evidence for formation of ether bonds was found, suggesting polymerization was due to formation of C-C bonds between catechol ligands. Uranyl was found to form outer sphere complexes with catechol at initial stages but over time (six months) polycatechol complexes were formed and precipitated from solution (forming humic-like material) while uranyl ions remained in solution. Our studies show that uranyl acts as a catalyst in catechol-polymerization. PMID:21396112

  9. The Dynamics of Coalition Formation on Complex Networks

    NASA Astrophysics Data System (ADS)

    Auer, S.; Heitzig, J.; Kornek, U.; Schöll, E.; Kurths, J.

    2015-08-01

    Complex networks describe the structure of many socio-economic systems. However, in studies of decision-making processes the evolution of the underlying social relations are disregarded. In this report, we aim to understand the formation of self-organizing domains of cooperation (“coalitions”) on an acquaintance network. We include both the network’s influence on the formation of coalitions and vice versa how the network adapts to the current coalition structure, thus forming a social feedback loop. We increase complexity from simple opinion adaptation processes studied in earlier research to more complex decision-making determined by costs and benefits, and from bilateral to multilateral cooperation. We show how phase transitions emerge from such coevolutionary dynamics, which can be interpreted as processes of great transformations. If the network adaptation rate is high, the social dynamics prevent the formation of a grand coalition and therefore full cooperation. We find some empirical support for our main results: Our model develops a bimodal coalition size distribution over time similar to those found in social structures. Our detection and distinguishing of phase transitions may be exemplary for other models of socio-economic systems with low agent numbers and therefore strong finite-size effects.

  10. Heat capacity contributions to the formation of inclusion complexes.

    PubMed

    Olvera, Angeles; Pérez-Casas, Silvia; Costas, Miguel

    2007-10-04

    An analysis scheme for the formation of the inclusion complexes in water is presented. It is exemplified for the case where the host is alpha-cyclodextrin and the guest is a linear alcohol (1-propanol to 1-octanol) or the isomers of 1-pentanol. Eight transfer isobaric heat capacities, DeltatCp, involving different initial and final states are evaluated at infinite dilution of the guest using both data determined in this work and from the literature. Apart from the usual definition for the inclusion heat capacity change, three inclusion transfers are used. The sign of each DeltatCp indicates if the transfer is an order-formation or an order-destruction process. From the DeltatCp data, the main contributions to the heat capacity of cyclodextrin complexation, namely, those due to dehydration of the hydrophobic section of the guest molecule, H-bond formation, formation of hydrophobic interactions, and release of water molecules from the cyclodextrin cavity, are estimated. The relative weight of each of these contributions to the DeltatCp values is discussed, providing a better characterization of the molecular recognition process involved in the inclusion phenomena.

  11. Segrosome Complex Formation during DNA Trafficking in Bacterial Cell Division.

    PubMed

    Oliva, María A

    2016-01-01

    Bacterial extrachromosomal DNAs often contribute to virulence in pathogenic organisms or facilitate adaptation to particular environments. The transmission of genetic information from one generation to the next requires sufficient partitioning of DNA molecules to ensure that at least one copy reaches each side of the division plane and is inherited by the daughter cells. Segregation of the bacterial chromosome occurs during or after replication and probably involves a strategy in which several protein complexes participate to modify the folding pattern and distribution first of the origin domain and then of the rest of the chromosome. Low-copy number plasmids rely on specialized partitioning systems, which in some cases use a mechanism that show striking similarity to eukaryotic DNA segregation. Overall, there have been multiple systems implicated in the dynamic transport of DNA cargo to a new cellular position during the cell cycle but most seem to share a common initial DNA partitioning step, involving the formation of a nucleoprotein complex called the segrosome. The particular features and complex topologies of individual segrosomes depend on both the nature of the DNA binding protein involved and on the recognized centromeric DNA sequence, both of which vary across systems. The combination of in vivo and in vitro approaches, with structural biology has significantly furthered our understanding of the mechanisms underlying DNA trafficking in bacteria. Here, I discuss recent advances and the molecular details of the DNA segregation machinery, focusing on the formation of the segrosome complex.

  12. Mercury(II) Penicillamine Complex Formation in Alkaline Aqueous Solution

    SciTech Connect

    Leung, B.O.; Jalilehvand, F.; Mah, V.

    2009-06-01

    The complex formation between mercury(II) and penicillamine (H{sub 2}Pen = 3,3'-dimethyl cysteine) in alkaline aqueous solutions (pH {approx}2) has been investigated with extended X-ray absorption fine structure (EXAFS) and {sup 199}Hg NMR spectroscopy. By varying the penicillamine concentration (C{sub H{sub 2}Pen} = 0.2--1.25 M) in {approx}0.1 M Hg(II) solutions, two coexisting major species [Hg(Pen){sub 2}]{sup 2-} and [Hg(Pen){sub 3}]{sub 4-} were characterized with mean Hg-S bond distances 2.34(2) and 2.44(2) {angstrom}, respectively. The [Hg(Pen){sub 2}]{sup 2-} complex with two deprotonated penicillamine ligands forms an almost linear S-Hg-S entity with two weak chelating Hg-N interactions at the mean Hg-N distance 2.52(2) {angstrom}. The same type of coordination is also found for the corresponding [Hg(Cys){sub 2}]{sup 2-} complex in alkaline aqueous solution with the mean bond distances Hg-S 2.34(2) {angstrom} and Hg-N 2.56(2) {angstrom}. The relative amounts of the [Hg(Pen){sub 2}]{sup 2-} and [Hg(Pen){sub 3}]{sup 4-} complexes were estimated by fitting linear combinations of the EXAFS oscillations to the experimental spectra. Also their {sup 199}Hg NMR chemical shifts were used to evaluate the complex formation, showing that the [Hg(Pen){sub 3}]{sup 4-} complex dominates already at moderate excess of the free ligand ([Pen{sup 2-}] > {approx} 0.1 M).

  13. Factors determining nestedness in complex networks.

    PubMed

    Jonhson, Samuel; Domínguez-García, Virginia; Muñoz, Miguel A

    2013-01-01

    Understanding the causes and effects of network structural features is a key task in deciphering complex systems. In this context, the property of network nestedness has aroused a fair amount of interest as regards ecological networks. Indeed, Bastolla et al. introduced a simple measure of network nestedness which opened the door to analytical understanding, allowing them to conclude that biodiversity is strongly enhanced in highly nested mutualistic networks. Here, we suggest a slightly refined version of such a measure of nestedness and study how it is influenced by the most basic structural properties of networks, such as degree distribution and degree-degree correlations (i.e. assortativity). We find that most of the empirically found nestedness stems from heterogeneity in the degree distribution. Once such an influence has been discounted - as a second factor - we find that nestedness is strongly correlated with disassortativity and hence - as random networks have been recently found to be naturally disassortative - they also tend to be naturally nested just as the result of chance.

  14. Factors Determining Nestedness in Complex Networks

    PubMed Central

    Jonhson, Samuel; Domínguez-García, Virginia; Muñoz, Miguel A.

    2013-01-01

    Understanding the causes and effects of network structural features is a key task in deciphering complex systems. In this context, the property of network nestedness has aroused a fair amount of interest as regards ecological networks. Indeed, Bastolla et al. introduced a simple measure of network nestedness which opened the door to analytical understanding, allowing them to conclude that biodiversity is strongly enhanced in highly nested mutualistic networks. Here, we suggest a slightly refined version of such a measure of nestedness and study how it is influenced by the most basic structural properties of networks, such as degree distribution and degree-degree correlations (i.e. assortativity). We find that most of the empirically found nestedness stems from heterogeneity in the degree distribution. Once such an influence has been discounted – as a second factor – we find that nestedness is strongly correlated with disassortativity and hence – as random networks have been recently found to be naturally disassortative – they also tend to be naturally nested just as the result of chance. PMID:24069264

  15. Secondary factors influencing cascade damage formation

    NASA Astrophysics Data System (ADS)

    Stoller, Roger E.; Guiriec, Sylvain G.

    2004-08-01

    Primary cascade damage production in iron has been extensively investigated by molecular dynamics, and the average defect production as a function of cascade energy and temperature is well characterized. However, preliminary results indicate several factors alter `normal' cascade evolution, leading to quite different defect production behavior. Further investigation of three such factors has been carried out: (1) primary knock-on atom (PKA) direction, (2) nearby free surfaces, and (3) pre-existing effects. Results of the investigation confirm these factors significantly impact damage production. Effects include: enhanced defect survival for PKA directions lying in close-packed {1 1 0} planes, increased point defect clustering and larger defect clusters in cascades initiated near a surface, and reduced defect survival in material containing defects. The origin and implications of these effects are discussed relative to the interpretation of certain experimental observations and parameters used in other modeling studies.

  16. Human factoring the procedures element in a complex manufacturing system

    SciTech Connect

    Caccamise, D.J.; Mecherikoff, M.

    1993-06-01

    As a result of Human Factors evaluations of procedures associated with incidents at Rocky Flats Plant (RFP) it was determined that the existing procedure format created significant opportunities for confusion in their attempt to convey information about a work process. For instance, there was no mechanism to clearly identify the participants and their roles during the instructions portion of the procedure. In addition, procedure authors frequently used complex logic to convey a series of contingent actions within steps. It was also difficult to discern the actual procedure steps from other types of information in the procedure. These and other inadequacies prompted the Human Factors Engineering (HFE) department to propose solutions to these problems that followed well-researched principles of cognitive psychology, dealing with how humans process information. Format and style contribute to procedure usability, and therefore to safety and efficiency in operations governed by the procedures. Since it was difficult to tie specific performance failures to specific format and style characteristics and thereby dearly define costs and benefits, it was difficult on that basis to sell the idea that changes in procedure format and style were really necessary to improve safety and efficiency. In addition, we found that the socio-political systems governing this process, particularly at the subprocess interface level, were not functioning efficiently. Both the technological aspects of the process and the socio-political aspects were contributing to waste and considerable re-work. Fixing the customer feedback loop to the process owners not only minimized re-work and waste, but also provided the data to persuade subprocess owners to make the necessary changes that heretofore were being met with great resistance.

  17. Scatter Factor Induces Blood Vessel Formation in vivo

    NASA Astrophysics Data System (ADS)

    Grant, Derrick S.; Kleinman, Hynda K.; Goldberg, Itzhak D.; Bhargava, Mahdu M.; Nickoloff, Brian J.; Kinsella, James L.; Polverini, Peter; Rosen, Eliot M.

    1993-03-01

    Scatter factor (also known as hepatocyte growth factor) is a glycoprotein secreted by stromal cells that stimulates cell motility and proliferation. In vitro, scatter factor stimulates vascular endothelial cell migration, proliferation, and organization into capillary-like tubes. Using two different in vivo assays, we showed that physiologic quantities of purified native mouse scatter factor and recombinant human hepatocyte growth factor induce angiogenesis (the formation of new blood vessels). The angiogenic activity was blocked by specific anti-scatter factor antibodies. Scatter factor induced cultured microvascular endothelial cells to accumulate and secrete significantly increased quantities of urokinase, an enzyme associated with development of an invasive endothelial phenotype during angiogenesis. We further showed that immunoreactive scatter factor is present surrounding sites of blood vessel formation in psoriatic skin. These findings suggest that scatter factor may act as a paracrine mediator in pathologic angiogenesis associated with human inflammatory disease.

  18. Scatter factor induces blood vessel formation in vivo.

    PubMed Central

    Grant, D S; Kleinman, H K; Goldberg, I D; Bhargava, M M; Nickoloff, B J; Kinsella, J L; Polverini, P; Rosen, E M

    1993-01-01

    Scatter factor (also known as hepatocyte growth factor) is a glycoprotein secreted by stromal cells that stimulates cell motility and proliferation. In vitro, scatter factor stimulates vascular endothelial cell migration, proliferation, and organization into capillary-like tubes. Using two different in vivo assays, we showed that physiologic quantities of purified native mouse scatter factor and recombinant human hepatocyte growth factor induce angiogenesis (the formation of new blood vessels). The angiogenic activity was blocked by specific anti-scatter factor antibodies. Scatter factor induced cultured microvascular endothelial cells to accumulate and secrete significantly increased quantities of urokinase, an enzyme associated with development of an invasive endothelial phenotype during angiogenesis. We further showed that immunoreactive scatter factor is present surrounding sites of blood vessel formation in psoriatic skin. These findings suggest that scatter factor may act as a paracrine mediator in pathologic angiogenesis associated with human inflammatory disease. Images Fig. 1 Fig. 2 Fig. 3 Fig. 5 PMID:7680481

  19. The ribosome-associated complex antagonizes prion formation in yeast.

    PubMed

    Amor, Alvaro J; Castanzo, Dominic T; Delany, Sean P; Selechnik, Daniel M; van Ooy, Alex; Cameron, Dale M

    2015-01-01

    The number of known fungal proteins capable of switching between alternative stable conformations is steadily increasing, suggesting that a prion-like mechanism may be broadly utilized as a means to propagate altered cellular states. To gain insight into the mechanisms by which cells regulate prion formation and toxicity we examined the role of the yeast ribosome-associated complex (RAC) in modulating both the formation of the [PSI(+)] prion - an alternative conformer of Sup35 protein - and the toxicity of aggregation-prone polypeptides. The Hsp40 RAC chaperone Zuo1 anchors the RAC to ribosomes and stimulates the ATPase activity of the Hsp70 chaperone Ssb. We found that cells lacking Zuo1 are sensitive to over-expression of some aggregation-prone proteins, including the Sup35 prion domain, suggesting that co-translational protein misfolding increases in Δzuo1 strains. Consistent with this finding, Δzuo1 cells exhibit higher frequencies of spontaneous and induced prion formation. Cells expressing mutant forms of Zuo1 lacking either a C-terminal charged region required for ribosome association, or the J-domain responsible for Ssb ATPase stimulation, exhibit similarly high frequencies of prion formation. Our findings are consistent with a role for the RAC in chaperoning nascent Sup35 to regulate folding of the N-terminal prion domain as it emerges from the ribosome.

  20. The ribosome-associated complex antagonizes prion formation in yeast

    PubMed Central

    Amor, Alvaro J; Castanzo, Dominic T; Delany, Sean P; Selechnik, Daniel M; van Ooy, Alex; Cameron, Dale M

    2015-01-01

    Abstract The number of known fungal proteins capable of switching between alternative stable conformations is steadily increasing, suggesting that a prion-like mechanism may be broadly utilized as a means to propagate altered cellular states. To gain insight into the mechanisms by which cells regulate prion formation and toxicity we examined the role of the yeast ribosome-associated complex (RAC) in modulating both the formation of the [PSI+] prion – an alternative conformer of Sup35 protein – and the toxicity of aggregation-prone polypeptides. The Hsp40 RAC chaperone Zuo1 anchors the RAC to ribosomes and stimulates the ATPase activity of the Hsp70 chaperone Ssb. We found that cells lacking Zuo1 are sensitive to over-expression of some aggregation-prone proteins, including the Sup35 prion domain, suggesting that co-translational protein misfolding increases in Δzuo1 strains. Consistent with this finding, Δzuo1 cells exhibit higher frequencies of spontaneous and induced prion formation. Cells expressing mutant forms of Zuo1 lacking either a C-terminal charged region required for ribosome association, or the J-domain responsible for Ssb ATPase stimulation, exhibit similarly high frequencies of prion formation. Our findings are consistent with a role for the RAC in chaperoning nascent Sup35 to regulate folding of the N-terminal prion domain as it emerges from the ribosome. PMID:25739058

  1. Simulations of photochemical smog formation in complex urban areas

    NASA Astrophysics Data System (ADS)

    Muilwijk, C.; Schrijvers, P. J. C.; Wuerz, S.; Kenjereš, S.

    2016-12-01

    In the present study we numerically investigated the dispersion of photochemical reactive pollutants in complex urban areas by applying an integrated Computational Fluid Dynamics (CFD) and Computational Reaction Dynamics (CRD) approach. To model chemical reactions involved in smog generation, the Generic Reaction Set (GRS) approach is used. The GRS model was selected since it does not require detailed modeling of a large set of reactive components. Smog formation is modeled first in the case of an intensive traffic emission, subjected to low to moderate wind conditions in an idealized two-dimensional street canyon with a building aspect ratio (height/width) of one. It is found that Reactive Organic Components (ROC) play an important role in the chemistry of smog formation. In contrast to the NOx/O3 photochemical steady state model that predicts a depletion of the (ground level) ozone, the GRS model predicts generation of ozone. Secondly, the effect of direct sunlight and shadow within the street canyon on the chemical reaction dynamics is investigated for three characteristic solar angles (morning, midday and afternoon). Large differences of up to one order of magnitude are found in the ozone production for different solar angles. As a proof of concept for real urban areas, the integrated CFD/CRD approach is applied for a real scale (1 × 1 km2) complex urban area (a district of the city of Rotterdam, The Netherlands) with high traffic emissions. The predicted pollutant concentration levels give realistic values that correspond to moderate to heavy smog. It is concluded that the integrated CFD/CRD method with the GRS model of chemical reactions is both accurate and numerically robust, and can be used for modeling of smog formation in complex urban areas.

  2. Formation of gold mineralization in ultramafic alkalic magmatic complexes

    NASA Astrophysics Data System (ADS)

    Ryabchikov, I. D.; Kogarko, L. N.; Sazonov, A. M.; Kononkova, N. N.

    2016-06-01

    Study of mineral inclusions within alluvial gold particles of the Guli Complex (East Siberia) and findings of lode gold in rocks of the same intrusion have demonstrated that gold mineralization occurs in interstitions of both early high-magnesium rocks (dunite) and later alkalic and carbonatite rocks. In dunite the native gold occurs in association with Fe-Ni sulfides (monosulfide solid solution, pentlandite, and heazlewoodite). Formation of the gold-bearing alloys took place under a low oxygen potential over a broad range of temperatures: from those close to 600°C down to below 400°C.

  3. Redox reactions and complex formation of transplutonium elements in solutions

    SciTech Connect

    Krot, N.N.; Myasoedov, B.F.

    1986-01-01

    This paper gives a brief analysis of the kinetics and mechanism of a number of redox processes and the complex formation of transplutonium elements in unusual oxidation states. The composition and strength of complexes of TPE with various addends have been determined. The new experimental data on the oxidation potentials of americium and berkelium ions in solutions are cited in abbreviated form. It follows from the data that in phosphoric acid solutions, when the H/sub 3/PO/sub 4/ concentration is increased from 10 to 15 M, the oxidation potential of the couple Am(IV)-Am(III) decreases. The oxidation potentials of the couples Am(VI)-Am(V), Cm(V)-Cm(IV), and Bk(IV)Bk(III) are also presented.

  4. Cu(II) complex formation with xylitol in alkaline solutions.

    PubMed

    Norkus, Eugenijus; Vaiciūniene, Jūrate; Vuorinen, Tapani; Gaidamauskas, Ernestas; Reklaitis, Jonas; Jääskeläinen, Anna-Stiina; Crans, Debbie C

    2004-02-25

    The formation of four Cu(II)-xylitol complexes was observed in aqueous alkaline solutions (11.0< or =pH< or =14.0, I=1.0, 20 degrees C) by means of direct current polarography and VIS spectrophotometry. Mononuclear hydroxy complexes, CuXyl(OH)- (log beta=17.7 +/- 0.5), CuXyl(OH)2(2-) (log beta=20.2 +/- 0.3) and CuXyl2(OH)2(4-) (log beta=22.4 +/- 0.3), are formed at high ligand-to-metal ratios (L:M> or =10), whereas dinuclear complex Cu2Xyl (log beta=29.2 +/- 0.3) is the predominant species at low ligand-to-metal ratio (L:M=0.5). Diffusion coefficients and molar absorptivities of the complex species were determined. pH variable 13C NMR suggested that pKa values of xylitol are rather similar and equal to 13.8 +/- 0.2, 13.9 +/- 0.1 and 13.9 +/- 0.2 for OH-groups adjacent to (C-1,C-5), (C-3) and (C-2,C-4) carbon atoms, respectively.

  5. Characterization of Hydrogen Complex Formation in III-V Semiconductors

    SciTech Connect

    Williams, Michael D

    2006-09-28

    Atomic hydrogen has been found to react with some impurity species in semiconductors. Hydrogenation is a methodology for the introduction of atomic hydrogen into the semiconductor for the express purpose of forming complexes within the material. Efforts to develop hydrogenation as an isolation technique for AlGaAs and Si based devices failed to demonstrate its commercial viability. This was due in large measure to the low activation energies of the formed complexes. Recent studies of dopant passivation in long wavelength (0.98 - 1.55m) materials suggested that for the appropriate choice of dopants much higher activation energies can be obtained. This effort studied the formation of these complexes in InP, This material is extensively used in optoelectronics, i.e., lasers, modulators and detectors. The experimental techniques were general to the extent that the results can be applied to other areas such as sensor technology, photovoltaics and to other material systems. The activation energies for the complexes have been determined and are reported in the scientific literature. The hydrogenation process has been shown by us to have a profound effect on the electronic structure of the materials and was thoroughly investigated. The information obtained will be useful in assessing the long term reliability of device structures fabricated using this phenomenon and in determining new device functionalities.

  6. HCF-1 self-association via an interdigitated Fn3 structure facilitates transcriptional regulatory complex formation.

    PubMed

    Park, Jihye; Lammers, Fabienne; Herr, Winship; Song, Ji-Joon

    2012-10-23

    Host-cell factor 1 (HCF-1) is an unusual transcriptional regulator that undergoes a process of proteolytic maturation to generate N- (HCF-1(N)) and C- (HCF-1(C)) terminal subunits noncovalently associated via self-association sequence elements. Here, we present the crystal structure of the self-association sequence 1 (SAS1) including the adjacent C-terminal HCF-1 nuclear localization signal (NLS). SAS1 elements from each of the HCF-1(N) and HCF-1(C) subunits form an interdigitated fibronectin type 3 (Fn3) tandem repeat structure. We show that the C-terminal NLS recruited by the interdigitated SAS1 structure is required for effective formation of a transcriptional regulatory complex: the herpes simplex virus VP16-induced complex. Thus, HCF-1(N)-HCF-1(C) association via an integrated Fn3 structure permits an NLS to facilitate formation of a transcriptional regulatory complex.

  7. Thermodynamics for complex formation between palladium(ii) and oxalate.

    PubMed

    Pilný, Radomír; Lubal, Přemysl; Elding, Lars I

    2014-08-28

    Complex formation between [Pd(H2O)4](2+) and oxalate (ox = C2O4(2-)) has been studied spectrophoto-metrically in aqueous solution at variable temperature, ionic strength and pH. Thermodynamic parameters at 298.2 K and 1.00 mol dm(-3) HClO4 ionic medium for the complex formation [Pd(H2O)4](2+) + H2ox ⇄ [Pd(H2O)2(ox)] + 2H3O(+) with equilibrium constant K1,H (in mol dm(-3)) are log10K1,H = 3.38 ± 0.08, ΔH = -33 ± 3 kJ mol(-1), and ΔS = -48 ± 11 J K(-1) mol(-1), as determined from spectrophotometric equilibrium titrations at 15.0, 20.0, 25.0 and 31.0 °C. Thermodynamic overall stability constants β (in (mol dm(-3))(-n), n = 1,2) for [Pd(H2O)2(ox)] and [Pd(ox)2](2-) at zero ionic strength and 298.2 K, defined as the equilibrium constants for the reaction Pd(2+) + nox(2-) ⇄ [Pd(ox)n](2-2n) (water molecules omitted) are log10β = 9.04 ± 0.06 and log10β = 13.1 ± 0.3, respectively, calculated by use of Specific Ion Interaction Theory from spectrophotometric titrations with initial hydrogen ion concentrations of 1.00, 0.100 and 0.0100 mol dm(-3) and ionic strengths of 1.00, 2.00 or 3.00 mol dm(-3). The values derived together with literature data give estimated overall stability constants for Pd(ii) compounds such as [Pd(en)(ox)] and cis-[Pd(NH3)2Cl2], some of them analogs to Pt(ii) complexes used in cancer treatment. The palladium oxalato complexes are significantly more stable than palladium(ii) complexes with monodentate O-bonding ligands. A comparison between several different palladium complexes shows that different parameters contribute to the stability variations observed. These are discussed together with the so-called chelate effect.

  8. Interference-mediated synaptonemal complex formation with embedded crossover designation

    PubMed Central

    Zhang, Liangran; Espagne, Eric; de Muyt, Arnaud; Zickler, Denise; Kleckner, Nancy E.

    2014-01-01

    Biological systems exhibit complex patterns at length scales ranging from the molecular to the organismic. Along chromosomes, events often occur stochastically at different positions in different nuclei but nonetheless tend to be relatively evenly spaced. Examples include replication origin firings, formation of chromatin loops along chromosome axes and, during meiosis, localization of crossover recombination sites (“crossover interference”). We present evidence in the fungus Sordaria macrospora that crossover interference is part of a broader pattern that includes synaptonemal complex (SC) nucleation. This pattern comprises relatively evenly spaced SC nucleation sites, among which a subset are crossover sites that show a classical interference distribution. This pattern ensures that SC forms regularly along the entire length of the chromosome as required for the maintenance of homolog pairing while concomitantly having crossover interactions locally embedded within the SC structure as required for both DNA recombination and structural events of chiasma formation. This pattern can be explained by a threshold-based designation and spreading interference process. This model can be generalized to give diverse types of related and/or partially overlapping patterns, in two or more dimensions, for any type of object. PMID:25380597

  9. Gel phase formation in dilute triblock copolyelectrolyte complexes

    DOE PAGES

    Srivastava, Samanvaya; Andreev, Marat; Levi, Adam E.; ...

    2017-02-23

    Assembly of oppositely charged triblock copolyelectrolytes into phase-separated gels at low polymer concentrations (<1% by mass) has been observed in scattering experiments and molecular dynamics simulations. Here we show that in contrast to uncharged, amphiphilic block copolymers that form discrete micelles at low concentrations and enter a phase of strongly interacting micelles in a gradual manner with increasing concentration, the formation of a dilute phase of individual micelles is prevented in polyelectrolyte complexation-driven assembly of triblock copolyelectrolytes. Gel phases form and phase separate almost instantaneously on solvation of the copolymers. Furthermore, molecular models of self-assembly demonstrate the presence of oligo-chainmore » aggregates in early stages of copolyelectrolyte assembly, at experimentally unobservable polymer concentrations. Finally, our discoveries contribute to the fundamental understanding of the structure and pathways of complexation-driven assemblies, and raise intriguing prospects for gel formation at extraordinarily low concentrations, with applications in tissue engineering, agriculture, water purification and theranostics.« less

  10. A complex postnatal mental health intervention: Australian translational formative evaluation.

    PubMed

    Rowe, Heather J; Wynter, Karen H; Burns, Joanna K; Fisher, Jane R W

    2016-01-07

    Reducing the burden of postnatal maternal mental health problems is an international public health priority. We developed What Were We Thinking (WWWT), a psychoeducation programme for primary postnatal health care that addresses known but neglected risks. We then demonstrated evidence of its effects in a before-and-after controlled study in preventing maternal postnatal mental health problems among women without a psychiatric history participating in the intervention compared to usual care (AOR 0.43; 95% CI 0.21, 0.89) when conducted by specialist nurses. Testing its effectiveness when implemented in routine primary care requires changes at practitioner, organizational and health system levels. This paper describes a programme of translational formative evaluation to inform the protocol for a cluster RCT. Following the UK Medical Research Council (MRC) Guidance for evaluating complex interventions, we conducted a translational formative evaluation using mixed methods. Collection and analysis of postnatal health service documents, semi-structured interviews, group discussions and an online survey were used to investigate service provision, consumers' needs and expectations, clinicians' attitudes and clinical practice, and the implications for health service delivery. Participants were expectant parents, health care providers, health service managers and government policy makers. Results documented current clinical practice, staff training needs, necessary service modifications to standardize advice to parents and include fathers, key priorities and drivers of government health policy, and informed a model of costs and expected health and social outcomes. Implementation of WWWT into routine postnatal care requires adjustments to clinical practice. Staff training, modifications to service opening hours and economic implications for the health system also need to be considered. The MRC Guidance for developing and evaluating complex interventions is a useful framework

  11. Soil microstructure and factors of its formation

    NASA Astrophysics Data System (ADS)

    Alekseeva, T. V.

    2007-06-01

    The microstructural stability of soils of different geneses (steppe soils, tropical soils, and subtropical soils) developed from marine clay, loess, and weathering crusts was studied by the method of successive treatments with chemical reagents destroying the particular clay-aggregating components. The following dispersing agents were used: (1) H2O (pH 5.5), (2) 0.1 N NaCl (pH 6), (3) 0.002% Na2CO3 (pH 8.7), (4) 0.1 N NaOH (pH 11.5), (5) the Tamm reagent (pH 3.2), and (6) 0.1 N NaOH (pH 11.5). The properties of the clay subfractions obtained in the course of these treatments were studied by a set of analytical methods, including X-ray diffractometry, Mössbauer spectroscopy, and magnetic measurements. It was shown that soil microaggregates are formed under the impact of a number of physicochemical processes; the content and properties of inorganic components (clay minerals in soils with a high CEC and iron oxides in soils with a low CEC) are the controlling factors. The structure of the parent materials is transformed to different degrees to form the soil structure. For example, autonomous nondifferentiated soils inherit, to some extent, the specific microorganization of the parent material. At the same time, the redistribution of substances in the soil profile and in the landscape may exert a substantial influence on the soil structure and microstructure. This is particularly true for autonomous differentiated soils, turbated soils, accumulative soils, polylithogenic soils, and polygenetic soils. The properties of the obtained subfractions of the clay (the mineralogical composition, the Fe2+/(Fe2+ + Fe3+) ratio, the magnetic susceptibility, and the Cha/Cfa ratio) attest to the spatial heterogeneity of the composition and properties of the mineral and organic aggregated compounds in soils.

  12. Investigation of the Composition and Formation Constant of Molecular Complexes

    PubMed Central

    Sahai, R.; Loper, G. L.; Lin, S. H.; Eyring, H.

    1974-01-01

    It has been the purpose of the present paper to investigate and explore the conditions under which the linear relation between Δ/CD0 and Δ in the Hanna-Ashbaugh-Foster-Fyfe equation for the evaluation of equilibrium constants holds, (CD0 is initial concentration of a donor and Δ is the observed chemical shift relative to the chemical shift of the acceptor) to obtain the equation representing the exact linear relation between Δ/CD0 and Δ, when the linear relation between Δ/CD0 and Δ holds, and to discuss how to use the Job method in nuclear magnetic resonance measurements to determine the stoichiometry of molecular complexes. We have found that the conventional belief that CD0 should always be chosen to be much greater than CA0 (initial concentration of acceptor) is not necessarily always true and the exact linear relation between Δ/CD0 and Δ is represented by the equation Δ/CD0 = K1Δ0/(1 + K1CA0) - K1Δ/(1 + K1CA0)2, where K1 is the formation constant of the complex. It is shown that in the Job method of nuclear magnetic resonance measurements one has to plot ΔCA0 against the mole fraction, and the mole fraction at the maximum should give us the composition of the complex. Theoretical results have been verified experimentally on the weak interaction between naphthalene and methyl iodide. PMID:16592155

  13. Formation factor logging by electrical methods. Comparison of formation factor logs obtained in situ and in the laboratory.

    PubMed

    Löfgren, Martin; Neretnieks, Ivars

    2003-03-01

    In this paper, a new in situ method for obtaining the formation factor, which is essential for the matrix diffusion, is described and tested in intrusive igneous rock. The method is based on electrical resistivity measurements in rock where the pore water and rock resistivities are essential parameters. The method is based on electromigration instead of diffusion as in traditional diffusion experiments. In previous works, quantitative formation factors of rock have been obtained by electrical methods in the laboratory. Here, a similar approach is used in situ. An in situ logging campaign was performed by SKB during 2000 in the 1700-m-deep borehole KLX02 in Laxemar, Sweden. The rock resistivity was measured with the slimhole Dual Laterolog from Antares. The groundwater resistivity was measured with the Difference Flow Meter from Posiva. A formation factor log was obtained with the maximum vertical resolution of 10 cm. In order to validate the log, 100 rock samples were taken from the bore core, and a formation factor log was obtained by using electrical methods in the laboratory. Both direct current (DC) and alternating current (AC) were used. The measurements on the core confirmed that the in situ log was quantitative, but with a possible systematic error. The in situ formation factors were on average about 1/3 to 1/5 of the laboratory formation factors, depending on depth.

  14. Cadmium(II) complex formation with cysteine and penicillamine.

    PubMed

    Jalilehvand, Farideh; Leung, Bonnie O; Mah, Vicky

    2009-07-06

    The complex formation between cadmium(II) and the ligands cysteine (H(2)Cys) and penicillamine (H(2)Pen = 3,3'-dimethylcysteine) in aqueous solutions, having C(Cd(II)) approximately 0.1 mol dm(-3) and C(H(2)L) = 0.2-2 mol dm(-3), was studied at pH = 7.5 and 11.0 by means of (113)Cd NMR and Cd K- and L(3)-edge X-ray absorption spectroscopy. For all cadmium(II)-cysteine molar ratios, the mean Cd-S and Cd-(N/O) bond distances were found in the ranges 2.52-2.54 and 2.27-2.35 A, respectively. The corresponding cadmium(II)-penicillamine complexes showed slightly shorter Cd-S bonds, 2.50-2.53 A, but with the Cd-(N/O) bond distances in a similar wide range, 2.28-2.33 A. For the molar ratio C(H(2)L)/C(Cd(II)) = 2, the (113)Cd chemical shifts, in the range 509-527 ppm at both pH values, indicated complexes with distorted tetrahedral CdS(2)N(N/O) coordination geometry. With a large excess of cysteine (molar ratios C(H(2)Cys)/C(Cd(II)) >or= 10), complexes with CdS(4) coordination geometry dominate, consistent with the (113)Cd NMR chemical shifts, delta approximately 680 ppm at pH 7.5 and 636-658 ppm at pH 11.0, and their mean Cd-S distances were 2.53 +/- 0.02 A. At pH 7.5, the complexes are almost exclusively sulfur-coordinated as [Cd(S-cysteinate)(4)](n-), while at higher pH, the deprotonation of the amine groups promotes chelate formation. At pH 11.0, a minor amount of the [Cd(Cys)(3)](4-) complex with CdS(3)N coordination is formed. For the corresponding penicillamine solutions with molar ratios C(H(2)Pen)/C(Cd(II)) >or= 10, the (113)Cd NMR chemical shifts, delta approximately 600 ppm at pH 7.5 and 578 ppm at pH 11.0, together with the average bond distances, Cd-S 2.53 +/- 0.02 A and Cd-(N/O) 2.30-2.33 A, indicate that [Cd(penicillaminate)(3)](n-) complexes with chelating CdS(3)(N/O) coordination dominate already at pH 7.5 and become mixed with CdS(2)N(N/O) complexes at pH 11.0. The present study reveals differences between cysteine and penicillamine as ligands to the

  15. Enhanced CO2 hydrate formation kinetic under organo-mineral complex environment

    NASA Astrophysics Data System (ADS)

    Kyung, D.; Lee, W.

    2012-12-01

    CO2 hydrate formation under marine sediments can be one of the feasible options to mitigate atmospheric concentration of CO2, main source of global warming. For the better application of CO2 sequestration via hydrate form under ocean, it is indispensable to understand the effects of marine environmental factors on hydrate formation kinetic and equilibrium. In this study, we investigated the effect of organo-mineral complex (i.e., Na-montmorillonite (Na-MMT) and glycine complex) on hydrate formation kinetic both experimentally and computationally. Organo-mineral complex suspension showed much more favorable hydrate formation kinetic (2-6 min) than pure water control (48-80 min). TEM image showed that glycine are well distributed and strongly adsorbed on Na-MMT surface and FT/IR results (i.e., increased frequency of N-H stretch) also proved that amine part of glycine can make strong hydrogen bonding with silicon atoms of Na-MMT. Molecular dynamics (MD) simulation was performed to fully understand the CO2 hydrate nucleation on the organo-mineral complex and its result showed that high concentration of CO2 molecules are located near Na-MMT surface and glycine attached on Na-MMT can attract water molecules to form intermediate hydrate structure. This one plays a key role in complete hydrate formation as nucleation seeds and can significantly enhance the hydrate formation kinetic. This fundamental knowledge could provide idea to select proper CO2 storage site under marine sediments and be applied to in-situ swapping technology to recover CH4 from deep sea gas hydrate deposits and sequester the CO2 to CH4 hydrate layer.

  16. Dynamical complexity in the perception-based network formation model

    NASA Astrophysics Data System (ADS)

    Jo, Hang-Hyun; Moon, Eunyoung

    2016-12-01

    Many link formation mechanisms for the evolution of social networks have been successful to reproduce various empirical findings in social networks. However, they have largely ignored the fact that individuals make decisions on whether to create links to other individuals based on cost and benefit of linking, and the fact that individuals may use perception of the network in their decision making. In this paper, we study the evolution of social networks in terms of perception-based strategic link formation. Here each individual has her own perception of the actual network, and uses it to decide whether to create a link to another individual. An individual with the least perception accuracy can benefit from updating her perception using that of the most accurate individual via a new link. This benefit is compared to the cost of linking in decision making. Once a new link is created, it affects the accuracies of other individuals' perceptions, leading to a further evolution of the actual network. As for initial actual networks, we consider both homogeneous and heterogeneous cases. The homogeneous initial actual network is modeled by Erdős-Rényi (ER) random networks, while we take a star network for the heterogeneous case. In any cases, individual perceptions of the actual network are modeled by ER random networks with controllable linking probability. Then the stable link density of the actual network is found to show discontinuous transitions or jumps according to the cost of linking. As the number of jumps is the consequence of the dynamical complexity, we discuss the effect of initial conditions on the number of jumps to find that the dynamical complexity strongly depends on how much individuals initially overestimate or underestimate the link density of the actual network. For the heterogeneous case, the role of the highly connected individual as an information spreader is also discussed.

  17. Ubisemiquinone is the electron donor for superoxide formation by complex III of heart mitochondria.

    PubMed

    Turrens, J F; Alexandre, A; Lehninger, A L

    1985-03-01

    Much evidence indicates that superoxide is generated from O2 in a cyanide-sensitive reaction involving a reduced component of complex III of the mitochondrial respiratory chain, particularly when antimycin A is present. Although it is generally believed that ubisemiquinone is the electron donor to O2, little experimental evidence supporting this view has been reported. Experiments with succinate as electron donor in the presence of antimycin A in intact rat heart mitochondria, which contain much superoxide dismutase but little catalase, showed that myxothiazol, which inhibits reduction of the Rieske iron-sulfur center, prevented formation of hydrogen peroxide, determined spectrophotometrically as the H2O2-peroxidase complex. Similarly, depletion of the mitochondria of their cytochrome c also inhibited formation of H2O2, which was restored by addition of cytochrome c. These observations indicate that factors preventing the formation of ubisemiquinone also prevent H2O2 formation. They also exclude ubiquinol, which remains reduced under these conditions, as the reductant of O2. Since cytochrome b also remains fully reduced when myxothiazol is added to succinate- and antimycin A-supplemented mitochondria, reduced cytochrome b may also be excluded as the reductant of O2. These observations, which are consistent with the Q-cycle reactions, by exclusion of other possibilities leave ubisemiquinone as the only reduced electron carrier in complex III capable of reducing O2 to O2-.

  18. Complex formation dynamics in a single-molecule electronic device

    PubMed Central

    Wen, Huimin; Li, Wengang; Chen, Jiewei; He, Gen; Li, Longhua; Olson, Mark A.; Sue, Andrew C.-H.; Stoddart, J. Fraser; Guo, Xuefeng

    2016-01-01

    Single-molecule electronic devices offer unique opportunities to investigate the properties of individual molecules that are not accessible in conventional ensemble experiments. However, these investigations remain challenging because they require (i) highly precise device fabrication to incorporate single molecules and (ii) sufficient time resolution to be able to make fast molecular dynamic measurements. We demonstrate a graphene-molecule single-molecule junction that is capable of probing the thermodynamic and kinetic parameters of a host-guest complex. By covalently integrating a conjugated molecular wire with a pendent crown ether into graphene point contacts, we can transduce the physical [2]pseudorotaxane (de)formation processes between the electron-rich crown ether and a dicationic guest into real-time electrical signals. The conductance of the single-molecule junction reveals two-level fluctuations that are highly dependent on temperature and solvent environments, affording a nondestructive means of quantitatively determining the binding and rate constants, as well as the activation energies, for host-guest complexes. The thermodynamic processes reveal the host-guest binding to be enthalpy-driven and are consistent with conventional 1H nuclear magnetic resonance titration experiments. This electronic device opens up a new route to developing single-molecule dynamics investigations with microsecond resolution for a broad range of chemical and biochemical applications. PMID:28138528

  19. Formation of Cluster Complexes by Cluster-Cluster-Collisions

    NASA Astrophysics Data System (ADS)

    Ichihashi, Masahiko; Odaka, Hideho

    2015-03-01

    Multi-element clusters are interested in their chemical and physical properties, and it is expected that they are utilized as catalysts, for example. Their properties critically depend on the size, composition and atomic ordering, and it should be important to adjust the above parameters for their functionality. One of the ways to form a multi-element cluster is to employ a low-energy collision between clusters. Here, we show characteristic results obtained in the collision between a neutral Ar cluster and a size-selected Co cluster ion. Low-energy collision experiment was accomplished by using a newly developed merging-beam apparatus. Cobalt cluster ions were produced by laser ablation, and mass-selected. On the other hand, argon clusters were prepared by the supersonic expansion of Ar gas. Both cluster beams were merged together in an ion guide, and ionic cluster complexes were mass-analyzed. In the collision of Co2+ and ArN, Co2Arn+ (n = 1 - 30) were observed, and the total intensity of Co2Arn+ (n >= 1) is inversely proportional to the relative velocity between Co2+ and ArN. This suggests that the charge-induced dipole interaction between Co2+ and a neutral Ar cluster is dominant in the formation of the cluster complex, Co2+Arn.

  20. Amyloid fibril formation by macrophage migration inhibitory factor

    SciTech Connect

    Lashuel, Hilal A. . E-mail: hilal.lashuel@epfl.ch; Aljabari, Bayan; Sigurdsson, Einar M.; Metz, Christine N.; Leng Lin; Callaway, David J.E.; Bucala, Richard

    2005-12-16

    We demonstrate herein that human macrophage migration inhibitory factor (MIF), a pro-inflammatory cytokine expressed in the brain and not previously considered to be amyloidogenic, forms amyloid fibrils similar to those derived from the disease associated amyloidogenic proteins {beta}-amyloid and {alpha}-synuclein. Acid denaturing conditions were found to readily induce MIF to undergo amyloid fibril formation. MIF aggregates to form amyloid-like structures with a morphology that is highly dependent on pH. The mechanism of MIF amyloid formation was probed by electron microscopy, turbidity, Thioflavin T binding, circular dichroism spectroscopy, and analytical ultracentrifugation. The fibrillar structures formed by MIF bind Congo red and exhibit the characteristic green birefringence under polarized light. These results are consistent with the notion that amyloid fibril formation is not an exclusive property of a select group of amyloidogenic proteins, and contribute to a better understanding of the factors which govern protein conformational changes and amyloid fibril formation in vivo.

  1. Geminin Inhibits a Late Step in the Formation of Human Pre-replicative Complexes*

    PubMed Central

    Wu, Min; Lu, Wenyan; Santos, Ruth E.; Frattini, Mark G.; Kelly, Thomas J.

    2014-01-01

    The initial step in initiation of eukaryotic DNA replication involves the assembly of pre-replicative complexes (pre-RCs) at origins of replication during the G1 phase of the cell cycle. In metazoans initiation is inhibited by the regulatory factor Geminin. We have purified the human pre-RC proteins, studied their interactions in vitro with each other and with origin DNA, and analyzed the effects of HsGeminin on formation of DNA-protein complexes. The formation of an initial complex containing the human origin recognition complex (HsORC), HsCdt1, HsCdc6, and origin DNA is cooperative, involving all possible binary interactions among the components. Maximal association of HsMCM2–7, a component of the replicative helicase, requires HsORC, HsCdc6, HsCdt1, and ATP, and is driven by interactions of HsCdt1 and HsCdc6 with multiple HsMCM2–7 subunits. Formation of stable complexes, resistant to high salt, requires ATP hydrolysis. In the absence of HsMCM proteins, HsGeminin inhibits the association of HsCdt1 with DNA or with HsORC-HsCdc6-DNA complexes. However, HsGeminin does not inhibit recruitment of HsMCM2–7 to DNA to form complexes containing all of the pre-RC proteins. In fact, HsGeminin itself is a component of such complexes, and interacts directly with the HsMcm3 and HsMcm5 subunits of HsMCM2–7, as well as with HsCdt1. Although HsGeminin does not prevent the initial formation of DNA-protein complexes containing the pre-RC proteins, it strongly inhibits the formation of stable pre-RCs that are resistant to high salt. We suggest that bound HsGeminin prevents transition of the pre-RC to a state that is competent for initiation of DNA replication. PMID:25231993

  2. p300 is involved in formation of the TBP-TFIIA-containing basal transcription complex, TAC.

    PubMed

    Mitsiou, Dimitra J; Stunnenberg, Hendrik G

    2003-09-01

    We have recently identified a novel basal transcription complex, TAC, that is present and active in embryonal carcinoma (EC) cells but not in other adult cells such as COS7. In the search for factors involved in TAC formation, we found that expression of the adenoviral 12S E1A oncoprotein abolishes TAC formation in EC cells. This effect of E1A depends on its N-terminal domain that is essential for cell differentiation and that targets the transcriptional coactivators p300 and PCAF. Expression of p300 lacking its major E1A interaction domain, CH3, restores TAC formation in the presence of E1A, in a bromodomain- and HAT domain-dependent manner. Consistently, the unprocessed TFIIAalphabeta precursor that is selectively assembled into TAC is acetylated preferentially compared with the processed subunits present in 'free' TFIIA. Intriguingly, expression of p300 in COS7 cells that do not contain detectable levels of TAC instigates formation of TAC from endogenous components. Our data suggest that p300 plays a role in formation of the TBP-TFIIA-containing basal transcription complex, TAC.

  3. Cyclodextrins in pharmaceutical formulations I: structure and physicochemical properties, formation of complexes, and types of complex.

    PubMed

    Jambhekar, Sunil S; Breen, Philip

    2016-02-01

    Cyclodextrins are cyclic oligosaccharides that have been recognized as pharmaceutical adjuvants for the past 20 years. The molecular structure of these glucose derivatives, which approximates a truncated cone, bucket, or torus, generates a hydrophilic exterior surface and a nonpolar interior cavity. Cyclodextrins can interact with appropriately sized drug molecules to yield an inclusion complex. These noncovalent inclusion complexes offer a variety of advantages over the noncomplexed form of a drug. Cyclodextrins are primarily used to enhance the aqueous solubility, physical chemical stability, and bioavailability of drugs. Their other applications include preventing drug-drug interactions, converting liquid drugs into microcrystalline powders, minimizing gastrointestinal and ocular irritation, and reducing or eliminating unpleasant taste and smell. Here, we discuss the physical chemical properties of various cyclodextrins, including the effects of substitutions on these properties. Additionally, we report on the regulatory status of their use, commercial products containing cyclodextrins, toxicological considerations, and the forces involved in complex formation. We also highlight the types of complex formed and discuss the methods used to determine the types of complex present.

  4. Relationship of Complexity Factor Ratings With Operational Errors

    DTIC Science & Technology

    2007-05-01

    and their descriptions was initially derived from the 19 complexity factors identified by Mogford et al. (1994). Subject Matter Experts ( SMEs ) from...in Table 1. Note that only two extra factors were added by the SMEs , yet there are 22 factors in the list. The “mix of aircraft with different...performance characteristics” and “VFR versus IFR traffic” factors were combined in the original list but were separated into two distinct factors for

  5. Carbon–heteroatom bond formation catalysed by organometallic complexes

    PubMed Central

    Hartwig, John F.

    2010-01-01

    At one time the synthetic chemist’s last resort, reactions catalysed by transition metals are now the preferred method for synthesizing many types of organic molecule. A recent success in this type of catalysis is the discovery of reactions that form bonds between carbon and heteroatoms (such as nitrogen, oxygen, sulphur, silicon and boron) via complexes of transition metals with amides, alkoxides, thiolates, silyl groups or boryl groups. The development of these catalytic processes has been supported by the discovery of new elementary reactions that occur at metal–heteroatom bonds and by the identification of factors that control these reactions. Together, these findings have led to new synthetic processes that are in daily use and have formed a foundation for the development of processes that are likely to be central to synthetic chemistry in the future. PMID:18800130

  6. cAMP prevents TNF-induced apoptosis through inhibiting DISC complex formation in rat hepatocytes.

    PubMed

    Bhattacharjee, Rajesh; Xiang, Wenpei; Wang, Yinna; Zhang, Xiaoying; Billiar, Timothy R

    2012-06-22

    Tumor necrosis factor α (TNF) is a pleiotropic proinflammatory cytokine that plays a role in immunity and the control of cell proliferation, cell differentiation, and apoptosis. The pleiotropic nature of TNF is due to the formation of different signaling complexes upon the binding of TNF to its receptor, TNF receptor type 1 (TNFR1). TNF induces apoptosis in various mammalian cells when the cells are co-treated with a transcription inhibitor like actinomycin D (ActD). When TNFR1 is activated, it recruits an adaptor protein, TNF receptor-associated protein with death domain (TRADD), through its cytoplasmic death effector domain (DED). TRADD, in turn, recruits other signaling proteins, including TNF receptor-associated protein 2 (TRAF2) and receptor-associated protein kinase (RIPK) 1, to form a complex. Subsequently, this complex combines with FADD and procaspase-8, converts into a death-inducing signaling complex (DISC) to induce apoptosis. Cyclic AMP (cAMP) is a second messenger that regulates various cellular processes such as cell proliferation, gene expression, and apoptosis. cAMP analogues are reported to act as anti-apoptotic agents in various cell types, including hepatocytes. We found that a cAMP analogue, dibutyryl cAMP (db-cAMP), inhibits TNF+ActD-induced apoptosis in rat hepatocytes. The protein kinase A (PKA) inhibitor KT-5720 reverses this inhibitory effect of cAMP on apoptosis. Cytoprotection by cAMP involves down-regulation of various apoptotic signal regulators like TRADD and FADD and inhibition of caspase-8 and caspase-3 cleavage. We also found that cAMP exerts its affect at the proximal level of TNF signaling by inhibiting the formation of the DISC complex upon the binding of TNF to TNFR1. In conclusion, our study shows that cAMP prevents TNF+ActD-induced apoptosis in rat hepatocytes by inhibiting DISC complex formation.

  7. Stereospecific formation of dinuclear vanadium(V) tartrato complexes.

    PubMed

    Gáliková, Jana; Schwendt, Peter; Tatiersky, Jozef; Tracey, Alan S; Zák, Zdirad

    2009-09-07

    The first dinuclear nonperoxido tartrato complexes of vanadium(V), (NMe(4))(2)[V(2)O(4)((2R,3R)-H(2)tart)(2)] x 6 H(2)O (1), (NMe(4))(2)[V(2)O(2)((2R,3R)-tart)((2S,3S)-tart)] (2), (NEt(4))(2)[V(2)O(2)((2R,3R)-tart)((2S,3S)-tart)] (3) (tart = tartrato(4-) = C(4)H(2)O(6)(4-)) have been prepared from water-ethanol medium and characterized by X-ray structure analysis and spectral methods. The formation of the complexes has been found to be stereospecific; the composition and structure of anions containing one or both enantiomers of the ligand are profoundly different. The structure of anions in 1-3 also differs significantly from the structure of other dinuclear vanadium(V) alpha-hydroxycarboxylato complexes, but, interestingly, the geometry of the [V(2)O(2)((2R,3R)-tart)((2S,3S)-tart)](2-) ion resembles the structure of the [(VO)(2)((2R,3R)-tart)((2S,3S)-tart)](4-) ion which has a vanadium(IV) center. Using Raman and (51)V NMR spectroscopy the solvent dependent mutual transformations of [V(4)O(8)((2R,3R)-tart)(2)](4-) (V(4)L(2)-RR), [V(4)O(8)((2S,3S)-tart)(2)](4-) (V(4)L(2)-SS), [V(2)O(4)((2R,3R)-H(2)tart)(2)](2-) (V(2)L(2)-RR), [V(2)O(4)((2S,3S)-H(2)tart)(2)](2-) (V(2)L(2)-SS), and [V(2)O(2)((2R,3R)-tart)((2S,3S)-tart)](2-) (V(2)L(2)-rac) have been established. In aqueous solution the following reactions take place; 2 V(2)L(2)-rac --> V(2)L(2)-RR + V(2)L(2)-SS followed by partial decomposition, V(2)L(2)-RR --> V(4)L(2)-RR + 2 L (V(2)L(2)-SS --> V(4)L(2)-SS + 2 L). On the other hand V(2)L(2)-rac is stable in CH(3)CN solution while V(2)L(2)-RR (V(2)L(2)-SS) decomposes into several species.

  8. Adhesion and formation of microbial biofilms in complex microfluidic devices

    SciTech Connect

    Kumar, Aloke; Karig, David K; Neethirajan, Suresh; Suresh, Anil K; Srijanto, Bernadeta R; Mukherjee, Partha P; Retterer, Scott T; Doktycz, Mitchel John

    2012-01-01

    Shewanella oneidensis is a metal reducing bacterium, which is of interest for bioremediation and clean energy applications. S. oneidensis biofilms play a critical role in several situations such as in microbial energy harvesting devices. Here, we use a microfluidic device to quantify the effects of hydrodynamics on the biofilm morphology of S. oneidensis. For different rates of fluid flow through a complex microfluidic device, we studied the spatiotemporal dynamics of biofilms, and we quantified several morphological features such as spatial distribution, cluster formation and surface coverage. We found that hydrodynamics resulted in significant differences in biofilm dynamics. The baffles in the device created regions of low and high flow in the same device. At higher flow rates, a nonuniform biofilm develops, due to unequal advection in different regions of the microchannel. However, at lower flow rates, a more uniform biofilm evolved. This depicts competition between adhesion events, growth and fluid advection. Atomic force microscopy (AFM) revealed that higher production of extra-cellular polymeric substances (EPS) occurred at higher flow velocities.

  9. Structural basis of complement membrane attack complex formation

    PubMed Central

    Serna, Marina; Giles, Joanna L.; Morgan, B. Paul; Bubeck, Doryen

    2016-01-01

    In response to complement activation, the membrane attack complex (MAC) assembles from fluid-phase proteins to form pores in lipid bilayers. MAC directly lyses pathogens by a ‘multi-hit' mechanism; however, sublytic MAC pores on host cells activate signalling pathways. Previous studies have described the structures of individual MAC components and subcomplexes; however, the molecular details of its assembly and mechanism of action remain unresolved. Here we report the electron cryo-microscopy structure of human MAC at subnanometre resolution. Structural analyses define the stoichiometry of the complete pore and identify a network of interaction interfaces that determine its assembly mechanism. MAC adopts a ‘split-washer' configuration, in contrast to the predicted closed ring observed for perforin and cholesterol-dependent cytolysins. Assembly precursors partially penetrate the lipid bilayer, resulting in an irregular β-barrel pore. Our results demonstrate how differences in symmetric and asymmetric components of the MAC underpin a molecular basis for pore formation and suggest a mechanism of action that extends beyond membrane penetration. PMID:26841837

  10. Structural basis of complement membrane attack complex formation.

    PubMed

    Serna, Marina; Giles, Joanna L; Morgan, B Paul; Bubeck, Doryen

    2016-02-04

    In response to complement activation, the membrane attack complex (MAC) assembles from fluid-phase proteins to form pores in lipid bilayers. MAC directly lyses pathogens by a 'multi-hit' mechanism; however, sublytic MAC pores on host cells activate signalling pathways. Previous studies have described the structures of individual MAC components and subcomplexes; however, the molecular details of its assembly and mechanism of action remain unresolved. Here we report the electron cryo-microscopy structure of human MAC at subnanometre resolution. Structural analyses define the stoichiometry of the complete pore and identify a network of interaction interfaces that determine its assembly mechanism. MAC adopts a 'split-washer' configuration, in contrast to the predicted closed ring observed for perforin and cholesterol-dependent cytolysins. Assembly precursors partially penetrate the lipid bilayer, resulting in an irregular β-barrel pore. Our results demonstrate how differences in symmetric and asymmetric components of the MAC underpin a molecular basis for pore formation and suggest a mechanism of action that extends beyond membrane penetration.

  11. Integrin activation and focal complex formation in cardiac hypertrophy

    NASA Technical Reports Server (NTRS)

    Laser, M.; Willey, C. D.; Jiang, W.; Cooper, G. 4th; Menick, D. R.; Zile, M. R.; Kuppuswamy, D.

    2000-01-01

    Cardiac hypertrophy is characterized by both remodeling of the extracellular matrix (ECM) and hypertrophic growth of the cardiocytes. Here we show increased expression and cytoskeletal association of the ECM proteins fibronectin and vitronectin in pressure-overloaded feline myocardium. These changes are accompanied by cytoskeletal binding and phosphorylation of focal adhesion kinase (FAK) at Tyr-397 and Tyr-925, c-Src at Tyr-416, recruitment of the adapter proteins p130(Cas), Shc, and Nck, and activation of the extracellular-regulated kinases ERK1/2. A synthetic peptide containing the Arg-Gly-Asp (RGD) motif of fibronectin and vitronectin was used to stimulate adult feline cardiomyocytes cultured on laminin or within a type-I collagen matrix. Whereas cardiocytes under both conditions showed RGD-stimulated ERK1/2 activation, only collagen-embedded cells exhibited cytoskeletal assembly of FAK, c-Src, Nck, and Shc. In RGD-stimulated collagen-embedded cells, FAK was phosphorylated only at Tyr-397 and c-Src association occurred without Tyr-416 phosphorylation and p130(Cas) association. Therefore, c-Src activation is not required for its cytoskeletal binding but may be important for additional phosphorylation of FAK. Overall, our study suggests that multiple signaling pathways originate in pressure-overloaded heart following integrin engagement with ECM proteins, including focal complex formation and ERK1/2 activation, and many of these pathways can be activated in cardiomyocytes via RGD-stimulated integrin activation.

  12. Role of thiol-complex formation in 2-hydroxyethyl- methacrylate-induced toxicity in vitro.

    PubMed

    Samuelsen, J T; Kopperud, H M; Holme, J A; Dragland, I S; Christensen, T; Dahl, J E

    2011-02-01

    Methacrylate monomers that are found to leach from cured resin-based dental materials induce biological effects in vitro. The underlying mechanisms have not been fully elucidated although involvement of increased cellular reactive oxygen species (ROS) and DNA-damage has been suggested. In this in vitro study we have elucidated the impact of a commonly used methacrylate monomer, HEMA, on the level and oxidation state of cellular glutathione, intracellular ROS level, as well as the formation of complex between HEMA and glutathione. HEMA exposure rapidly led to increased level of ROS and reduced level of GSH (reduced form of glutathione). Antioxidants effectively counteracted the ROS increase, but had no effect on the GSH depletion. No change in glutathione-disulphide (GSSG; oxidized form of glutathione) concentration was detected in the HEMA treated cells, showing that oxidation of glutathione was not responsible for the reduced GSH concentration. Further we demonstrated spontaneous formation of a complex between HEMA and GSH. In conclusion, we showed that exposure to HEMA led to drop in cellular glutathione level probably caused by complex formation with HEMA. A similar covalent binding of HEMA to macromolecules combined with increased level of cellular ROS due to lower levels of GSH is suggested to be important factors triggering the toxic response.

  13. 3D structure and formation of hydrothermal vent complexes in the Møre Basin

    NASA Astrophysics Data System (ADS)

    Kjoberg, Sigurd; Schmiedel, Tobias; Planke, Sverre; Svensen, Henrik H.; Galland, Oliver; Jerram, Dougal A.

    2016-04-01

    The mid-Norwegian Møre margin is regarded as a type example of a volcanic rifted margin, with its formation usually related to the influence of the Icelandic plume activity. The area is characterized by the presence of voluminous basaltic complexes such as extrusive lava sequences, intrusive sills and dikes, and hydrothermal vent complexes within the Møre Basin. Emplacement of hydrothermal vent complexes is accommodated by deformation of the host rock. The edges of igneous intrusions mobilize fluids by heat transfer into the sedimentary host rock (aureoles). Fluid expansion may lead to formation of piercing structures due to upward fluid migration. Hydrothermal vent complexes induce bending of overlying strata, leading to the formation of dome structures at the paleo-surface. These dome structures are important as they indicate the accommodation created for the intrusions by deformation of the upper layers of the stratigraphy, and may form important structures in many volcanic margins. Both the morphological characteristics of the upper part and the underlying feeder-structure (conduit-zone) can be imaged and studied on 3D seismic data. Seismic data from the Tulipan prospect located in the western part of the Møre Basin have been used in this study. The investigation focusses on (1) the vent complex geometries, (2) the induced surface deformation patterns, (3) the relation to the intrusions (heat source), as well as (4) the emplacement depth of the hydrothermal vent complexes. We approach this by doing a detailed 3D seismic interpretation of the Tulipan seismic data cube. The complexes formed during the initial Eocene, and are believed to be a key factor behind the rapid warming event called the Paleocene-Eocene thermal maximum (PETM). The newly derived understanding of age, eruptive deposits, and formation of hydrothermal vent complexes in the Møre Basin enables us to contribute to the general understanding of the igneous plumbing system in volcanic basins and

  14. Spectrophotometric and spectrofluorimetric determination of certain diuretics through ternary complex formation with eosin and lead (II).

    PubMed

    Omar, Mahmoud A

    2010-01-01

    Simple and sensitive spectrophotometric and spectrofluorimetric methods have been developed for the determination of hydrochlorothiazide (I), indapamide (II) and xipamide(III) based on ternary complex formation with eosin and lead (II) in the presence of methylcellulose as surfactant. The methods do not involve solvent extraction. For spectrophotometric method, the ternary complex showed an absorption maximum at 543 nm. The factors affecting the formation of ternary complex were studied and optimized. The method obeys Beer's law over concentration range of 8-40 microg mL(-1). A fluorescence quenching method for the determination of the cited drugs by forming this ternary complex was also investigated for the purpose of enhancing the sensitivity of the determination. The analytical performance of both methods was fully validated, and the results were satisfactory. The methods have been successfully applied for the determination of the studied drugs in their pharmaceutical tablets and the results obtained ware in good agreement with those obtained by the reference method. Common excipients used as additives in tablets do not interfere with the proposed methods.

  15. Silver(I) complex formation with cysteine, penicillamine, and glutathione.

    PubMed

    Leung, Bonnie O; Jalilehvand, Farideh; Mah, Vicky; Parvez, Masood; Wu, Qiao

    2013-04-15

    The complex formation between silver(I) and cysteine (H2Cys), penicillamine (H2Pen), and glutathione (H3Glu) in alkaline aqueous solution was examined using extended X-ray absorption fine structure (EXAFS) and (109)Ag NMR spectroscopic techniques. The complexes formed in 0.1 mol dm(-3) Ag(I) solutions with cysteine and penicillamine were investigated for ligand/Ag(I) (L/Ag) mole ratios increasing from 2.0 to 10.0. For the series of cysteine solutions (pH 10-11) a mean Ag-S bond distance of 2.45 ± 0.02 Å consistently emerged, while for penicillamine (pH 9) the average Ag-S bond distance gradually increased from 2.40 to 2.44 ± 0.02 Å. EXAFS and (109)Ag NMR spectra of a concentrated Ag(I)-cysteine solution (C(Ag(I)) = 0.8 mol dm(-3), L/Ag = 2.2) showed a mean Ag-S bond distance of 2.47 ± 0.02 Å and δ((109)Ag) 1103 ppm, consistent with prevailing, partially oligomeric AgS3 coordinated species, while for penicillamine (C(Ag(I)) = 0.5 mol dm(-3), L/Ag = 2.0) the mean Ag-S bond distance of 2.40 ± 0.02 Å and δ((109)Ag) 922 ppm indicate that mononuclear AgS2 coordinated complexes dominate. For Ag(I)-glutathione solutions (C(Ag(I)) = 0.01 mol dm(-3), pH ∼11), mononuclear AgS2 coordinated species with a mean Ag-S bond distance of 2.36 ± 0.02 Å dominate for L/Ag mole ratios from 2.0 to 10.0. The crystal structure of the silver(I)-cysteine compound (NH4)Ag2(HCys)(Cys)·H2O (1) precipitating at pH ∼10 was solved and showed a layer structure with both AgS3 and AgS3N coordination to the cysteinate ligands. A redetermination of the crystal structure of Ag(HPen)·H2O (2) confirmed the proposed digonal AgS2 coordination environment to bridging thiolate sulfur atoms in polymeric intertwining chains forming a double helix. A survey of Ag-S bond distances for crystalline Ag(I) complexes with S-donor ligands in different AgS2, AgS2(O/N), and AgS3 coordination environments was used, together with a survey of (109)Ag NMR chemical shifts, to assist assignments of the Ag

  16. Perfluoroalkyl Cobalt(III) Fluoride and Bis(perfluoroalkyl) Complexes: Catalytic Fluorination and Selective Difluorocarbene Formation.

    PubMed

    Leclerc, Matthew C; Bayne, Julia M; Lee, Graham M; Gorelsky, Serge I; Vasiliu, Monica; Korobkov, Ilia; Harrison, Daniel J; Dixon, David A; Baker, R Tom

    2015-12-30

    Four perfluoroalkyl cobalt(III) fluoride complexes have been synthesized and characterized by elemental analysis, multinuclear NMR spectroscopy, X-ray crystallography, and powder X-ray diffraction. The remarkable cobalt fluoride (19)F NMR chemical shifts (-716 to -759 ppm) were studied computationally, and the contributing paramagnetic and diamagnetic factors were extracted. Additionally, the complexes were shown to be active in the catalytic fluorination of p-toluoyl chloride. Furthermore, two examples of cobalt(III) bis(perfluoroalkyl)complexes were synthesized and their reactivity studied. Interestingly, abstraction of a fluoride ion from these complexes led to selective formation of cobalt difluorocarbene complexes derived from the trifluoromethyl ligand. These electrophilic difluorocarbenes were shown to undergo insertion into the remaining perfluoroalkyl fragment, demonstrating the elongation of a perfluoroalkyl chain arising from a difluorocarbene insertion on a cobalt metal center. The reactions of both the fluoride and bis(perfluoroalkyl) complexes provide insight into the potential catalytic applications of these model systems to form small fluorinated molecules as well as fluoropolymers.

  17. Natural Product Screening Reveals Naphthoquinone Complex I Bypass Factors

    PubMed Central

    Mevers, Emily; Higgins, Kathleen W.; Fomina, Yevgenia; Zhang, Jianming; Mandinova, Anna; Newman, David; Shaw, Stanley Y.; Clardy, Jon; Mootha, Vamsi K.

    2016-01-01

    Deficiency of mitochondrial complex I is encountered in both rare and common diseases, but we have limited therapeutic options to treat this lesion to the oxidative phosphorylation system (OXPHOS). Idebenone and menadione are redox-active molecules capable of rescuing OXPHOS activity by engaging complex I-independent pathways of entry, often referred to as “complex I bypass.” In the present study, we created a cellular model of complex I deficiency by using CRISPR genome editing to knock out Ndufa9 in mouse myoblasts, and utilized this cell line to develop a high-throughput screening platform for novel complex I bypass factors. We screened a library of ~40,000 natural product extracts and performed bioassay-guided fractionation on a subset of the top scoring hits. We isolated four plant-derived 1,4-naphthoquinone complex I bypass factors with structural similarity to menadione: chimaphilin and 3-chloro-chimaphilin from Chimaphila umbellata and dehydro-α-lapachone and dehydroiso-α-lapachone from Stereospermum euphoroides. We also tested a small number of structurally related naphthoquinones from commercial sources and identified two additional compounds with complex I bypass activity: 2-methoxy-1,4-naphthoquinone and 2-methoxy-3-methyl-1,4,-naphthoquinone. The six novel complex I bypass factors reported here expand this class of molecules and will be useful as tool compounds for investigating complex I disease biology. PMID:27622560

  18. Natural Product Screening Reveals Naphthoquinone Complex I Bypass Factors.

    PubMed

    Vafai, Scott B; Mevers, Emily; Higgins, Kathleen W; Fomina, Yevgenia; Zhang, Jianming; Mandinova, Anna; Newman, David; Shaw, Stanley Y; Clardy, Jon; Mootha, Vamsi K

    2016-01-01

    Deficiency of mitochondrial complex I is encountered in both rare and common diseases, but we have limited therapeutic options to treat this lesion to the oxidative phosphorylation system (OXPHOS). Idebenone and menadione are redox-active molecules capable of rescuing OXPHOS activity by engaging complex I-independent pathways of entry, often referred to as "complex I bypass." In the present study, we created a cellular model of complex I deficiency by using CRISPR genome editing to knock out Ndufa9 in mouse myoblasts, and utilized this cell line to develop a high-throughput screening platform for novel complex I bypass factors. We screened a library of ~40,000 natural product extracts and performed bioassay-guided fractionation on a subset of the top scoring hits. We isolated four plant-derived 1,4-naphthoquinone complex I bypass factors with structural similarity to menadione: chimaphilin and 3-chloro-chimaphilin from Chimaphila umbellata and dehydro-α-lapachone and dehydroiso-α-lapachone from Stereospermum euphoroides. We also tested a small number of structurally related naphthoquinones from commercial sources and identified two additional compounds with complex I bypass activity: 2-methoxy-1,4-naphthoquinone and 2-methoxy-3-methyl-1,4,-naphthoquinone. The six novel complex I bypass factors reported here expand this class of molecules and will be useful as tool compounds for investigating complex I disease biology.

  19. Formation of a highly stable complex between BN 50730 [tetrahydro-4,7,8,10 methyl-1(chloro-2 phenyl)-6 (methoxy-4 phenyl-carbamoyl)-9 pyrido [4',3'-4,5] thieno [3,2-f] triazolo-1,2,4 [4,3-a] diazepine-1,4] and the platelet-activating factor receptor in rabbit platelet membranes.

    PubMed

    Silva, C L; Cruz, H N; Violante, F A; Cordeiro, R S; Martins, M A; Noël, F

    1996-01-26

    BN 50730 [tetrahydro-4,7,8,10 methyl-1(chloro-2 phenyl)-6 (methoxy-4 phenyl-carbamoyl)-9 pyrido [4',3'-4,5] thieno [3,2-f] triazolo-1,2,4 [4,3-alpha] diazepine-1,4], a novel platelet-activating factor (PAF) receptor antagonist with a hetrazepine structure, decreased the maximal number of binding sites (Bmax) of [3H]PAF in rabbit platelet membranes without altering its dissociation constant. Platelet aggregation induced by 1 microM PAF was prevented by preincubation with 1 microM BN 50730. The washing of the platelets preincubated with BN 50730 failed to revert its inhibitory effects. We conclude that BN 50730 acts as a non-competitive antagonist of the PAF receptor, due to the formation of a highly stable drug-receptor complex.

  20. Formation of Gold(III) Alkyls from Gold Alkoxide Complexes

    PubMed Central

    2017-01-01

    The gold(III) methoxide complex (C∧N∧C)AuOMe (1) reacts with tris(p-tolyl)phosphine in benzene at room temperature under O abstraction to give the methylgold product (C∧N∧C)AuMe (2) together with O=P(p-tol)3 ((C∧N∧C) = [2,6-(C6H3tBu-4)2pyridine]2–). Calculations show that this reaction is energetically favorable (ΔG = −32.3 kcal mol–1). The side products in this reaction, the Au(II) complex [Au(C∧N∧C)]2 (3) and the phosphorane (p-tol)3P(OMe)2, suggest that at least two reaction pathways may operate, including one involving (C∧N∧C)Au• radicals. Attempts to model the reaction by DFT methods showed that PPh3 can approach 1 to give a near-linear Au–O–P arrangement, without phosphine coordination to gold. The analogous reaction of (C∧N∧C)AuOEt, on the other hand, gives exclusively a mixture of 3 and (p-tol)3P(OEt)2. Whereas the reaction of (C∧N∧C)AuOR (R = But, p-C6H4F) with P(p-tol)3 proceeds over a period of hours, compounds with R = CH2CF3, CH(CF3)2 react almost instantaneously, to give 3 and O=P(p-tol)3. In chlorinated solvents, treatment of the alkoxides (C∧N∧C)AuOR with phosphines generates [(C∧N∧C)Au(PR3)]Cl, via Cl abstraction from the solvent. Attempts to extend the synthesis of gold(III) alkoxides to allyl alcohols were unsuccessful; the reaction of (C∧N∧C)AuOH with an excess of CH2=CHCH2OH in toluene led instead to allyl alcohol isomerization to give a mixture of gold alkyls, (C∧N∧C)AuR′ (R′ = −CH2CH2CHO (10), −CH2CH(CH2OH)OCH2CH=CH2 (11)), while 2-methallyl alcohol affords R′ = CH2CH(Me)CHO (12). The crystal structure of 11 was determined. The formation of Au–C instead of the expected Au–O products is in line with the trend in metal–ligand bond dissociation energies for Au(III): M–H > M–C > M–O.

  1. Preliminary Study for a Tetrahedron Formation: Quality Factors and Visualization

    NASA Technical Reports Server (NTRS)

    Guzman, Jose J.; Schiff, Conrad; Bauer, Frank (Technical Monitor)

    2002-01-01

    Spacecraft flying in tetrahedron formations are excellent for electromagnetic and plasma studies. The quality of the science recorded is strongly affected by the tetrahedron evolution. This paper is a preliminary study on the computation of quality factors and visualization for a formation of four or five satellites. Four of the satellites are arranged geometrically in a tetrahedron shape. If a fifth satellite is present, it is arbitrarily initialized at the geometric center of the tetrahedron. The fifth satellite could act as a collector or as a spare spacecraft. Tetrahedron natural coordinates are employed for the initialization. The natural orbit evolution is visualized in geocentric equatorial inertial and in geocentric solar magnetospheric coordinates.

  2. Genetic and Environmental Factors in Complex Neurodevelopmental Disorders

    PubMed Central

    van Loo, K.M.J; Martens, G.J.M

    2007-01-01

    Complex neurodevelopmental disorders, such as schizophrenia, autism, attention deficit (hyperactivity) disorder, (manic) depressive illness and addiction, are thought to result from an interaction between genetic and environmental factors. Association studies on candidate genes and genome-wide linkage analyses have identified many susceptibility chromosomal regions and genes, but considerable efforts to replicate association have been surprisingly often disappointing. Here, we summarize the current knowledge of the genetic contribution to complex neurodevelopmental disorders, focusing on the findings from association and linkage studies. Furthermore, the contribution of the interaction of the genetic with environmental and epigenetic factors to the aetiology of complex neurodevelopmental disorders as well as suggestions for future research are discussed. PMID:19412416

  3. From polyadenylation to splicing: Dual role for mRNA 3' end formation factors.

    PubMed

    Misra, Ashish; Green, Michael R

    2016-01-01

    Recent genome-wide protein-RNA interaction studies have significantly reshaped our understanding of the role of mRNA 3' end formation factors in RNA biology. Originally thought to function solely in mediating cleavage and polyadenylation of mRNAs during their maturation, 3' end formation factors have now been shown to play a role in alternative splicing, even at internal introns--an unanticipated role for factors thought only to act at the 3' end of the mRNA. Here, we discuss the recent advances in our understanding of the role of 3' end formation factors in promoting global changes in alternative splicing at internal exon-intron junctions and how they act as cofactors for well known splicing regulators. Additionally, we review the mechanism by which these factors affect the recruitment of early intron recognition components to the 5' and 3' splice site. Our understanding of the roles of 3' end formation factors is still evolving, and the final picture might be more complex than originally envisioned.

  4. Factors relating to dental stain formation in the rat.

    PubMed

    McDonald, J L; Schemehorn, B R; Stookey, G K

    1985-05-01

    A series of studies was conducted to investigate the use of the rat as an in vivo model for studies of dental stain and to identify dietary factors which influence stain formation in this model. It was determined that appreciable amounts of stain formed on the molar teeth of rats provided a synthetic diet containing lactalbumin, and the amount of stain increased throughout a four-week test period. Stain formation was also observed when rats were provided their diet by gastric intubation. Topical applications of chlorhexidine generally resulted in an increase in stain formation, as did the presence of tea in the drinking water. These studies support the use of the rat for investigations of dental stain.

  5. Charge-transfer complex formation between o-chloranil and a series of polynuclear aromatic hydrocarbons

    NASA Astrophysics Data System (ADS)

    Chakraborty, Biswanath; Mukherjee, Asok K.; Seal, Bejoy K.

    2001-02-01

    The equilibrium constants, enthalpies and entropies of formation of molecular electron donor-acceptor (EDA) complexes of o-chloranil with a series of aromatic hydrocarbons have been determined spectrophotometrically. Spectroscopic and thermodynamic aspects of these complexes have been analysed.

  6. Reactions of a Dinitrogen Complex of Molybdenum: Formation of a Carbon-Nitrogen Bond.

    ERIC Educational Resources Information Center

    Busby, David C.; And Others

    1981-01-01

    Reports a procedure for the formation of alkyldiazenido complexes of molybdenum in the absence of dioxygen, suitable for inclusion in an advanced inorganic chemistry laboratory. Includes background information and experimental procedures for two complexes. (SK)

  7. Two quorum sensing systems control biofilm formation and virulence in members of the Burkholderia cepacia complex

    PubMed Central

    Suppiger, Angela; Schmid, Nadine; Aguilar, Claudio; Pessi, Gabriella; Eberl, Leo

    2013-01-01

    The Burkholderia cepacia complex (Bcc) consists of 17 closely related species that are problematic opportunistic bacterial pathogens for cystic fibrosis patients and immunocompromised individuals. These bacteria are capable of utilizing two different chemical languages: N-acyl homoserine lactones (AHLs) and cis-2-unsaturated fatty acids. Here we summarize the current knowledge of the underlying molecular architectures of these communication systems, showing how they are interlinked and discussing how they regulate overlapping as well as specific sets of genes. A particular focus is laid on the role of these signaling systems in the formation of biofilms, which are believed to be highly important for chronic infections. We review genes that have been implicated in the sessile lifestyle of this group of bacteria. The new emerging role of the intracellular second messenger cyclic dimeric guanosine monophosphate (c-di-GMP) as a downstream regulator of the fatty acid signaling cascade and as a key factor in biofilm formation is also discussed. PMID:23799665

  8. In vivo formation and binding of SeHg complexes to the erythrocyte surface.

    PubMed

    Cherdwongcharoensuk, Duangrudee; Oliveira, Maria João; Aguas, Artur Perez

    2010-08-01

    The in vivo dynamics of selenium (Se) and mercury (Hg) interaction was studied in mouse tissues using direct visualization of individual Se, Hg, and SeHg particles on the surface of circulating erythrocytes. This high-resolution detection of Se and Hg was obtained by scanning electron microscopy coupled to X-ray microanalysis. BALB/c mice were injected in the peritoneal cavity with Se and Hg salts, and the animals were sacrificed 3 min after the Hg injection. Only a minority (9%) of the metal dots seen on mouse liver erythrocytes were SeHg complexes when Se and Hg salts were mixed together before injection. In contrast, the majority (73%) of metal dots on liver erythrocytes were SeHg complexes if Se was injected at least 5 min before Hg injection. All metal dots on liver erythrocytes were of SeHg complexes if Se was injected 9 or 12 min before the Hg injection. We conclude that the formation of stable in vivo SeHg complexes requires preliminary interaction of Se with a putative serum factor before complexes between Se and Hg are formed and are bound to the erythrocyte cell surface.

  9. cAMP prevents TNF-induced apoptosis through inhibiting DISC complex formation in rat hepatocytes

    SciTech Connect

    Bhattacharjee, Rajesh; Xiang, Wenpei; Wang, Yinna; Zhang, Xiaoying

    2012-06-22

    Highlights: Black-Right-Pointing-Pointer cAMP blocks cell death induced by TNF and actinomycin D in cultured hepatocytes. Black-Right-Pointing-Pointer cAMP blocks NF-{kappa}B activation induced by TNF and actinomycin D. Black-Right-Pointing-Pointer cAMP blocks DISC formation following TNF and actinomycin D exposure. Black-Right-Pointing-Pointer cAMP blocks TNF signaling at a proximal step. -- Abstract: Tumor necrosis factor {alpha} (TNF) is a pleiotropic proinflammatory cytokine that plays a role in immunity and the control of cell proliferation, cell differentiation, and apoptosis. The pleiotropic nature of TNF is due to the formation of different signaling complexes upon the binding of TNF to its receptor, TNF receptor type 1 (TNFR1). TNF induces apoptosis in various mammalian cells when the cells are co-treated with a transcription inhibitor like actinomycin D (ActD). When TNFR1 is activated, it recruits an adaptor protein, TNF receptor-associated protein with death domain (TRADD), through its cytoplasmic death effector domain (DED). TRADD, in turn, recruits other signaling proteins, including TNF receptor-associated protein 2 (TRAF2) and receptor-associated protein kinase (RIPK) 1, to form a complex. Subsequently, this complex combines with FADD and procaspase-8, converts into a death-inducing signaling complex (DISC) to induce apoptosis. Cyclic AMP (cAMP) is a second messenger that regulates various cellular processes such as cell proliferation, gene expression, and apoptosis. cAMP analogues are reported to act as anti-apoptotic agents in various cell types, including hepatocytes. We found that a cAMP analogue, dibutyryl cAMP (db-cAMP), inhibits TNF + ActD-induced apoptosis in rat hepatocytes. The protein kinase A (PKA) inhibitor KT-5720 reverses this inhibitory effect of cAMP on apoptosis. Cytoprotection by cAMP involves down-regulation of various apoptotic signal regulators like TRADD and FADD and inhibition of caspase-8 and caspase-3 cleavage. We also found

  10. Mode of formation and structural features of DNA-cationic liposome complexes used for transfection.

    PubMed

    Gershon, H; Ghirlando, R; Guttman, S B; Minsky, A

    1993-07-20

    Complexes formed between cationic liposomes and nucleic acids represent a highly efficient vehicle for delivery of DNA and RNA molecules into a large variety of eukaryotic cells. By using fluorescence, gel electrophoresis, and metal-shadowing electron microscopy techniques, the factors that affect the, yet unclear, interactions between DNA and cationic liposomes as well as the structural features of the resulting complexes have been elucidated. A model is suggested according to which cationic liposomes bind initially to DNA molecules to form clusters of aggregated vesicles along the nucleic acids. At a critical liposome density, two processes occur, namely, DNA-induced membrane fusion, indicated by lipid mixing studies, and liposome-induced DNA collapse, pointed out by the marked cooperativity of the encapsulation processes, by their modulations by DNA-condensing agents, and also by their conspicuous independence upon DNA length. The DNA collapse leads to the formation of condensed structures which can be completely encapsulated within the fused lipid bilayers in a fast, highly cooperative process since their exposed surface is substantially smaller than that of extended DNA molecules. The formation of the transfecting DNA-liposome complexes in which the nucleic acids are fully encapsulated within a positively-charged lipid bilayer is proposed, consequently, to be dominated by mutual effects exerted by the DNA and the cationic liposomes, leading to interrelated lipid fusion and DNA collapse.

  11. SOHLH2 is essential for synaptonemal complex formation during spermatogenesis in early postnatal mouse testes.

    PubMed

    Park, Miree; Lee, Youngeun; Jang, Hoon; Lee, Ok-Hee; Park, Sung-Won; Kim, Jae-Hwan; Hong, Kwonho; Song, Hyuk; Park, Se-Pill; Park, Yun-Yong; Ko, Jung Jae; Choi, Youngsok

    2016-02-12

    Spermatogenesis- and oogenesis-specific helix-loop-helix transcription factor 2 (SOHLH2) is exclusively expressed in germ cells of the gonads. Previous studies show that SOHLH2 is critical for spermatogenesis in mouse. However, the regulatory mechanism of SOHLH2 during early spermatogenesis is poorly understood. In the present study, we analyzed the gene expression profile of the Sohlh2-deficient testis and examined the role of SOHLH2 during spermatogenesis. We found 513 genes increased in abundance, while 492 genes decreased in abundance in 14-day-old Sohlh2-deficient mouse testes compared to wildtype mice. Gene ontology analysis revealed that Sohlh2 disruption effects the relative abundance of various meiotic genes during early spermatogenesis, including Spo11, Dmc1, Msh4, Prdm9, Sycp1, Sycp2, Sycp3, Hormad1, and Hormad2. Western blot analysis and immunostaining showed that SYCP3, a component of synaptonemal complex, was significantly less abundant in Sohlh2-deficient spermatocytes. We observed a lack of synaptonemal complex formation during meiosis in Sohlh2-deficient spermatocytes. Furthermore, we found that SOHLH2 interacted with two E-boxes on the mouse Sycp1 promoter and Sycp1 promoter activity increased with ectopically expressed SOHLH2. Taken together, our data suggest that SOHLH2 is critical for the formation of synaptonemal complexes via its regulation of Sycp1 expression during mouse spermatogonial differentiation.

  12. SOHLH2 is essential for synaptonemal complex formation during spermatogenesis in early postnatal mouse testes

    PubMed Central

    Park, Miree; Lee, Youngeun; Jang, Hoon; Lee, Ok-Hee; Park, Sung-Won; Kim, Jae-Hwan; Hong, Kwonho; Song, Hyuk; Park, Se-Pill; Park, Yun-Yong; Ko, Jung Jae; Choi, Youngsok

    2016-01-01

    Spermatogenesis- and oogenesis-specific helix-loop-helix transcription factor 2 (SOHLH2) is exclusively expressed in germ cells of the gonads. Previous studies show that SOHLH2 is critical for spermatogenesis in mouse. However, the regulatory mechanism of SOHLH2 during early spermatogenesis is poorly understood. In the present study, we analyzed the gene expression profile of the Sohlh2-deficient testis and examined the role of SOHLH2 during spermatogenesis. We found 513 genes increased in abundance, while 492 genes decreased in abundance in 14-day-old Sohlh2-deficient mouse testes compared to wildtype mice. Gene ontology analysis revealed that Sohlh2 disruption effects the relative abundance of various meiotic genes during early spermatogenesis, including Spo11, Dmc1, Msh4, Prdm9, Sycp1, Sycp2, Sycp3, Hormad1, and Hormad2. Western blot analysis and immunostaining showed that SYCP3, a component of synaptonemal complex, was significantly less abundant in Sohlh2-deficient spermatocytes. We observed a lack of synaptonemal complex formation during meiosis in Sohlh2-deficient spermatocytes. Furthermore, we found that SOHLH2 interacted with two E-boxes on the mouse Sycp1 promoter and Sycp1 promoter activity increased with ectopically expressed SOHLH2. Taken together, our data suggest that SOHLH2 is critical for the formation of synaptonemal complexes via its regulation of Sycp1 expression during mouse spermatogonial differentiation. PMID:26869299

  13. Photochemical formation of complexed HNO in low temperature matrices

    NASA Astrophysics Data System (ADS)

    Müller, R. P.; Murata, S.; Huber, J. Robert

    1982-04-01

    The molecule HNO complexed to N-methylenemethylamine (H 2CNCH 3) was prepared by photolyzing N,N-dimethylnitrosamine [(CH 3) 2NNO] in low temperature matrices. The infrared absorptions of six isotopic such complexed HNO species were measured and assigned. Based on these results a complex between HNO and the amine involving a hydrogen bond is proposed. The bands associated with the hydrogen bond, NH out-of-plane bend and N…HN stretch, were assigned. The NH stretch vibrational band of HNO is blue-shifted by complexation and has a linewidth < 1 cm -1.

  14. Improving the Factor Structure of Psychological Scales: The Expanded Format as an Alternative to the Likert Scale Format

    ERIC Educational Resources Information Center

    Zhang, Xijuan; Savalei, Victoria

    2016-01-01

    Many psychological scales written in the Likert format include reverse worded (RW) items in order to control acquiescence bias. However, studies have shown that RW items often contaminate the factor structure of the scale by creating one or more method factors. The present study examines an alternative scale format, called the Expanded format,…

  15. Double layer formation at the interface of complex plasmas

    SciTech Connect

    Yaroshenko, V. V.; Thoma, M. H.; Thomas, H. M.; Morfill, G. E.

    2008-08-15

    Necessary conditions are formulated for the generation of a double layer at the interface of a complex plasma and a particle-free electron-ion plasma in a weakly collisional discharge. Examples are calculated for realistic observed complex plasmas, and it is shown that situations of both ''smooth'' transitions and 'sharp' transitions can exist. The model can explain the abrupt boundaries observed.

  16. Regulation of Memory Formation by the Transcription Factor XBP1.

    PubMed

    Martínez, Gabriela; Vidal, René L; Mardones, Pablo; Serrano, Felipe G; Ardiles, Alvaro O; Wirth, Craig; Valdés, Pamela; Thielen, Peter; Schneider, Bernard L; Kerr, Bredford; Valdés, Jose L; Palacios, Adrian G; Inestrosa, Nibaldo C; Glimcher, Laurie H; Hetz, Claudio

    2016-02-16

    Contextual memory formation relies on the induction of new genes in the hippocampus. A polymorphism in the promoter of the transcription factor XBP1 was identified as a risk factor for Alzheimer's disease and bipolar disorders. XBP1 is a major regulator of the unfolded protein response (UPR), mediating adaptation to endoplasmic reticulum (ER) stress. Using a phenotypic screen, we uncovered an unexpected function of XBP1 in cognition and behavior. Mice lacking XBP1 in the nervous system showed specific impairment of contextual memory formation and long-term potentiation (LTP), whereas neuronal XBP1s overexpression improved performance in memory tasks. Gene expression analysis revealed that XBP1 regulates a group of memory-related genes, highlighting brain-derived neurotrophic factor (BDNF), a key component in memory consolidation. Overexpression of BDNF in the hippocampus reversed the XBP1-deficient phenotype. Our study revealed an unanticipated function of XBP1 in cognitive processes that is apparently unrelated to its role in ER stress.

  17. Direct evidence of an elongation factor-Tu/Ts·GTP·Aminoacyl-tRNA quaternary complex.

    PubMed

    Burnett, Benjamin J; Altman, Roger B; Ferguson, Angelica; Wasserman, Michael R; Zhou, Zhou; Blanchard, Scott C

    2014-08-22

    During protein synthesis, elongation factor-Tu (EF-Tu) bound to GTP chaperones the entry of aminoacyl-tRNA (aa-tRNA) into actively translating ribosomes. In so doing, EF-Tu increases the rate and fidelity of the translation mechanism. Recent evidence suggests that EF-Ts, the guanosine nucleotide exchange factor for EF-Tu, directly accelerates both the formation and dissociation of the EF-Tu-GTP-Phe-tRNA(Phe) ternary complex (Burnett, B. J., Altman, R. B., Ferrao, R., Alejo, J. L., Kaur, N., Kanji, J., and Blanchard, S. C. (2013) J. Biol. Chem. 288, 13917-13928). A central feature of this model is the existence of a quaternary complex of EF-Tu/Ts·GTP·aa-tRNA(aa). Here, through comparative investigations of phenylalanyl, methionyl, and arginyl ternary complexes, and the development of a strategy to monitor their formation and decay using fluorescence resonance energy transfer, we reveal the generality of this newly described EF-Ts function and the first direct evidence of the transient quaternary complex species. These findings suggest that EF-Ts may regulate ternary complex abundance in the cell through mechanisms that are distinct from its guanosine nucleotide exchange factor functions.

  18. Constructing the S-matrix With Complex Factorization

    SciTech Connect

    Schuster, Philip C.; Toro, Natalia; /Stanford U., ITP

    2009-06-19

    A remarkable connection between BCFW recursion relations and constraints on the S-matrix was made by Benincasa and Cachazo in 0705.4305, who noted that mutual consistency of different BCFW constructions of four-particle amplitudes generates nontrivial (but familiar) constraints on three-particle coupling constants - these include gauge invariance, the equivalence principle, and the lack of non-trivial couplings for spins > 2. These constraints can also be derived with weaker assumptions, by demanding the existence of four-point amplitudes that factorize properly in all unitarity limits with complex momenta. From this starting point, we show that the BCFW prescription can be interpreted as an algorithm for fully constructing a tree-level S-matrix, and that complex factorization of general BCFW amplitudes follows from the factorization of four-particle amplitudes. The allowed set of BCFW deformations is identified, formulated entirely as a statement on the three-particle sector, and using only complex factorization as a guide. Consequently, our analysis based on the physical consistency of the S-matrix is entirely independent of field theory. We analyze the case of pure Yang-Mills, and outline a proof for gravity. For Yang-Mills, we also show that the well-known scaling behavior of BCFW-deformed amplitudes at large z is a simple consequence of factorization. For gravity, factorization in certain channels requires asymptotic behavior {approx} 1/z{sup 2}.

  19. Formation and Stability of Manganese-Desferrioxamine B Complexes

    NASA Astrophysics Data System (ADS)

    Duckworth, O. W.; Sposito, G.

    2004-12-01

    Recent laboratory and field studies suggest that Mn(III) forms persistent aqueous complexes with high-affinity ligands, particularly those produced by microbes. Aqueous Mn(III) species thus may play a significant, as-yet largely unexplored role in biogeochemical processes. We determined stability constants for both Mn(II) and Mn(III) complexes with the common tri-hydroxamate siderophore, desferrioxamine B (DFOB). We found the thermodynamic stability constants of the species, MHDFOBx-2 [M = Mn(II), x = 2; M = Mn(III), x = 3] to be KMn(II) = 106.8 ± 0.1 and KMn(III) = 1029.2 ± 0.2 at 25° C. The Mn(III)HDFOB+ complex is stable for pH in the range 7.0 - 11.3, but at pH < 7.0, Mn(III)HDFOB+ decays by internal electron transfer, yielding oxidized DFOB products and Mn2+. For pH > 11.3, the complex decays by disproportionation, yielding Mn2+ and solid MnO2. The Mn(III)HDFOB+ complex may be formed by either the oxidation of aqueous Mn(II)-HDFOB complexes or the DFOB-promoted dissolution of solid manganese(III) oxides. The DFOB-promoted Mn(II) air-oxidation rate was found to be proportional to the concentration of Mn(II)-DFOB complexes. At pH > 6.5, the dissolution of manganite (γ -MnOOH) in the presence of DFOB is predominantly a non-reductive ligand-promoted reaction whose rate is proportional to the adsorbed surface concentration of DFOB. At pH < 6.5, Mn2+ is the dominant species resulting from manganite dissolution, thus implicating a reductive dissolution pathway. The results of this study have broad implications for the biogeochemical cycling of manganese, redox-active elements, and siderophores in natural waters and soils.

  20. Investigating the Effect of Complexity Factors in Gas Law Problems

    ERIC Educational Resources Information Center

    Schuttlefield, Jennifer D.; Kirk, John; Pienta, Norbert J.; Tang, Hui

    2012-01-01

    Undergraduate students were asked to complete gas law questions using a Web-based tool as a first step in our understanding of the role of cognitive load in chemistry word questions and in helping us assess student problem-solving. Each question contained five different complexity factors, which were randomly assigned by the tool so that a…

  1. Gas Phase Reactions of Ions Derived from Anionic Uranyl Formate and Uranyl Acetate Complexes.

    PubMed

    Perez, Evan; Hanley, Cassandra; Koehler, Stephen; Pestok, Jordan; Polonsky, Nevo; Van Stipdonk, Michael

    2016-12-01

    The speciation and reactivity of uranium are topics of sustained interest because of their importance to the development of nuclear fuel processing methods, and a more complete understanding of the factors that govern the mobility and fate of the element in the environment. Tandem mass spectrometry can be used to examine the intrinsic reactivity (i.e., free from influence of solvent and other condensed phase effects) of a wide range of metal ion complexes in a species-specific fashion. Here, electrospray ionization, collision-induced dissociation, and gas-phase ion-molecule reactions were used to create and characterize ions derived from precursors composed of uranyl cation (U(VI)O2(2+)) coordinated by formate or acetate ligands. Anionic complexes containing U(VI)O2(2+) and formate ligands fragment by decarboxylation and elimination of CH2=O, ultimately to produce an oxo-hydride species [U(VI)O2(O)(H)](-). Cationic species ultimately dissociate to make [U(VI)O2(OH)](+). Anionic complexes containing acetate ligands exhibit an initial loss of acetyloxyl radical, CH3CO2•, with associated reduction of uranyl to U(V)O2(+). Subsequent CID steps cause elimination of CO2 and CH4, ultimately to produce [U(V)O2(O)](-). Loss of CH4 occurs by an intra-complex H(+) transfer process that leaves U(V)O2(+) coordinated by acetate and acetate enolate ligands. A subsequent dissociation step causes elimination of CH2=C=O to leave [U(V)O2(O)](-). Elimination of CH4 is also observed as a result of hydrolysis caused by ion-molecule reaction with H2O. The reactions of other anionic species with gas-phase H2O create hydroxyl products, presumably through the elimination of H2. Graphical Abstract ᅟ.

  2. Gas Phase Reactions of Ions Derived from Anionic Uranyl Formate and Uranyl Acetate Complexes

    NASA Astrophysics Data System (ADS)

    Perez, Evan; Hanley, Cassandra; Koehler, Stephen; Pestok, Jordan; Polonsky, Nevo; Van Stipdonk, Michael

    2016-12-01

    The speciation and reactivity of uranium are topics of sustained interest because of their importance to the development of nuclear fuel processing methods, and a more complete understanding of the factors that govern the mobility and fate of the element in the environment. Tandem mass spectrometry can be used to examine the intrinsic reactivity (i.e., free from influence of solvent and other condensed phase effects) of a wide range of metal ion complexes in a species-specific fashion. Here, electrospray ionization, collision-induced dissociation, and gas-phase ion-molecule reactions were used to create and characterize ions derived from precursors composed of uranyl cation (UVIO2 2+) coordinated by formate or acetate ligands. Anionic complexes containing UVIO2 2+ and formate ligands fragment by decarboxylation and elimination of CH2=O, ultimately to produce an oxo-hydride species [UVIO2(O)(H)]-. Cationic species ultimately dissociate to make [UVIO2(OH)]+. Anionic complexes containing acetate ligands exhibit an initial loss of acetyloxyl radical, CH3CO2•, with associated reduction of uranyl to UVO2 +. Subsequent CID steps cause elimination of CO2 and CH4, ultimately to produce [UVO2(O)]-. Loss of CH4 occurs by an intra-complex H+ transfer process that leaves UVO2 + coordinated by acetate and acetate enolate ligands. A subsequent dissociation step causes elimination of CH2=C=O to leave [UVO2(O)]-. Elimination of CH4 is also observed as a result of hydrolysis caused by ion-molecule reaction with H2O. The reactions of other anionic species with gas-phase H2O create hydroxyl products, presumably through the elimination of H2.

  3. Effects of chemical and enzymatic modifications on starch-linoleic acid complex formation.

    PubMed

    Arijaje, Emily Oluwaseun; Wang, Ya-Jane

    2017-02-15

    This study investigated the complexation yield and physicochemical properties of soluble and insoluble starch complexes with linoleic acid when a β-amylase treatment was applied to acetylated and debranched potato starch. The degree of acetylation was generally higher in the soluble complexes than in the insoluble ones. The insoluble complexes from the acetylated starch displayed the V-type pattern, whereas, the soluble complexes displayed a mixture of either the A-/V-type or the B-/V-type pattern. Acetylation decreased onset and peak melting temperatures for the insoluble complexes, whereas no melting endotherm was observed in the soluble complexes. Acetylation substantially increased the amount of complexed linoleic acid in the insoluble complexes, but had little positive effect on the formation of the soluble complexes. The β-amylase treatment significantly increased the complexed linoleic content in both soluble and insoluble complexes for the low acetylated starch, but not for the high acetylated starch.

  4. The Effect of Complex Formation upon the Redox Potentials of Metallic Ions. Cyclic Voltammetry Experiments.

    ERIC Educational Resources Information Center

    Ibanez, Jorge G.; And Others

    1988-01-01

    Describes experiments in which students prepare in situ soluble complexes of metal ions with different ligands and observe and estimate the change in formal potential that the ion undergoes upon complexation. Discusses student formation and analysis of soluble complexes of two different metal ions with the same ligand. (CW)

  5. A Model Incorporating Some of the Mechanical and Biochemical Factors Underlying Clot Formation and Dissolution in Flowing Blood

    DOE PAGES

    Anand, M.; Rajagopal, K.; Rajagopal, K. R.

    2003-01-01

    Multiple interacting mechanisms control the formation and dissolution of clots to maintain blood in a state of delicate balance. In addition to a myriad of biochemical reactions, rheological factors also play a crucial role in modulating the response of blood to external stimuli. To date, a comprehensive model for clot formation and dissolution, that takes into account the biochemical, medical and rheological factors, has not been put into place, the existing models emphasizing either one or the other of the factors. In this paper, after discussing the various biochemical, physiologic and rheological factors at some length, we develop a modelmore » for clot formation and dissolution that incorporates many of the relevant crucial factors that have a bearing on the problem. The model, though just a first step towards understanding a complex phenomenon, goes further than previous models in integrating the biochemical, physiologic and rheological factors that come into play.« less

  6. The Formation and Thermochemical Properties of Multiligand Complexes

    DTIC Science & Technology

    1987-08-25

    complexes, binary solvent systems, mass spectrometry, chemi- , .. luminescence, thermochemistry , kinetics V BSTRACT (Continue on reverse if necessary and...Involving Sulfides and Phosphonates ...... I Thermochemistry of Multiligand Cluster Ions*..................... 6 II. BIBLIOGRAPHY...and to explore relationships with the thermochemistry of binary soutions in the condensed phase. The results of this research have formed the basis

  7. Dynamics of Research Team Formation in Complex Networks

    NASA Astrophysics Data System (ADS)

    Sun, Caihong; Wan, Yuzi; Chen, Yu

    Most organizations encourage the formation of teams to accomplish complicated tasks, and vice verse, effective teams could bring lots benefits and profits for organizations. Network structure plays an important role in forming teams. In this paper, we specifically study the dynamics of team formation in large research communities in which knowledge of individuals plays an important role on team performance and individual utility. An agent-based model is proposed, in which heterogeneous agents from research communities are described and empirically tested. Each agent has a knowledge endowment and a preference for both income and leisure. Agents provide a variable input (‘effort’) and their knowledge endowments to production. They could learn from others in their team and those who are not in their team but have private connections in community to adjust their own knowledge endowment. They are allowed to join other teams or work alone when it is welfare maximizing to do so. Various simulation experiments are conducted to examine the impacts of network topology, knowledge diffusion among community network, and team output sharing mechanisms on the dynamics of team formation.

  8. [COMPLEX ASSESSMENT OF ENVIRONMENTAL FACTORS AND POSTVACCINAL IMMUNE STATE].

    PubMed

    Kryazhev, D A; Boev, M V; Tulina, L M; Neplokhov, A A; Boev, V M

    2016-01-01

    This article was written on the base of the analysis of data of protocols of annual serological sturdies of the post-vaccination immunity status in indicator groups of populations, the analysis of samples of drinking water air and soil with the assessment of the socio-economic development of mono-towns and rural settlements. In the article there is reflected the comprehensive assessment of environmental factors and specific features of the formation of socio-economic conditions of rural communities and mono towns. There was performed a comparative assessment of the status of post-vaccination immunity to infections controlled by specific means of prevention, in different age groups in mono towns and rural settlements. There was established a dependence of the formation of post-vaccination immunity on the state of environmental factors.

  9. Social complexity as a proximate and ultimate factor in communicative complexity

    PubMed Central

    Freeberg, Todd M.; Dunbar, Robin I. M.; Ord, Terry J.

    2012-01-01

    The ‘social complexity hypothesis’ for communication posits that groups with complex social systems require more complex communicative systems to regulate interactions and relations among group members. Complex social systems, compared with simple social systems, are those in which individuals frequently interact in many different contexts with many different individuals, and often repeatedly interact with many of the same individuals in networks over time. Complex communicative systems, compared with simple communicative systems, are those that contain a large number of structurally and functionally distinct elements or possess a high amount of bits of information. Here, we describe some of the historical arguments that led to the social complexity hypothesis, and review evidence in support of the hypothesis. We discuss social complexity as a driver of communication and possible causal factor in human language origins. Finally, we discuss some of the key current limitations to the social complexity hypothesis—the lack of tests against alternative hypotheses for communicative complexity and evidence corroborating the hypothesis from modalities other than the vocal signalling channel. PMID:22641818

  10. Dorsal-Mediated Repression Requires the Formation of a Multiprotein Repression Complex at the Ventral Silencer

    PubMed Central

    Valentine, Scott A.; Chen, Guoqing; Shandala, Tatiana; Fernandez, Joseph; Mische, Sheenah; Saint, Robert; Courey, Albert J.

    1998-01-01

    Dorsal functions as both an activator and repressor of transcription to determine dorsoventral fate in the Drosophila melanogaster embryo. Repression by Dorsal requires the corepressor Groucho (Gro) and is mediated by silencers termed ventral repression regions (VRRs). A VRR in zerknüllt (zen) contains Dorsal binding sites as well as an essential element termed AT2. We have identified and purified an AT2 DNA binding activity in embryos and shown it to consist of cut (ct) and dead ringer (dri) gene products. Studies of loss-of-function mutations in ct and dri demonstrate that both genes are required for the activity of the AT2 site. Dorsal and Dri both bind Gro, acting cooperatively to recruit it to the DNA. Thus, ventral repression may require the formation of a multiprotein complex at the VRR. This complex includes Dorsal, Gro, and additional DNA binding proteins, which appear to convert Dorsal from an activator to a repressor by enabling it to recruit Gro to the template. By showing how binding site context can dramatically alter transcription factor function, these findings help clarify the mechanisms responsible for the regulatory specificity of transcription factors. PMID:9774673

  11. Chemical complexity and star-formation in merging galaxies

    NASA Astrophysics Data System (ADS)

    Davis, T. A.; Heiderman, A.; Iono, D.; VIXENS Team

    2013-03-01

    When galaxies merge the resulting conditions are some of the most extreme found anywhere in nature. Large gas flows, shocks and active black holes all can affect the ISM. Nearby merging galaxies with strong starbursts are the only places where we can conduct detailed study of star formation in conditions that mimic those under which the majority of stars in the universe formed. Here we study molecular gas tracers in 8 galaxies selected from the VIRUS-P Investigation of the eXtreme ENvironments of Starbursts (VIXENS) survey. Each galaxy has also been observed using the integral field unit spectrograph VIRUS-P, allowing us to investigate the relation between the chemical state of the gas, star formation and total gas content. Full details can be found in Heiderman et al. (2011). Here we report on new results obtained from IRAM-30m/NRO-45m 3mm line surveys towards 14 positions in these 8 merging galaxies. We detect ≈ 25 different molecular transitions towards these objects, many which have never been observed in these galaxies before. Our measurements show that the mean fraction of dense gas increases in later-stage mergers (Fig. 1, left), as does the average optical depth of the gas. Molecular diagnostic diagrams (Fig. 1, right) show that molecular regions we probe are, in general, UV photon dominated. Triggered AGN activity, and/or cosmic ray ionisation (from SNe II in the starburst) are not yet energetically important in determining the state of the gas.

  12. Protein-free parallel triple-stranded DNA complex formation

    PubMed Central

    Shchyolkina, A. K.; Timofeev, E. N.; Lysov, Yu. P.; Florentiev, V. L.; Jovin, T. M.; Arndt-Jovin, D. J.

    2001-01-01

    A 14 nt DNA sequence 5′-AGAATGTGGCAAAG-3′ from the zinc finger repeat of the human KRAB zinc finger protein gene ZNF91 bearing the intercalator 2-methoxy,6-chloro,9-amino acridine (Acr) attached to the sugar–phosphate backbone in various positions has been shown to form a specific triple helix (triplex) with a 16 bp hairpin (intramolecular) or a two-stranded (intermolecular) duplex having the identical sequence in the same (parallel) orientation. Intramolecular targets with the identical sequence in the antiparallel orientation and a non-specific target sequence were tested as controls. Apparent binding constants for formation of the triplex were determined by quantitating electrophoretic band shifts. Binding of the single-stranded oligonucleotide probe sequence to the target led to an increase in the fluorescence anisotropy of acridine. The parallel orientation of the two identical sequence segments was confirmed by measurement of fluorescence resonance energy transfer between the acridine on the 5′-end of the probe strand as donor and BODIPY-Texas Red on the 3′-amino group of either strand of the target duplex as acceptor. There was full protection from OsO4-bipyridine modification of thymines in the probe strand of the triplex, in accordance with the presumed triplex formation, which excluded displacement of the homologous duplex strand by the probe–intercalator conjugate. The implications of these results for the existence of protein-independent parallel triplexes are discussed. PMID:11160932

  13. Effect of pH on complex formation between debranched waxy rice starch and fatty acids.

    PubMed

    Yotsawimonwat, Songwut; Sriroth, Klanarong; Kaewvichit, Sayam; Piyachomkwan, Kaukoon; Jane, Jay-Lin; Sirithunyalug, Jakkapan

    2008-08-15

    Complex formations between debranched waxy rice starch (DBS) and fatty acids (FA) of different hydrocarbon chain lengths (8:0, 10:0, 12:0, 14:0, 16:0, and 18:0) were studied in an aqueous solution by measuring the blue colour stained with iodine. The objective of this study was to understand the effects of the solubility and hydrophobicity of guest molecules (FA) on the complex formation with DBS. Lauric acid (12:0) displayed the greatest complex forming ability with DBS by showing the least blue colour developed with iodine. The effect of pH (3-7) on the DBS/FA complex formation was evaluated by measuring the iodine-scanning spectra of the mixture. Short-chain FA (8:0) displayed less complex formation at pH>or=5, above the pK(a) of fatty acid (approximately 4.8), which suggested that the charge formation of the short-chain FA caused a lower partitioning of the FA into the hydrophobic cavity of the DBS single helix. On the contrary, FA of 10:0-18:0 displayed an increased complex formation at pH>5, which could be attributed to increased solubility of these longer-chain FA at a dissociated and ionized form. The hydrocarbon chain length of the FA had an important impact on the extent of the complex formation. A FA that had a shorter hydrocarbon chain was more soluble in an aqueous solution and more readily formed a complex with DBS. At pH 6 and 7 (above the pK(a)), 10:0 formed less inclusion complexes with DBS than did 12:0. Iodine-scanning spectra showed that the absorbances of all iodine-stained DBS/FA solutions at higher wavelength were substantially lower than that of the iodine-stained DBS alone, suggesting that FA preferentially formed inclusion complexes with DBS of longer chains.

  14. Module Based Complexity Formation: Periodic Patterning in Feathers and Hairs

    PubMed Central

    Chuong, Cheng-Ming; Yeh, Chao-Yuan; Jiang, Ting-Xin; Widelitz, Randall

    2012-01-01

    Patterns describe order which emerges from homogeneity. Complex patterns on the integument are striking because of their visibility throughout an organism's lifespan. Periodic patterning is an effective design because the ensemble of hair or feather follicles (modules) allows the generation of complexity, including regional variations and cyclic regeneration, giving the skin appendages a new lease on life. Spatial patterns include the arrangements of feathers and hairs in specified number, size, and spacing. We explore how a field of equivalent progenitor cells can generate periodically arranged modules based on genetic information, physical-chemical rules and developmental timing. Reconstitution experiments suggest a competitive equilibrium regulated by activators / inhibitors involving Turing reaction-diffusion. Temporal patterns result from oscillating stem cell activities within each module (micro-environment regulation), reflected as growth (anagen) and resting (telogen) phases during the cycling of feather and hair follicles. Stimulating modules with activators initiates the spread of regenerative hair waves, while global inhibitors outside each module (macro-environment) prevent this. Different wave patterns can be simulated by Cellular Automata principles. Hormonal status and seasonal changes can modulate appendage phenotypes, leading to “organ metamorphosis”, with multiple ectodermal organ phenotypes generated from the same precursors. We discuss potential evolutionary novel steps using this module based complexity in several amniote integument organs, exemplified by the spectacular peacock feather pattern. We thus explore the application of the acquired knowledge of patterning in tissue engineering. New hair follicles can be generated after wounding. Hairs and feathers can be reconstituted through self-organization of dissociated progenitor cells. PMID:23539312

  15. The formation and study of titanium, zirconium, and hafnium complexes

    NASA Technical Reports Server (NTRS)

    Wilson, Bobby; Sarin, Sam; Smith, Laverne; Wilson, Melanie

    1989-01-01

    Research involves the preparation and characterization of a series of Ti, Zr, Hf, TiO, and HfO complexes using the poly(pyrazole) borates as ligands. The study will provide increased understanding of the decomposition of these coordination compounds which may lead to the production of molecular oxygen on the Moon from lunar materials such as ilmenite and rutile. The model compounds are investigated under reducing conditions of molecular hydrogen by use of a high temperature/pressure stainless steel autoclave reactor and by thermogravimetric analysis.

  16. Studies on chalcone derivatives: Complex formation, thermal behavior, stability constant and antioxidant activity

    NASA Astrophysics Data System (ADS)

    El-Sayed, Yusif S.; Gaber, M.

    2015-02-01

    The chalcone 3-[4‧-dimethylaminophenyl]-1-(2-pyridyl) prop-2-en-1-one (DMAPP) and 3-(4‧-diethylaminophenyl)-1-(2-pyridinyl) prop-2-en-1-one abbreviated as DEAPP have been synthesized and characterized with IR, 1H NMR, 13C NMR spectroscopic techniques as described previously (El-Daly et al., 2008; Gaber et al., 2009; El-Sayed, 2013). By using UV visible spectroscopy method the mole fraction ratio for copper with DMAPP and DEAPP complexes were determined and it was found to be 1:1. The stability constants of this complex have been determined by Job's method. The stability constant (Kf) of copper with DMAPP and DEAPP complexes in universal buffer pH = 3.2 was determined to be 9.9 × 104 and 5.2 × 104 respectively. The effect of Cu(II) ion on the emission spectrum of the free chalcone is also assigned. Adherence to Beer's law and Ringbom optimum concentration ranges are determined. The thermal decomposition of the metal complexes is studied by TGA technique. The kinetic parameters like activation energy, pre-exponential factor and entropy of activation are estimated. The structure of complexes was energetically optimized through molecular mechanics applying MM+ force field coupled with molecular dynamics simulation. The bond lengths and bond angles have been calculated to confirm the geometry of the ligands and their Cu(II) complexes. The mode of interaction of the chalcone to copper nanoparticles was studied. The apparent association constants of the colloidal copper nanoparticles:chalcone complexes in solution were evaluated using the spectral method and compared with the formation constant of the Cu(II) chalcone complexes. Antioxidant activity of these chalcones was evaluated by using 1,1‧-diphenyl-2-picrylhydrazyl (DPPHrad) radicals scavenging method, which showed that the antioxidant activity of DMAPP has higher value than the DEAPP. Semi-empirical study results showed that DMAPP have higher dipole moment than DEAPP [1].

  17. Direct inhibition of the NOTCH transcription factor complex.

    PubMed

    Moellering, Raymond E; Cornejo, Melanie; Davis, Tina N; Del Bianco, Cristina; Aster, Jon C; Blacklow, Stephen C; Kung, Andrew L; Gilliland, D Gary; Verdine, Gregory L; Bradner, James E

    2009-11-12

    Direct inhibition of transcription factor complexes remains a central challenge in the discipline of ligand discovery. In general, these proteins lack surface involutions suitable for high-affinity binding by small molecules. Here we report the design of synthetic, cell-permeable, stabilized alpha-helical peptides that target a critical protein-protein interface in the NOTCH transactivation complex. We demonstrate that direct, high-affinity binding of the hydrocarbon-stapled peptide SAHM1 prevents assembly of the active transcriptional complex. Inappropriate NOTCH activation is directly implicated in the pathogenesis of several disease states, including T-cell acute lymphoblastic leukaemia (T-ALL). The treatment of leukaemic cells with SAHM1 results in genome-wide suppression of NOTCH-activated genes. Direct antagonism of the NOTCH transcriptional program causes potent, NOTCH-specific anti-proliferative effects in cultured cells and in a mouse model of NOTCH1-driven T-ALL.

  18. Direct inhibition of the NOTCH transcription factor complex

    PubMed Central

    Moellering, Raymond E.; Cornejo, Melanie; Davis, Tina N.; Del Bianco, Cristina; Aster, Jon C.; Blacklow, Stephen C.; Kung, Andrew L.; Gilliland, D. Gary; Verdine, Gregory L.; Bradner, James E.

    2010-01-01

    Direct inhibition of transcription factor complexes remains a central challenge in the discipline of ligand discovery. In general, these proteins lack surface involutions suitable for high-affinity binding by small molecules. Here we report the design of synthetic, cell-permeable, stabilized α-helical peptides that target a critical protein–protein interface in the NOTCH transactivation complex. We demonstrate that direct, high-affinity binding of the hydrocarbon-stapled peptide SAHM1 prevents assembly of the active transcriptional complex. Inappropriate NOTCH activation is directly implicated in the pathogenesis of several disease states, including T-cell acute lymphoblastic leukaemia (T-ALL). The treatment of leukaemic cells with SAHM1 results in genome-wide suppression of NOTCH-activated genes. Direct antagonism of the NOTCH transcriptional program causes potent, NOTCH-specific anti-proliferative effects in cultured cells and in a mouse model of NOTCH1-driven T-ALL. PMID:19907488

  19. Colony-Stimulating Factor-1 Signaling Suppresses Renal Crystal Formation

    PubMed Central

    Taguchi, Kazumi; Kitamura, Hiroshi; Yasui, Takahiro; Naiki, Taku; Hamamoto, Shuzo; Ando, Ryosuke; Mizuno, Kentaro; Kawai, Noriyasu; Tozawa, Keiichi; Asano, Kenichi; Tanaka, Masato; Miyoshi, Ichiro; Kohri, Kenjiro

    2014-01-01

    We recently reported evidence suggesting that migrating macrophages (Mϕs) eliminate renal crystals in hyperoxaluric mice. Mϕs can be inflammatory (M1) or anti-inflammatory (M2), and colony-stimulating factor-1 (CSF-1) mediates polarization to the M2Mϕ phenotype. M2Mϕs promote renal tissue repair and regeneration, but it is not clear whether these cells are involved in suppressing renal crystal formation. We investigated the role of M2Mϕs in renal crystal formation during hyperoxaluria using CSF-1–deficient mice, which lack M2Mϕs. Compared with wild-type mice, CSF-1–deficient mice had significantly higher amounts of renal calcium oxalate crystal deposition. Treatment with recombinant human CSF-1 increased the expression of M2-related genes and markedly decreased the number of renal crystals in both CSF-1–deficient and wild-type mice. Flow cytometry of sorted renal Mϕs showed that CSF-1 deficiency resulted in a smaller population of CD11b+F4/80+CD163+CD206hi cells, which represent M2-like Mϕs. Additionally, transfusion of M2Mϕs into CSF-1–deficient mice suppressed renal crystal deposition. In vitro phagocytosis assays with calcium oxalate monohydrate crystals showed a higher rate of crystal phagocytosis by M2-polarized Mϕs than M1-polarized Mϕs or renal tubular cells. Gene array profiling showed that CSF-1 deficiency resulted in disordered M2- and stone-related gene expressions. Collectively, our results provide compelling evidence for a suppressive role of CSF-1 signaling in renal crystal formation. PMID:24578130

  20. Formation of Au and tetrapyridyl porphyrin complexes in superfluid helium.

    PubMed

    Feng, Cheng; Latimer, Elspeth; Spence, Daniel; Al Hindawi, Aula M A A; Bullen, Shem; Boatwright, Adrian; Ellis, Andrew M; Yang, Shengfu

    2015-07-14

    Binary clusters containing a large organic molecule and metal atoms have been formed by the co-addition of 5,10,15,20-tetra(4-pyridyl)porphyrin (H2TPyP) molecules and gold atoms to superfluid helium nanodroplets, and the resulting complexes were then investigated by electron impact mass spectrometry. In addition to the parent ion H2TPyP yields fragments mainly from pyrrole, pyridine and methylpyridine ions because of the stability of their ring structures. When Au is co-added to the droplets the mass spectra are dominated by H2TPyP fragment ions with one or more Au atoms attached. We also show that by switching the order in which Au and H2TPyP are added to the helium droplets, different types of H2TPyP-Au complexes are clearly evident from the mass spectra. This study suggests a new route for the control over the growth of metal-organic compounds inside superfluid helium nanodroplets.

  1. Flow induced streamer formation in particle laden complex flows

    NASA Astrophysics Data System (ADS)

    Debnath, Nandini; Hassanpourfard, Mahtab; Ghosh, Ranajay; Trivedi, Japan; Thundat, Thomas; Kumar, Aloke

    2016-11-01

    We study the combined flow of a polyacrylamide (PAM)solution with polystyrene (PS) nanoparticles, through a microfluidic device containing an array of micropillars. The flow is characterized by a very low Reynolds number (Re<<1). We find that for exceeding a critical Weissenberg number (Wi >= 20), PS nanoparticles localize near pillar walls to form thin slender string-like structures, which we call 'streamers' due to their morphology. Post-formation, these streamers show significant viscous behavior for short observational time-scales, and at longer observational time scales elastic response dominates. Our abiotic streamers could provide a framework for understanding similar structures that often form in biological systems. PhD student, Department of Mechanical Engineering.

  2. NDMA formation during drinking water treatment: A multivariate analysis of factors influencing formation.

    PubMed

    Leavey-Roback, Shannon L; Sugar, Catherine A; Krasner, Stuart W; Suffet, Irwin H Mel

    2016-05-15

    The formation of the carcinogen N-nitrosodimethylamine (NDMA) during drinking water treatment has raised concerns in the drinking water industry. Many bench-scale laboratory tests and pilot plant studies have been completed to try to determine which factors during water treatment increase or decrease the amount of NDMA formed in drinking water. This study used data from over 20 drinking water treatment plants in the United States and Canada to determine which factors are most highly correlated with the NDMA concentration in delivered water using a mixed effects model with a random intercept. This type of analysis has not been used previously with trihalomethane (THM) models due to the fact that those studies did not sample such a large number and range of plants as was done in this NDMA study. Ultraviolet absorbance at 254 nm (UV254) in the plant influent and pre-chlorination time used at the plant were highly correlated in all models with NDMA concentration in finished water as well as the percentage change between NDMA formation potential in the plant influent and actual formation in the finished water. Specifically, an increase in UV254 absorbance in a model was associated with an increase in NDMA and an increase in pre-chlorination time in a model was associated with a decrease in NDMA. Other water quality parameters including sucralose concentration in the plant influent, polyDADMAC polymer dose, pH, and chlorine-to-ammonia weight ratio used in the plant were also correlated with NDMA concentration in the distribution system. Lastly, NDMA precursor loading was correlated with the use of polyDADMAC (where precursors were added) and the use of ozone and granular activated carbon (GAC) treatment (where precursors were removed).

  3. Subcellular location for the formation of the retinol/retinol-binding protein complex in rat liver

    SciTech Connect

    Crumbaugh, L.M.; Green, E.L.; Smith, J.E.

    1986-03-01

    Retinol complexes with retinol-binding protein (RBP) within the hepatocyte, however the subcellular location where complex formation occurs has not previously been identified. A model similar to that of lipoproteins formation has been hypothesized. The authors have identified the initial site of retinol/RBP complex formation. Furthermore, the authors have elucidated the progression of the complex through the subcellular organelles. Intravenous injections of /sup 3/H-retinol suspended in Tween 40 were administered to vitamin A depleted rats. After intervals of 2, 3, 4, 5, 10, 15, 20, and 30 minutes the rat livers were removed and fractions enriched in rough and smooth microsomes and Golgi apparatus were prepared. Extracts of these subcellular fractions were chromatographed on Sephadex G-100. Simultaneous elution of /sup 3/H-retinol and immunoreactive RBP indicated the presence of the complex. The retinol/RBP complex was observed in rough microsomes 2 minute after the injection of /sup 3/H-retinal. The complex appeared subsequently in smooth microsomes and Golgi apparatus. The complex was first detected serum around 10 minutes after injection. Based on the data, they believe that the retinol/RBP complex formation occurs in rough microsomes.

  4. A developmental framework for complex plasmodesmata formation revealed by large-scale imaging of the Arabidopsis leaf epidermis.

    PubMed

    Fitzgibbon, Jessica; Beck, Martina; Zhou, Ji; Faulkner, Christine; Robatzek, Silke; Oparka, Karl

    2013-01-01

    Plasmodesmata (PD) form tubular connections that function as intercellular communication channels. They are essential for transporting nutrients and for coordinating development. During cytokinesis, simple PDs are inserted into the developing cell plate, while during wall extension, more complex (branched) forms of PD are laid down. We show that complex PDs are derived from existing simple PDs in a pattern that is accelerated when leaves undergo the sink-source transition. Complex PDs are inserted initially at the three-way junctions between epidermal cells but develop most rapidly in the anisocytic complexes around stomata. For a quantitative analysis of complex PD formation, we established a high-throughput imaging platform and constructed PDQUANT, a custom algorithm that detected cell boundaries and PD numbers in different wall faces. For anticlinal walls, the number of complex PDs increased with increasing cell size, while for periclinal walls, the number of PDs decreased. Complex PD insertion was accelerated by up to threefold in response to salicylic acid treatment and challenges with mannitol. In a single 30-min run, we could derive data for up to 11k PDs from 3k epidermal cells. This facile approach opens the door to a large-scale analysis of the endogenous and exogenous factors that influence PD formation.

  5. Probabilistic Multi-Factor Interaction Model for Complex Material Behavior

    NASA Technical Reports Server (NTRS)

    Abumeri, Galib H.; Chamis, Christos C.

    2010-01-01

    Complex material behavior is represented by a single equation of product form to account for interaction among the various factors. The factors are selected by the physics of the problem and the environment that the model is to represent. For example, different factors will be required for each to represent temperature, moisture, erosion, corrosion, etc. It is important that the equation represent the physics of the behavior in its entirety accurately. The Multi-Factor Interaction Model (MFIM) is used to evaluate the divot weight (foam weight ejected) from the external launch tanks. The multi-factor has sufficient degrees of freedom to evaluate a large number of factors that may contribute to the divot ejection. It also accommodates all interactions by its product form. Each factor has an exponent that satisfies only two points - the initial and final points. The exponent describes a monotonic path from the initial condition to the final. The exponent values are selected so that the described path makes sense in the absence of experimental data. In the present investigation, the data used were obtained by testing simulated specimens in launching conditions. Results show that the MFIM is an effective method of describing the divot weight ejected under the conditions investigated. The problem lies in how to represent the divot weight with a single equation. A unique solution to this problem is a multi-factor equation of product form. Each factor is of the following form (1 xi/xf)ei, where xi is the initial value, usually at ambient conditions, xf the final value, and ei the exponent that makes the curve represented unimodal that meets the initial and final values. The exponents are either evaluated by test data or by technical judgment. A minor disadvantage may be the selection of exponents in the absence of any empirical data. This form has been used successfully in describing the foam ejected in simulated space environmental conditions. Seven factors were required

  6. Formation, Migration, and Reactivity of Au CO Complexes on Gold Surfaces

    DOE PAGES

    Wang, Jun; McEntee, Monica; Tang, Wenjie; ...

    2016-01-12

    Here, we report experimental as well as theoretical evidence that suggests Au CO complex formation upon the exposure of CO to active sites (step edges and threading dislocations) on a Au(111) surface. Room-temperature scanning tunneling microscopy (STM), X-ray photoelectron spectroscopy, transmission infrared spectroscopy, and density functional theory calculations point to Au CO complex formation and migration. Room-temperature STM of the Au(111) surface at CO pressures in the range from 10^ 8 to 10^ 4 Torr (dosage up to 10^6 langmuir) indicates Au atom extraction from dislocation sites of the herringbone reconstruction, mobile Au CO complex formation and diffusion, and Aumore » adatom cluster formation on both elbows and step edges on the Au surface. The formation and mobility of the Au CO complex result from the reduced Au Au bonding at elbows and step edges leading to stronger Au CO bonding and to the formation of a more positively charged CO (CO +) on Au. These studies indicate that the mobile Au CO complex is involved in the Au nanoparticle formation and reactivity, and that the positive charge on CO increases due to the stronger adsorption of CO at Au sites with lower coordination numbers.« less

  7. Formation, Migration, and Reactivity of Au CO Complexes on Gold Surfaces

    SciTech Connect

    Wang, Jun; McEntee, Monica; Tang, Wenjie; Neurock, Matthew; Baddorf, Arthur P.; Maksymovych, Petro; Yates, Jr, John T.

    2016-01-12

    Here, we report experimental as well as theoretical evidence that suggests Au CO complex formation upon the exposure of CO to active sites (step edges and threading dislocations) on a Au(111) surface. Room-temperature scanning tunneling microscopy (STM), X-ray photoelectron spectroscopy, transmission infrared spectroscopy, and density functional theory calculations point to Au CO complex formation and migration. Room-temperature STM of the Au(111) surface at CO pressures in the range from 10^ 8 to 10^ 4 Torr (dosage up to 10^6 langmuir) indicates Au atom extraction from dislocation sites of the herringbone reconstruction, mobile Au CO complex formation and diffusion, and Au adatom cluster formation on both elbows and step edges on the Au surface. The formation and mobility of the Au CO complex result from the reduced Au Au bonding at elbows and step edges leading to stronger Au CO bonding and to the formation of a more positively charged CO (CO +) on Au. These studies indicate that the mobile Au CO complex is involved in the Au nanoparticle formation and reactivity, and that the positive charge on CO increases due to the stronger adsorption of CO at Au sites with lower coordination numbers.

  8. Complex Formation History of Highly Evolved Basaltic Shergottite, Zagami

    NASA Technical Reports Server (NTRS)

    Niihara, T.; Misawa, K.; Mikouchi, T.; Nyquist, L. E.; Park, J.; Hirata, D.

    2012-01-01

    Zagami, a basaltic shergottite, contains several kinds of lithologies such as Normal Zagami consisting of Fine-grained (FG) and Coarse-grained (CG), Dark Mottled lithology (DML), and Olivine-rich late-stage melt pocket (DN). Treiman and Sutton concluded that Zagami (Normal Zagami) is a fractional crystallization product from a single magma. It has been suggested that there were two igneous stages (deep magma chamber and shallow magma chamber or surface lava flow) on the basis of chemical zoning features of pyroxenes which have homogeneous Mg-rich cores and FeO, CaO zoning at the rims. Nyquist et al. reported that FG has a different initial Sr isotopic ratio than CG and DML, and suggested the possibility of magma mixing on Mars. Here we report new results of petrology and mineralogy for DML and the Olivine-rich lithology (we do not use DN here), the most evolved lithology in this rock, to understand the relationship among lithologies and reveal Zagami s formation history

  9. Microbanded manganese formations; protoliths in the Franciscan Complex, California

    USGS Publications Warehouse

    Huebner, J. Stephen; Flohr, Marta J.

    1990-01-01

    The Buckeye manganese deposit, 93 km southeast of San Francisco in the California Coast Ranges, preserves a geologic history that provides clues to the origin of numerous lenses of manganese carbonate, oxides, and silicates that occur with interbedded radiolarian chert and metashale of the Franciscan Complex. Compositionally and mineralogically laminated Mn-rich protoliths were deformed and dismembered, in a manner that mimics in smaller scale the deformation of the host complex, and then were incipiently metamorphosed at blueschistfacies conditions. Eight phases occur as almost monomineralic protoliths and mixtures: rhodochrosite, caryopilite, chlorite, gageite, taneyamalite, braunite, hausmannite, and laminated chert (quartz). Braunite, gageite, and some chlorite and caryopilite layers were deposited as gel-like materials; rhodochrosite, most caryopilite, and at least some hausmannite layers as lutites; and the chert as turbidites of radiolarian sand. Some gel-like materials are now preserved as transparent, sensibly isotropic relics of materials that fractured or shattered when deformed, creating curved surfaces. In contrast, the micrites flowed between the fragments of gel-like materials. The orebody and most of its constituent minerals have unusually Mn-rich compositions that are described by the system MnO-SiO2-O2-CO2-H2O. High values of Mn/Fe and U/Th, and low concentrations of Co, Cu, and Ni, distinguish the Buckeye deposit from many high-temperature hydrothermal deposits and hydrogenous or diagenetic manganese and ferromanganese nodules and pavements. This chemical signature suggests that ore deposition was related to fluids from the sediment column and seawater. Tungsten is associated exclusively with gageite, in concentrations as high as 80 parts per million. The source of the manganese is unknown; because basalts do not occur near the deposit, it was probably manganese leached from the sediment column by reducing solutions. Low concentrations of calcium

  10. Study on the mechanism of copper-ammonia complex decomposition in struvite formation process and enhanced ammonia and copper removal.

    PubMed

    Peng, Cong; Chai, Liyuan; Tang, Chongjian; Min, Xiaobo; Song, Yuxia; Duan, Chengshan; Yu, Cheng

    2017-01-01

    Heavy metals and ammonia are difficult to remove from wastewater, as they easily combine into refractory complexes. The struvite formation method (SFM) was applied for the complex decomposition and simultaneous removal of heavy metal and ammonia. The results indicated that ammonia deprivation by SFM was the key factor leading to the decomposition of the copper-ammonia complex ion. Ammonia was separated from solution as crystalline struvite, and the copper mainly co-precipitated as copper hydroxide together with struvite. Hydrogen bonding and electrostatic attraction were considered to be the main surface interactions between struvite and copper hydroxide. Hydrogen bonding was concluded to be the key factor leading to the co-precipitation. In addition, incorporation of copper ions into the struvite crystal also occurred during the treatment process.

  11. An illustration of the complexity of continent formation

    NASA Technical Reports Server (NTRS)

    Burke, Kevin

    1988-01-01

    It was pointed out that a consensus may be emerging in crustal growth models, considering the clustering of most growth curves and their uncertainties. Curves most distant from this clustering represent models involving extensive recycling of continental material back into the mantle, but the author wondered if geochemical signatures for this would be recognizable considering the lack of evidence from seismic tomography for discrete mantle reservoirs, and the likelihood of core-mantle interaction based on recent high pressure experiments. Unreactivated Archean rocks represent only 2 percent of present continental area, and the author was uncomfortable about basing inferences on what the early Earth was like on such a small amount of information. He feels that the hypothesis of continental assembly that needs testing is that of banging together of island arcs, such as in Indonesia today. As an example of how complex this process can be, the author described the geology of the Caribbean arc system, which shows evidence for reversals of subduction polarity, numerous collisional events, and substantial strike-slip movements. It seemed unlikely to the author that Archean examples would have been less complicated.

  12. Oxidative peptide /and amide/ formation from Schiff base complexes

    NASA Technical Reports Server (NTRS)

    Strehler, B. L.; Li, M. P.; Martin, K.; Fliss, H.; Schmid, P.

    1982-01-01

    One hypothesis of the origin of pre-modern forms of life is that the original replicating molecules were specific polypeptides which acted as templates for the assembly of poly-Schiff bases complementary to the template, and that these polymers were then oxidized to peptide linkages, probably by photo-produced oxidants. A double cycle of such anti-parallel complementary replication would yield the original peptide polymer. If this model were valid, the Schiff base between an N-acyl alpha mino aldehyde and an amino acid should yield a dipeptide in aqueous solution in the presence of an appropriate oxidant. In the present study it is shown that the substituted dipeptide, N-acetyl-tyrosyl-tyrosine, is produced in high yield in aqueous solution at pH 9 through the action of H2O2 on the Schiff-base complex between N-acetyl-tyrosinal and tyrosine and that a great variety of N-acyl amino acids are formed from amino acids and aliphatic aldehydes under similar conditions.

  13. Interferogram formation in the presence of complex and large deformation

    USGS Publications Warehouse

    Yun, S.-H.; Zebker, H.; Segall, P.; Hooper, A.; Poland, M.

    2007-01-01

    Sierra Negra volcano in Isabela island, Gala??pagos, erupted from October 22 to October 30 in 2005. During the 8 days of eruption, the center of Sierra Negra's caldera subsided about 5.4 meters. Three hours prior to the onset of the eruption, an earthquake (Mw 5.4) occurred, near the caldera. Because of the large and complex phase gradient due to the huge subsidence and the earthquake, it is difficult to form an interferogram inside the caldera that spans the eruption. The deformation is so large and spatially variable that the approximations used in existing InSAR software (ROI, ROI_PAC, DORIS, GAMMA) cannot properly coregister SAR image pairs spanning the eruption. We have developed here a two-step algorithm that can form intra-caldera interferograms from these data. The first step involves a "rubber-sheeting" SAR image coregistration. In the second step we use range offset estimates to mitigate the steep phase gradient. Using this new algorithm, we retrieve an interferogram with the best coverage to date inside the caldera of Sierra Negra. Copyright 2007 by the American Geophysical Union.

  14. Structure of soybean serine acetyltransferase and formation of the cysteine regulatory complex as a molecular chaperone

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Serine acetyltransferase (SAT) catalyzes the limiting reaction in plant and microbial biosynthesis of cysteine. In addition to its enzymatic function, SAT forms a macromolecular complex with O-acetylserine sulfhydrylase (OASS). Formation of the cysteine regulatory complex (CRC) is a critical biochem...

  15. Relativistic effect on enthalpy of formation for transition-metal complexes

    NASA Astrophysics Data System (ADS)

    Nakajima, Yuya; Seino, Junji; Nakai, Hiromi

    2017-04-01

    This Letter examines the enthalpy of formation for 12 transition metal diatomic molecules and 23 transition metal complexes from the viewpoint of effect of the relativistic effect by using the infinite-order Douglas-Kroll-Hess method with the local unitary transformation and three types of pseudopotentials for several levels of theory. The spin-orbit effect contribution to the enthalpy of formation is more than 10 kcal/mol for third transition metal complexes. Frozen orbital approximation at the outermost orbitals in pseudopotential methods shows a contribution to the enthalpy of formation that is more than two times larger than those of inner core orbitals.

  16. The chitosan-gelatin (bio)polyelectrolyte complexes formation in an acidic medium.

    PubMed

    Voron'ko, Nicolay G; Derkach, Svetlana R; Kuchina, Yuliya A; Sokolan, Nina I

    2016-03-15

    The interaction of cationic polysaccharide chitosan and gelatin accompanied by the stoichiometric (bio)polyelectrolyte complexes formation has been studied by the methods of capillary viscometry, UV and FTIR spectroscopy and dispersion of light scattering. Complexes were formed in the aqueous phase, with pH being less than the isoelectric point of gelatin (pIgel). The particle size of the disperse phase increases along with the growth of the relative viscosity in comparison with sols of the individual components-polysaccharide and gelatin. Possible models and mechanism of (bio)polyelectrolyte complexes formation have been discussed. It was shown that the complex formation takes place not only due to the hydrogen bonds, but also due to the electrostatic interactions between the positively charged amino-groups of chitosan and negatively charged amino acid residues (glutamic Glu and aspartic Asp acids) of gelatin.

  17. [Contribution of enthalpy to the energetics of complex formation of aromatic ligands with DNA].

    PubMed

    Kostiukov, V V; Khomutova, N M; Evstigneev, M P

    2011-01-01

    The energy contributions of electrostatic, van der Waals interactions, hydrogen bonds, and interactions of charge transfer type to the enthalpy of complex formation of the double-stand DNA with the antitumor antibiotics daunomycin, nogalamycin, and novantron, as well as the mutagens ethidium bromide and proflavine have been calculated. According to the calculations, the van der Waals component (except for nogalamycin) is energetically favorable during complex formation of the antibiotics with DNA, and the contributions of H bonds and electrostatic interactions are unfavorable, with the probability of charge transfer in the complexes being low. It has been shown that the relatively low value of the experimental enthalpy of binding is the sum of components greater in absolute value and different in the sign, which is the cause of large errors in estimating the total enthalpy of complex formation of aromatic ligands with DNA.

  18. Isolation and mass spectrometry of transcription factor complexes.

    PubMed

    Sebastiaan Winkler, G; Lacomis, Lynne; Philip, John; Erdjument-Bromage, Hediye; Svejstrup, Jesper Q; Tempst, Paul

    2002-03-01

    Protocols are described that enable the isolation of novel proteins associated with a known protein and the subsequent identification of these proteins by mass spectrometry. We review the basics of nanosample handling and of two complementary approaches to mass analysis, and provide protocols for the entire process. The protein isolation procedure is rapid and based on two high-affinity chromatography steps. The method does not require previous knowledge of complex composition or activity and permits subsequent biochemical characterization of the isolated factor. As an example, we provide the procedures used to isolate and analyze yeast Elongator, a histone acetyltransferase complex important for transcript elongation, which led to the identification of three novel subunits.

  19. Suilysin-induced Platelet-Neutrophil Complexes Formation is Triggered by Pore Formation-dependent Calcium Influx

    PubMed Central

    Zhang, Shengwei; Zheng, Yuling; Chen, Shaolong; Huang, Shujing; Liu, Keke; Lv, Qingyu; Jiang, Yongqiang; Yuan, Yuan

    2016-01-01

    Platelet activation and platelet–neutrophil interactions have been found to be involved in inflammation, organ failure and soft-tissue necrosis in bacterial infections. Streptococcus suis, an emerging human pathogen, can cause streptococcal toxic-shock syndrome (STSS) similarly to Streptococcus pyogenes. Currently, S. suis–platelet interactions are poorly understood. Here, we found that suilysin (SLY), the S. suis cholesterol-dependent cytolysin (CDC), was the sole stimulus of S. suis that induced platelet-neutrophil complexes (PNC) formation. Furthermore, P-selectin released in α-granules mediated PNC formation. This process was triggered by the SLY-induced pore forming-dependent Ca2+ influx. Moreover, we demonstrated that the Ca2+ influx triggered an MLCK-dependent pathway playing critical roles in P-selectin activation and PNC formation, however, PLC-β-IP3/DAG-MLCK and Rho-ROCK-MLCK signalling were not involved. Additionally, the “outside-in” signalling had a smaller effect on the SLY-induced P-selectin release and PNC formation. Interestingly, other CDCs including pneumolysin and streptolysin O have also been found to induce PNC formation in a pore forming-dependent Ca2+ influx manner. It is possible that the bacterial CDC-mediated PNC formation is a similar response mechanism used by a wide range of bacteria. These findings may provide useful insight for discovering potential therapeutic targets for S. suis-associated STSS. PMID:27830834

  20. Oil Formation Volume Factor Determination Through a Fused Intelligence

    NASA Astrophysics Data System (ADS)

    Gholami, Amin

    2016-12-01

    Volume change of oil between reservoir condition and standard surface condition is called oil formation volume factor (FVF), which is very time, cost and labor intensive to determine. This study proposes an accurate, rapid and cost-effective approach for determining FVF from reservoir temperature, dissolved gas oil ratio, and specific gravity of both oil and dissolved gas. Firstly, structural risk minimization (SRM) principle of support vector regression (SVR) was employed to construct a robust model for estimating FVF from the aforementioned inputs. Subsequently, an alternating conditional expectation (ACE) was used for approximating optimal transformations of input/output data to a higher correlated data and consequently developing a sophisticated model between transformed data. Eventually, a committee machine with SVR and ACE was constructed through the use of hybrid genetic algorithm-pattern search (GA-PS). Committee machine integrates ACE and SVR models in an optimal linear combination such that makes benefit of both methods. A group of 342 data points was used for model development and a group of 219 data points was used for blind testing the constructed model. Results indicated that the committee machine performed better than individual models.

  1. Review: Formation of Peptide Radical Ions Through Dissociative Electron Transfer in Ternary Metal-Ligand-Peptide Complexes

    SciTech Connect

    Chu, Ivan K.; Laskin, Julia

    2011-12-31

    The formation and fragmentation of odd-electron ions of peptides and proteins is of interest to applications in biological mass spectrometry. Gas-phase redox chemistry occurring during collision-induced dissociation of ternary metal-ligand-peptide complexes enables the formation of a variety of peptide radicals including the canonical radical cations, M{sup +{sm_bullet}}, radical dications, [M{sup +}H]{sup 2+{sm_bullet}}, radical anions, [M-2H]{sup -{sm_bullet}}. In addition, odd-electron peptide ions with well-defined initial location of the radical site are produced through side chain losses from the radical ions. Subsequent fragmentation of these species provides information on the role of charge and the location of the radical site on the competition between radical-induced and proton-driven fragmentation of odd-electron peptide ions. This account summarizes current understanding of the factors that control the efficiency of the intramolecular electron transfer (ET) in ternary metal-ligand-peptide complexes resulting in formation of odd-electron peptide ions. Specifically, we discuss the effect of the metal center, the ligand and the peptide structure on the competition between the ET, proton transfer (PT), and loss of neutral peptide and neutral peptide fragments from the complex. Fundamental studies of the structures, stabilities, and the energetics and dynamics of fragmentation of such complexes are also important for detailed molecular-level understanding of photosynthesis and respiration in biological systems.

  2. A transcription factor network controls cell migration and fate decisions in the developing zebrafish pineal complex

    PubMed Central

    Clanton, Joshua A.; Dean, Benjamin J.; Gamse, Joshua T.

    2016-01-01

    The zebrafish pineal complex consists of four cell types (rod and cone photoreceptors, projection neurons and parapineal neurons) that are derived from a single pineal complex anlage. After specification, parapineal neurons migrate unilaterally away from the rest of the pineal complex whereas rods, cones and projection neurons are non-migratory. The transcription factor Tbx2b is important for both the correct number and migration of parapineal neurons. We find that two additional transcription factors, Flh and Nr2e3, negatively regulate parapineal formation. Flh induces non-migratory neuron fates and limits the extent of parapineal specification, in part by activation of Nr2e3 expression. Tbx2b is positively regulated by Flh, but opposes Flh action during specification of parapineal neurons. Loss of parapineal neuron specification in Tbx2b-deficient embryos can be partially rescued by loss of Nr2e3 or Flh function; however, parapineal migration absolutely requires Tbx2b activity. We conclude that cell specification and migration in the pineal complex are regulated by a network of at least three transcription factors. PMID:27317804

  3. Investigation of cu-BTA complex formation during Cu chemical mechanical planarization process

    NASA Astrophysics Data System (ADS)

    Cho, Byoung-Jun; Shima, Shohei; Hamada, Satomi; Park, Jin-Goo

    2016-10-01

    The effect of Cu surface conditions on Cu-BTA complex formation was investigated using contact angle, electrochemical impedance spectroscopy, spectroscopic ellipsometry and XPS measurements which is of interest to Cu Chemical Mechanical Planarization (CMP) process. During Cu CMP process BTA is widely used as a corrosion inhibitor, reacts with Cu and forms a strong Cu-BTA complex. Thus, it is very essential to remove Cu-BTA complex during post-Cu CMP cleaning process as Cu-BTA complex causes severe problems such as particle contamination and watermark due to its hydrophobic nature. In this report, the Cu-BTA complex formation at various Cu surfaces (as received, pure Cu and Cu oxide) was investigated in order to understand its adsorption reaction and develop effective post-Cu CMP cleaning process.

  4. Electrochemical detection of oligopeptides through the precolumn formation of biuret complexes.

    PubMed

    Tsai, H Y; Weber, S G

    1991-04-12

    The relatively slow kinetics of formation of the electroactive Cu(II)-peptide complexes from larger (greater than 6 amino acids) peptides requires relatively high temperature and long reaction times for a postcolumn reactor. The precolumn incubation of bradykinin, Tyr8-bradykinin and insulin A chain with biuret reagent for 20 min at 60 degrees C leads to the formation of biuret complexes which can be subjected to chromatography in acidic or basic eluents. These complexes are detected electrochemically with a sensitivity similar to the Cu(II)-(ala)3 complex (1 nC/pmol at 1.0 ml/min). The influence of the column-packing material on the electrochemical detector response of the Cu-peptide complexes has also been studied.

  5. Inhibitory effects of NAMI-A-like ruthenium complexes on prion neuropeptide fibril formation.

    PubMed

    Wang, Xuesong; Zhu, Dengsen; Zhao, Cong; He, Lei; Du, Weihong

    2015-05-01

    Prion diseases are a group of infectious and fatal neurodegenerative disorders caused by the conformational conversion of a cellular prion protein (PrP) into its abnormal isoform PrP(Sc). PrP106-126 resembles PrP(Sc) in terms of physicochemical and biological characteristics and is used as a common model for the treatment of prion diseases. Inhibitory effects on fibril formation and neurotoxicity of the prion neuropeptide PrP106-126 have been investigated using metal complexes as potential inhibitors. Nevertheless, the binding mechanism between metal complexes and the peptide remains unclear. The present study is focused on the interaction of PrP106-126 with NAMI-A and NAMI-A-like ruthenium complexes, including KP418, KP1019, and KP1019-2. Results demonstrated that these ruthenium complexes could bind to PrP106-126 in a distinctive binding mode through electrostatic and hydrophobic interactions. NAMI-A-like ruthenium complexes can also effectively inhibit the aggregation and fibril formation of PrP106-126. The complex KP1019 demonstrated the optimal inhibitory ability upon peptide aggregation, and cytotoxicity because of its large aromatic ligand contribution. The studied complexes could also regulate the copper redox chemistry of PrP106-126 and effectually inhibit the formation of reactive oxygen species. Given these findings, ruthenium complexes with relatively low cellular toxicity may be used to develop potential pharmaceutical products against prion diseases.

  6. Complex Formation in the Ternary System Tl(III)-CN(-)-Cl(-) in Aqueous Solution. A (205)Tl NMR Study.

    PubMed

    Berg, Katja E.; Blixt, Johan; Glaser, Julius

    1996-11-20

    The existence of mixed complexes of the general formula Tl(CN)(m)()Cl(n)()(3)(-)(m)()(-)(n)() (m + n complexes have been identified, and their compositions, chemical shifts, (205)Tl-(13)C spin-spin coupling constants, and peak integrals were determined and used to calculate the stability constants, beta = [Tl(CN)(m)()Cl(n)()(3)(-)(m)()(-)(n)()]/{[Tl(3+)][CN(-)](m)()[Cl(-)](n)()}. Very good agreement was obtained between the equilibrium constants determined in this work and those estimated by a theoretical formula using the stability constants for the binary complexes and a statistical factor. Specific interaction coefficients have been calculated for the Tl(CN)(m)()(3)(-)(m)() (1 complexes. Some interesting correlations were found for the obtained NMR parameters. The stepwise formation constants for addition of one cyanide ligand, log K(CN), show linear dependence on both the spin-spin coupling constants, (1)J((205)Tl-(13)C), and the chemical shifts, delta(Tl). Also the interatomic distance, d(Tl-C), is linearly correlated to the spin-spin coupling constant. The correlations are discussed in terms of the Ramsey equation, involving bond properties, stereochemistry, and stability of the complexes. Since (1)J((205)Tl-(13)C) also shows linear dependence on the Tl-CN force constant, it is concluded that the above correlations reflect the Tl-CN bond strength. Thus, the most important factor contributing to the thermodynamic stability of the complexes is the enthalpy term, dominated by formation of very strong sigma-bonds between cyanide and thallium. These trends may prove useful for spectral/structural assignments but also for estimation of metal-to-ligand bond distances and stability constants for complexes which exist only in low concentration.

  7. Effects of chemical and enzymatic modifications on starch-oleic acid complex formation.

    PubMed

    Arijaje, Emily Oluwaseun; Wang, Ya-Jane

    2015-04-29

    The solubility of starch-inclusion complexes affects the digestibility and bioavailability of the included molecules. Acetylation with two degrees of substitution, 0.041 (low) and 0.091 (high), combined without or with a β-amylase treatment was employed to improve the yield and solubility of the inclusion complex between debranched potato starch and oleic acid. Both soluble and insoluble complexes were recovered and analyzed for their degree of acetylation, complexation yields, molecular size distributions, X-ray diffraction patterns, and thermal properties. Acetylation significantly increased the amount of recovered soluble complexes as well as the complexed oleic acid in both soluble and insoluble complexes. High-acetylated debranched-only starch complexed the highest amount of oleic acid (38.0 mg/g) in the soluble complexes; low-acetylated starch with or without the β-amylase treatment resulted in the highest complexed oleic acid in the insoluble complexes (37.6-42.9 mg/g). All acetylated starches displayed the V-type X-ray pattern, and the melting temperature generally decreased with acetylation. The results indicate that starch acetylation with or without the β-amylase treatment can improve the formation and solubility of the starch-oleic acid complex.

  8. Control of cell fate by the formation of an architecturally complex bacterial community

    PubMed Central

    Vlamakis, Hera; Aguilar, Claudio; Losick, Richard; Kolter, Roberto

    2008-01-01

    Bacteria form architecturally complex communities known as biofilms in which cells are held together by an extracellular matrix. Biofilms harbor multiple cell types, and it has been proposed that within biofilms individual cells follow different developmental pathways, resulting in heterogeneous populations. Here we demonstrate cellular differentiation within biofilms of the spore-forming bacterium Bacillus subtilis, and present evidence that formation of the biofilm governs differentiation. We show that motile, matrix-producing, and sporulating cells localize to distinct regions within the biofilm, and that the localization and percentage of each cell type is dynamic throughout development of the community. Importantly, mutants that do not produce extracellular matrix form unstructured biofilms that are deficient in sporulation. We propose that sporulation is a culminating feature of biofilm formation, and that spore formation is coupled to the formation of an architecturally complex community of cells. PMID:18381896

  9. Pathway of actin filament branch formation by Arp2/3 complex revealed by single-molecule imaging

    PubMed Central

    Smith, Benjamin A.; Daugherty-Clarke, Karen; Goode, Bruce L.; Gelles, Jeff

    2013-01-01

    Actin filament nucleation by actin-related protein (Arp) 2/3 complex is a critical process in cell motility and endocytosis, yet key aspects of its mechanism are unknown due to a lack of real-time observations of Arp2/3 complex through the nucleation process. Triggered by the verprolin homology, central, and acidic (VCA) region of proteins in the Wiskott-Aldrich syndrome protein (WASp) family, Arp2/3 complex produces new (daughter) filaments as branches from the sides of preexisting (mother) filaments. We visualized individual fluorescently labeled Arp2/3 complexes dynamically interacting with and producing branches on growing actin filaments in vitro. Branch formation was strikingly inefficient, even in the presence of VCA: only ∼1% of filament-bound Arp2/3 complexes yielded a daughter filament. VCA acted at multiple steps, increasing both the association rate of Arp2/3 complexes with mother filament and the fraction of filament-bound complexes that nucleated a daughter. The results lead to a quantitative kinetic mechanism for branched actin assembly, revealing the steps that can be stimulated by additional cellular factors. PMID:23292935

  10. [Studies by means of 1H NMR spectroscopy of complex formation of aromatic biologically active compounds with antibiotic topotecan].

    PubMed

    Mosunov, A A; Kostiukov, V V; Evstigneev, M P

    2012-01-01

    The analysis of heteroassociation of antibiotic topotecan (TPT) with aromatic biologically active compounds (BAC): caffeine, mutagens ethidium bromide and proflavine, antibiotic daunomycin, vitamins flavin-mononucleotide and nicotinamide, has been carried out in the work using 1H NMR spectroscopy data. The equilibrium constants of heteroassociation and induced chemical shifts of the protons have been obtained in the complexes with BAC. It is found that the complex formation TPT-BAC has the nature of stacking of the chromophores, additionally stabilized in the case of proflavine by intermolecular hydrogen bond. Calculation of the basic components of the Gibbs free energy of the complexation reactions is carried out, and the factors which stabilize and destabilize the heterocomplexes of molecules are revealed.

  11. Dapper1 promotes autophagy by enhancing the Beclin1-Vps34-Atg14L complex formation.

    PubMed

    Ma, Benyu; Cao, Weipeng; Li, Wenxia; Gao, Chan; Qi, Zhen; Zhao, Yan; Du, Jun; Xue, Hua; Peng, Junya; Wen, Jun; Chen, Hua; Ning, Yuanheng; Huang, Lei; Zhang, Hong; Gao, Xiang; Yu, Li; Chen, Ye-Guang

    2014-08-01

    Autophagy is an intracellular degradation process to clear up aggregated proteins or aged and damaged organelles. The Beclin1-Vps34-Atg14L complex is essential for autophagosome formation. However, how the complex formation is regulated is unclear. Here, we show that Dapper1 (Dpr1) acts as a critical regulator of the Beclin1-Vps34-Atg14L complex to promote autophagy. Dpr1 ablation in the central nervous system results in motor coordination defect and accumulation of p62 and ubiquitinated proteins. Dpr1 increases autophagosome formation as indicated by elevated puncta formation of LC3, Atg14L and DFCP1 (Double FYVE-containing protein 1). Conversely, loss of Dpr1 impairs LC3 lipidation and causes p62/SQSTM1 accumulation. Dpr1 directly interacts with Beclin1 and Atg14L and enhances the Beclin1-Vps34 interaction and Vps34 activity. Together, our findings suggest that Dpr1 enhances the Atg14L-Beclin1-Vps34 complex formation to drive autophagy.

  12. Characterization of novel components of the baculovirus per os infectivity factor complex.

    PubMed

    Peng, Ke; van Lent, Jan W M; Boeren, Sjef; Fang, Minggang; Theilmann, David A; Erlandson, Martin A; Vlak, Just M; van Oers, Monique M

    2012-05-01

    Baculovirus occlusion-derived virus (ODV) infects insect midgut cells under alkaline conditions, a process mediated by highly conserved per os infectivity factors (PIFs), P74 (PIF0), PIF1, PIF2, PIF3, PIF4, and PIF5 (ODV-E56). Previously, a multimolecular complex composed of PIF1, PIF2, PIF3, and P74 was identified which was proposed to play an essential role during ODV entry. Recently, more proteins have been identified that play important roles in ODV oral infectivity, including PIF4, PIF5, and SF58, which might work in concert with previously known PIFs to facilitate ODV infection. In order to understand the ODV entry mechanism, the identification of all components of the PIF complex is crucial. Hence, the aim of this study was to identify additional components of the PIF complex. Coimmunoprecipitation (CoIP) combined with proteomic analysis was used to identify the components of the Autographa californica multiple nucleopolyhedrovirus (AcMNPV) PIF complex. PIF4 and P95 (AC83) were identified as components of the PIF complex while PIF5 was not, and this was confirmed with blue native PAGE and a second CoIP. Deletion of the pif4 gene impaired complex formation, but deletion of pif5 did not. Differentially denaturing SDS-PAGE further revealed that PIF4 forms a stable complex with PIF1, PIF2, and PIF3. P95 and P74 are more loosely associated with this complex. Three other proteins, AC5, AC68, and AC108 (homologue of SF58), were also found by the proteomic analysis to be associated with the PIF complex. Finally the functional significance of the PIF protein interactions is discussed.

  13. Mass-dependent and -independent fractionation of isotopes in Ni and Pb chelate complex formation reactions

    NASA Astrophysics Data System (ADS)

    Nomura, Masao; Kudo, Takashi; Adachi, Atsuhiko; Aida, Masao; Fujii, Yasuhiko

    2013-11-01

    Mass independent fractionation (MIF) has been a very interesting topic in the field of inorganic isotope chemistry, in particular, geo- and cosmo- chemistry. In the present work, we studied the isotope fractionation of Ni(II) and Pb(II) ions in complex formation with chelating reagent EDTA. To obtain clear results on the mass dependence of the isotope fractionation, we have conducted long-distance ion exchange chromatography of Ni(II) and Pb(II), using chelate complex reagent EDTA. The results apparently show that the isotope fractionation in Ni complex formation system is governed by the mass dependent rule. On the other hand the isotope fractionation in the Pb complex system is governed by the mass independent rule or the nuclear volume effect.

  14. Mass-dependent and -independent fractionation of isotopes in Ni and Pb chelate complex formation reactions

    SciTech Connect

    Nomura, Masao; Kudo, Takashi; Adachi, Atsuhiko; Aida, Masao; Fujii, Yasuhiko

    2013-11-13

    Mass independent fractionation (MIF) has been a very interesting topic in the field of inorganic isotope chemistry, in particular, geo- and cosmo- chemistry. In the present work, we studied the isotope fractionation of Ni(II) and Pb(II) ions in complex formation with chelating reagent EDTA. To obtain clear results on the mass dependence of the isotope fractionation, we have conducted long-distance ion exchange chromatography of Ni(II) and Pb(II), using chelate complex reagent EDTA. The results apparently show that the isotope fractionation in Ni complex formation system is governed by the mass dependent rule. On the other hand the isotope fractionation in the Pb complex system is governed by the mass independent rule or the nuclear volume effect.

  15. Thermodynamics of cationic lipid-DNA complex formation as studied by isothermal titration calorimetry.

    PubMed

    Pozharski, Edwin; MacDonald, Robert C

    2002-07-01

    The detailed analysis of the cationic lipid-DNA complex formation by means of isothermal titration calorimetry is presented. Most experiments were done using 1,2-dioleyl-sn-glycero-3-ethylphosphocholine (EDOPC), but basic titrations were also done using DOTAP, DOTAP:DOPC, and DOTAP:DOPE mixtures. Complex formation was endothermic with less than 1 kcal absorbed per mole of lipid or DNA charge. This enthalpy change was attributed to DNA-DNA mutual repulsion within the lamellar complex. The exception was DOTAP:DOPE-containing lipoplex for which the enthalpy of formation was exothermic, presumably because of DOPE amine group protonation. Experimental conditions, namely, direction and titration increment as well as concentration of titrant, which dictate the structure of resulting lipoplex (whether lamellar complex or DNA-coated vesicle), were found to affect the apparent thermodynamics of complex formation. The structure, in turn, influences the biological properties of the lipoplex. If the titration of lipid into DNA was carried out in large increments, the DeltaH was larger than when the injection increments were smaller, a finding that is consistent with increased vesicle disruption under large increments and which is expected theoretically. Cationic lipid-DNA binding was weak in high ionic strength solutions, however, the effective binding constant is within micromolar range because of macromolecular nature of the interaction.

  16. Thermodynamics of cationic lipid-DNA complex formation as studied by isothermal titration calorimetry.

    PubMed Central

    Pozharski, Edwin; MacDonald, Robert C

    2002-01-01

    The detailed analysis of the cationic lipid-DNA complex formation by means of isothermal titration calorimetry is presented. Most experiments were done using 1,2-dioleyl-sn-glycero-3-ethylphosphocholine (EDOPC), but basic titrations were also done using DOTAP, DOTAP:DOPC, and DOTAP:DOPE mixtures. Complex formation was endothermic with less than 1 kcal absorbed per mole of lipid or DNA charge. This enthalpy change was attributed to DNA-DNA mutual repulsion within the lamellar complex. The exception was DOTAP:DOPE-containing lipoplex for which the enthalpy of formation was exothermic, presumably because of DOPE amine group protonation. Experimental conditions, namely, direction and titration increment as well as concentration of titrant, which dictate the structure of resulting lipoplex (whether lamellar complex or DNA-coated vesicle), were found to affect the apparent thermodynamics of complex formation. The structure, in turn, influences the biological properties of the lipoplex. If the titration of lipid into DNA was carried out in large increments, the DeltaH was larger than when the injection increments were smaller, a finding that is consistent with increased vesicle disruption under large increments and which is expected theoretically. Cationic lipid-DNA binding was weak in high ionic strength solutions, however, the effective binding constant is within micromolar range because of macromolecular nature of the interaction. PMID:12080142

  17. Role of complexes formation between drugs and penetration enhancers in transdermal delivery.

    PubMed

    Drakulić, Branko J; Juranić, Ivan O; Erić, Slavica; Zloh, Mire

    2008-11-03

    The use of chemical penetration enhancers (CPE) is growing due to their ability to improve drug delivery through the skin. A possible mechanism of penetration enhancement could involve the complex formation between drug and components in the pharmaceutical formulation, thus altering the physicochemical properties of the active substance. Here, modelling studies indicate that hydrocarbon and oxygen-containing terpenes (penetration enhancers) could form complexes with drugs. Satisfactory correlations have been obtained between the predicted molecular properties of enhancers and their enhancement effects.

  18. Biochemical and dietary factors of uric acid stone formation.

    PubMed

    Trinchieri, Alberto; Montanari, Emanuele

    2017-02-28

    The aim of this study was to compare the clinical characteristics of "pure" uric acid renal stone formers (UA-RSFs) with that of mixed uric acid/calcium oxalate stone formers (UC-RSFs) and to identify which urinary and dietary risk factors predispose to their formation. A total of 136 UA-RSFs and 115 UC-RSFs were extracted from our database of renal stone formers. A control group of 60 subjects without history of renal stones was considered for comparison. Data from serum chemistries, 24-h urine collections and 24-h dietary recalls were considered. UA-RSFs had a significantly (p = 0.001) higher body mass index (26.3 ± 3.6 kg/m(2)) than UC-RSFs, whereas body mass index of UA-RSFs was higher but not significantly than in controls (24.6 ± 4.7) (p = 0.108). The mean urinary pH was significantly lower in UA-RSFs (5.57 ± 0.58) and UC-RSFs (5.71 ± 0.56) compared with controls (5.83 ± 0.29) (p = 0.007). No difference of daily urinary uric acid excretion was observed in the three groups (p = 0.902). Daily urinary calcium excretion was significantly (p = 0.018) higher in UC-RSFs (224 ± 149 mg/day) than UA-RSFs (179 ± 115) whereas no significant difference was observed with controls (181 ± 89). UA-RSFs tend to have a lower uric acid fractional excretion (0.083 ± 0.045% vs 0.107+/-0.165; p = 0.120) and had significantly higher serum uric acid (5.33 ± 1.66 vs 4.78 ± 1.44 mg/dl; p = 0.007) than UC-RSFs. The mean energy, carbohydrate and vitamin C intakes were higher in UA-SFs (1987 ± 683 kcal, 272 ± 91 g, 112 ± 72 mg) and UC-SFs (1836 ± 74 kcal, 265 ± 117, 140 ± 118) with respect to controls (1474 ± 601, 188 ± 84, 76 ± 53) (p = 0.000). UA-RSFs should be differentiated from UC-RSFs as they present lower urinary pH, lower uric acid fractional excretion and higher serum uric acid. On the contrary, patients with UC-RSFs show urinary risk factors

  19. Some factors affecting cyclopropane acid formation in Escherichia coli

    PubMed Central

    Knivett, V. A.; Cullen, Julia

    1965-01-01

    1. The fatty acid composition of the extractable lipids of Escherichia coli varied with growth conditions. 2. The principal fatty acids were palmitic acid, hexadecenoic acid, octadecenoic acid and the cyclopropane acids, methylenehexadecanoic acid and methyleneoctadecanoic acid. 3. Cyclopropane acid formation from monoenoic acids was increased by acid media, poor oxygen supply, or high growth temperature. 4. Cyclopropane acid formation was decreased by alkaline media, well oxygenated conditions, the presence of citrate, or lack of Mg2+. PMID:5324304

  20. Communication: Structure, formation, and equilibration of ensembles of Ag-S complexes on an Ag surface

    SciTech Connect

    Russell, Selena M.; Kim, Yousoo; Liu, Da-Jiang; Evans, J. W.; Thiel, P. A.

    2013-02-15

    We have utilized conditions of very low temperature (4.7 K) and very low sulfur coverage to isolate and identify Ag-S complexes that exist on the Ag(111) surface. The experimental conditions are such that the complexes form at temperatures above the temperature of observation. These complexes can be regarded as polymeric chains of varying length, with an Ag4S pyramid at the core of each monomeric unit. Steps may catalyze the formation of the chains and this mechanism may be reflected in the chain length distribution.

  1. Differential proteolytic activation of factor VIII-von Willebrand factor complex by thrombin

    SciTech Connect

    Hill-Eubanks, D.C.; Parker, C.G.; Lollar, P. )

    1989-09-01

    Blood coagulation factor VIII (fVIII) is a plasma protein that is decreased or absent in hemophilia A. It is isolated as a mixture of heterodimers that contain a variably sized heavy chain and a common light chain. Thrombin catalyzes the activation of fVIII in a reaction that is associated with cleavages in both types of chain. The authors isolated a serine protease from Bothrops jararacussu snake venom that catalyzes thrombin-like heavy-chain cleavage but not light-chain cleavage in porcine fVIII as judged by NaDodSO{sub 4}/PAGE and N-terminal sequence analysis. Using a plasma-free assay of the ability of activated {sup 125}I-fVIII to function as a cofactor in the activation of factor X by factor IXa, they found that fVIII is activated by the venom enzyme. The venom enzyme-activated fVIII was isolated in stable form by cation-exchange HPLC. von Willebrand factor inhibited venom enzyme-activated fVIII but not thrombin-activated fVIII. These results suggest that the binding of fVIII to von Willebrand factor depends on the presence of an intact light chain and that activated fVIII must dissociate from von Willebrand factor to exert its cofactor effect. Thus, proteolytic activation of fVIII-von Willebrand factor complex appears to be differentially regulated by light-chain cleavage to dissociate the complex and heavy-chain cleavage to activate the cofactor function.

  2. Quantum statistical vibrational entropy and enthalpy of formation of helium-vacancy complex in BCC W

    NASA Astrophysics Data System (ADS)

    Wen, Haohua; Woo, C. H.

    2016-12-01

    High-temperature advance-reactor design and operation require knowledge of in-reactor materials properties far from the thermal ground state. Temperature-dependence due to the effects of lattice vibrations is important to the understanding and formulation of atomic processes involved in irradiation-damage accumulation. In this paper, we concentrate on the formation of He-V complex. The free-energy change in this regard is derived via thermodynamic integration from the phase-space trajectories generated from MD simulations based on the quantum fluctuation-dissipation relation. The change of frequency distribution of vibration modes during the complex formation is properly accounted for, and the corresponding entropy change avoids the classical ln(T) divergence that violates the third law. The vibrational enthalpy and entropy of formation calculated this way have significant effects on the He kinetics during irradiation.

  3. Structure and kinetics of formation of catechol complexes of ferric soybean lipoxygenase-1

    SciTech Connect

    Nelson, M.J.; Brennan, B.A.; Chase, D.B. |

    1995-11-21

    Ferric soybean lipoxygenase forms stable complexes with 4-substituted catechols. The structure of the complex between the enzyme and 3,4-dihydroxybenzonitrile has been studied by resonance Raman, electron paramagnetic resonance, visible, and X-ray spectroscopies. It is a bidentate iron-catecholate complex with at least one water ligand. The kinetics of formation of complexes between lipoxygenase and 3,4-dihydroxybenzonitrile and 3,4-dihydroxyacetophenone have been studied by stopped-flow spectroscopy. The data are consistent with two kinetically distinct, reversible steps. The pH dependence of the first step suggests that the substrate for the reaction is the catechol monoanion. When these results are combined, plausible mechanisms for the complexation reaction are suggested. 51 refs., 12 figs., 2 tabs.

  4. Effect of entropy-packing fraction relation on the formation of complex metallic materials

    NASA Astrophysics Data System (ADS)

    Tourki Samaei, Arash; Mohammadi, Ehsan

    2015-09-01

    By combining a number of elements to form complex metallic materials without a base element, it was recently shown that one can obtain rather complex structures, including random solute solutions, multi-phased mixtures and amorphous structures with/without nano-precipitations. Compared to conventional metallic materials, these complex ones could show excellent mechanical and physical properties across a wide range of temperatures, therefore being a promising advanced material for high-temperature applications; however, designing these complex materials, at present, still lacks a unified physical approach but relies on the choice of a few metallurgical parameters, such as atomic size mismatch, heat of mixing and valence electron concentration. Here, we identify a physical mechanism through the optimization of the excess configurational entropy of mixing in the control of phase formation in these metallic materials. The theoretical framework herein established is expected to provide a new paradigm in pursuit of complex metallic materials with superior properties.

  5. Recrystallized Impact Glasses of the Onaping Formation and the Sudbury Igneous Complex, Sudbury Structure, Ontario, Canada

    NASA Technical Reports Server (NTRS)

    Dressler, B. O.; Weiser, T.; Brockmeyer, P.

    1996-01-01

    The origin of the Sudbury Structure and of the associated heterolithic breccias of the Onaping Formation and the Sudbury Igneous Complex have been controversial. While an impact origin of the structure has gained wide acceptance over the last 15 years, the origin of the recrystallized Onaping Formation glasses and of the igneous complex is still being debated. Recently the interpretation of the breccias of the Onaping Formation as suevitic fall-back impact breccias has been challenged. The igneous complex is interpreted either as a differentiated impact melt sheet or as a combination of an upper impact melt represented by the granophyre, and a lower, impact-triggered magmatic body consisting of the norite-sublayer formations. The Onaping Formation contains glasses as fluidal and nonfluidal fragments of various shapes and sizes. They are recrystallized, and our research indicates that they are petrographically heterogeneous and span a wide range of chemical compositions. These characteristics are not known from glasses of volcanic deposits. This suggests an origin by shock vitrification, an interpretation consistent with their association with numerous and varied country rock clasts that exhibit microscopic shock metamorphic features. The recrystallized glass fragments represent individual solid-state and liquid-state vitrified rocks or relatively small melt pods. The basal member lies beneath the Gray and Black members of the Onaping Formation and, where not metamorphic, has an igneous matrix. Igneous-textured melt bodies occur in the upper two members and above the Basal Member. A comparison of the chemical compositions of recrystallized glasses and of the matrices of the Basal Member and the melt bodies with the components and the bulk composition of the igneous complex is inconclusive as to the origin of the igneous complex. Basal Member matrix and Melt Bodies, on average, are chemically similar to the granophyre of the Sudbury Igneous Complex, suggesting that

  6. A history of poly A sequences: from formation to factors to function.

    PubMed

    Edmonds, Mary

    2002-01-01

    Biological polyadenylation, first recognized as an enzymatic activity, remained an orphan enzyme until poly A sequences were found on the 3' ends of eukarvotic mRNAs. Their presence in bacteria viruses and later in archeae (ref. 338) established their universality. The lack of compelling evidence for a specific function limited attention to their cellular formation. Eventually the newer techniques of molecular biology and development of accurate nuclear processing extracts showed 3' end formation to be a two-step process. Pre-mRNA was first cleaved endonucleolytically at a specific site that was followed by sequential addition of AMPs from ATP to the 3' hydroxyl group at the end of mRNA. The site of cleavage was specified by a conserved hexanucleotide, AAUAAA, from 10 to 30 nt upstream of this 3' end. Extensive purification of these two activities showed that more than 10 polypeptides were needed for mRNA 3' end formation. Most of these were in complexes involved in the cleavage step. Two of the best characterized are CstF and CPSF, while two other remain partially purified but essential. Oddly, the specific proteins involved in phosphodiester bond hydrolysis have yet to be identified. The polyadenylation step occurs within the complex of poly A polymerase and poly A-binding protein, PABII, that controls poly A length. That the cleavage complex, CPSF, is also required for this step attests to a tight coupling of the two steps of 3' and formation. The reaction reconstituted from these RNA-free purified factors correctly processes pre-mRNAs. Meaningful analysis of the role of poly A in mRNA metabolism or function was possible once quantities of these proteins most often over-expressed from cDNA clones became available. The large number needed for two simple reactions of an endonuclease, a polymerase and a sequence recognition factor, pointed to 3' end formation as a regulated process. Polyadenylation itself had appeared to require regulation in cases where two poly A

  7. Stability of furosemide polymorphs and the effects of complex formation with β-cyclodextrin and maltodextrin.

    PubMed

    Garnero, Claudia; Chattah, Ana Karina; Longhi, Marcela

    2016-11-05

    The effect of the formation of supramolecular binary complexes with β-cyclodextrin and maltodextrin on the chemical and physical stability of the polymorphs I and II of furosemide was evaluated in solid state. The solid samples were placed under accelerated storage conditions and exposed to daylight into a stability chamber for a 6-month. Chemical stability was monitored by high performance liquid chromatography, while the physical stability was studied by solid state nuclear magnetic resonance, powder X-ray diffraction and scanning electron microscopy. Changes in the physical appearance of the samples were evaluated. The studies showed a significant stabilizing effect of β-cyclodextrin on furosemide form II. Our results suggest that the complex formation is a useful tool for improving the stability of furosemide polymorphs. These new complexes are promising candidates that can be used in the pharmaceutical industry for the preparation of alternative matrices that improve physicochemical properties.

  8. Theoretical predictions of hydrolysis and complex formation of the heaviest elements

    NASA Astrophysics Data System (ADS)

    Pershina, V.

    2000-07-01

    In the presentation, investigations of hydrolysis and complex formation of group 4, 5 and 6 elements, including the transactinide elements 104, 105 and 106 are described. They were carried out on the basis of results of relativistic calculations of the electronic structure of various hydrated, hydrolyzed and complex compounds of these elements using the fully relativistic ab initio density functional method with the GGA approximation for the exchange-correlation potential. Predictions of equilibria of hydrolysis or complex formation reactions have been made using a model which enables determination of free energy changes of the reactions as changes in the ionic and covalent contributions to the binding molecular energy separately. Those contributions were calculated using the Mulliken analysis of the electronic density distribution.

  9. Formation and stability of lanthanide complexes and their encapsulation into polymeric microspheres

    SciTech Connect

    Mumper, R.J.; Jay, M.

    1992-10-15

    The complexation of lanthanides (Ln) with dicarbonyl compounds (acetylacetone, acac; ethyl acetoacetate; 3-ethyl-2,4-pentanedione; 2,4-hexanedione; 3-methyl-2,4-pentanedione; and diethyl malonate) was investigated using a potentiometric titration technique. The ability of a dicarbonyl compound to complex with the lanthanide elements was greatly dependent on its pK{sub a} and on the pH of the titrated solution. Selected lanthanide complexes (Ln complexes) were incorporated into spherical poly(L-lactic acid)(PLA) matrices and irradiated in a nuclear reactor with neutrons to produce short-lived high-energy {Beta}-particle-emitting radioisotopes. The lanthanides investigated (Ho, Dy, Sm, and La) were chosen on the basis of their physical and nuclear properties. A transition element (Re) was also studied. The small decrease in the ionic radii of the lanthanides with increasing atomic number led to (a) greater ability to extract and complex from an aqueous solution with complexing agents, (b) larger formation and stability constants for the Ln complexes, (c) increased solubility of the Ln complexes in chloroform, and (d) increase in the maximum percent incorporation of the stable lanthanides in PLA spheres. Ho(aca) was found to be the most promising candidate of the complexes studied on the basis of the above observations and due to the favorable physical properties of {sup 165}Ho and nuclear properties of {sup 166}Ho. 21 refs., 5 figs., 4 tabs.

  10. Nanoparticles in plant extracts--factors which influence the formation of nanoparticles in black tea infusions.

    PubMed

    Gröning, R; Breitkreutz, J; Baroth, V; Müller, R S

    2001-10-01

    The influence of different factors on the formation of nanoparticles in freshly brewed tea extracts was investigated. A black tea infusion was observed during cooling using photon correlation spectroscopy (PCS). The mean particle size and the number of the nanoparticles increase with decreasing temperature. In the presence of caffeine more particles are formed within the infusion. To study the influence of slight structural differences between methylxanthines, the effect of the addition of caffeine to solutions of freshly prepared decaffeinated tea was compared to that of theophylline and theobromine. In the case of theophylline fewer nanoparticles were formed. Molecular modelling calculations were performed to evaluate the most probable geometries for caffeine-polyphenol complexes. A parallel position and a congruent orientation of the 6-membered ring of caffeine and the aromatic galloyl group is the most probable geometry.

  11. Lethal synergism between organic and inorganic wood preservatives via formation of an unusual lipophilic ternary complex

    SciTech Connect

    Sheng, Zhi-Guo; Li, Yan; Fan, Rui-Mei; Chao, Xi-Juan; Zhu, Ben-Zhan

    2013-02-01

    We have shown previously that exposing bacteria to wood preservatives pentachlorophenol (PCP) and copper-containing compounds together causes synergistic toxicity. However, it is not clear whether these findings also hold true in mammalian cells; and if so, what is the underlying molecular mechanism? Here we show that PCP and a model copper complex bis-(1,10-phenanthroline) cupric (Cu(OP){sub 2}), could also induce synergistic cytotoxicity in human liver cells. By the single crystal X-ray diffraction and atomic absorption spectroscopy assay, the synergism was found to be mainly due to the formation of a lipophilic ternary complex with unusual structural and composition characteristics and subsequent enhanced cellular copper uptake, which markedly promoted cellular reactive oxygen species (ROS) production, leading to apoptosis by decreasing mitochondrial membrane potential, increasing pro-apoptotic protein expression, releasing cytochrome c from mitochondria and activating caspase-3, and -9. Analogous results were observed with other polychlorinated phenols (PCPs) and Cu(OP){sub 2}. Synergistic cytotoxicity could be induced by PCP/Cu(OP){sub 2} via formation of an unusual lipophilic complex in HepG2 cells. The formation of ternary complexes with similar lipophilic character could be of relevance as a general mechanism of toxicity, which should be taken into consideration especially when evaluating the toxicity of environmental pollutants found at currently-considered non- or sub-toxic concentrations. -- Highlights: ► The combination of PCP/Cu(OP){sub 2} induces synergistic cytotoxicity in HepG2 cells. ► The synergism is mainly due to forming a lipophilic ternary complex between them. ► The formation of lipophilic ternary complex enhances cellular copper uptake. ► PCP/Cu(OP){sub 2} stimulates the cellular ROS production. ► The ROS promoted by PCP/Cu(OP){sub 2} induces mitochondria-dependent apoptosis.

  12. Baculovirus per os infectivity factors form a complex on the surface of occlusion-derived virus.

    PubMed

    Peng, Ke; van Oers, Monique M; Hu, Zhihong; van Lent, Jan W M; Vlak, Just M

    2010-09-01

    Five highly conserved per os infectivity factors, PIF1, PIF2, PIF3, PIF4, and P74, have been reported to be essential for oral infectivity of baculovirus occlusion-derived virus (ODV) in insect larvae. Three of these proteins, P74, PIF1, and PIF2, were thought to function in virus binding to insect midgut cells. In this paper evidence is provided that PIF1, PIF2, and PIF3 form a stable complex on the surface of ODV particles of the baculovirus Autographa californica multinucleocapsid nucleopolyhedrovirus (AcMNPV). The complex could withstand 2% SDS-5% beta-mercaptoethanol with heating at 50 degrees C for 5 min. The complex was not formed when any of the genes for PIF1, PIF2, or PIF3 was deleted, while reinsertion of these genes into AcMNPV restored the complex. Coimmunoprecipitation analysis independently confirmed the interactions of the three PIF proteins and revealed in addition that P74 is also associated with this complex. However, deletion of the p74 gene did not affect formation of the PIF1-PIF2-PIF3 complex. Electron microscopy analysis showed that PIF1 and PIF2 are localized on the surface of the ODV with a scattered distribution. This distribution did not change for PIF1 or PIF2 when the gene for PIF2 or PIF1 protein was deleted. We propose that PIF1, PIF2, PIF3, and P74 form an evolutionarily conserved complex on the ODV surface, which has an essential function in the initial stages of baculovirus oral infection.

  13. Tissue factor de-encryption, thrombus formation, and thiol-disulfide exchange.

    PubMed

    Chen, Vivien M Y

    2013-02-01

    Tissue factor (TF) by forming a complex with factor VIIa (FVIIa) initiates blood coagulation. It was traditionally believed that the separation of FVIIa in circulation from subendothelial TF was the main control that was preventing spontaneous initiation of thrombosis and that circulating cells and endothelium did not express TF protein at rest in healthy individuals. However, TF has been detected in healthy human plasma and animal models of thrombosis, which indicate that TF in circulation can contribute to thrombin generation and fibrin formation after an activation event. Circulating TF-and indeed, most of the TF on the cell surface-is "encrypted" or coagulation inactive. The de-encryption step involves exposure of phosphatidylserine (PS), but PS exposure alone is insufficient for full TF activity. Allosteric disulfide bonds control protein function by mediating conformal change through the formation and breaking of disulfide bonds. TF contains a typical surface exposed allosteric bond in the membrane proximal fibronectin type III domain. Thiol-disulfide exchange involving this disulfide is implicated in TF activation with the formation of the disulfide bond corresponding with the active conformation of TF and free thiol or thiol-modified forms corresponding with encryption. Although the exact mechanism by which TF de-encryption occurs remains a subject of debate, thiol blockade and inhibition of oxidoreductases show an important role for thiol-disulfide reactions in platelet-independent pathways of coagulation in vitro and in vivo. In particular, redox active extracellular protein disulfide isomerase is involved in the earliest stages of thrombus initiation and has proven to be a potential target for antithrombotic drug development.

  14. Complexes of triggered star formation in supergiant shell of Holmberg II

    NASA Astrophysics Data System (ADS)

    Egorov, Oleg V.; Lozinskaya, Tatiana A.; Moiseev, Alexei V.; Shchekinov, Yuri A.

    2017-01-01

    We report a detailed analysis of all regions of current star formation in the walls of the supergiant H I shell (SGS) in the galaxy Holmberg II based on observations with a scanning Fabry-Perot interferometer at the Russian 6-m telescope. We compare the structure and kinematics of ionized gas with that of atomic hydrogen and with the stellar population of the SGS. Our deep Hα images and archival images taken by the Hubble Space Telescope demonstrate that current star formation episodes are larger and more complicated than previously thought: they represent unified star-forming complexes with sizes of several hundred pc rather than `chains' of separate bright nebulae in the walls of the SGS. The fact that we are dealing with unified complexes is evidenced by identified faint shell-like structures of ionized and neutral gas which connect several distinct bright H II regions. Formation of such complexes is due to the feedback of stars with very inhomogeneous ambient gas in the walls of the SGS. The arguments supporting an idea about the triggering of star formation in SGS by the H I supershells collision are presented. We also found a faint ionized supershell inside the H I SGS expanding with a velocity of no greater than 10-15 km s-1. Five OB stars located inside the inner supershell are sufficient to account for its radiation, although a possibility of leakage of ionizing photons from bright H II regions is not ruled out as well.

  15. Formation Control With Size Scaling Via a Complex Laplacian-Based Approach.

    PubMed

    Han, Zhimin; Wang, Lili; Lin, Zhiyun; Zheng, Ronghao

    2016-10-01

    We consider the control of formations of a leader-follower network, where the objective is to steer a team of multiple mobile agents into a formation of variable size. We assume that the shape description of the formation is known to all the agents, which is captured by a complex-valued Laplacian associated with the sensing graph, but the size scaling of the formation is not known or only known to two agents, called the leaders in the network. A distributed linear control strategy is developed in this paper such that the agents converge to the desired formation shape, for which the size of the formation is determined by the two leaders. Moreover, in order to make all agents in a formation move with a common velocity, the distributed control law also incorporates a velocity consensus component, which is implemented with the help of a communication network that may, in general, be of different topology from the sensing graph. Both the setup of single-integrator kinematics and the one of double-integrator dynamics are addressed in the same framework except that the acceleration control in the double-integrator setup has an extra damping term.

  16. Polyelectrolyte complexes stabilize and controllably release vascular endothelial growth factor.

    PubMed

    Huang, Min; Vitharana, Samadhi N; Peek, Laura J; Coop, Tina; Berkland, Cory

    2007-05-01

    Angiogenesis has long been a desired therapeutic approach to improve clinical outcomes of conditions typified by ischemia. Vascular endothelial growth factor (VEGF) has demonstrated the ability to generate new blood vessels in vivo, but trials using intravenous delivery have not yet produced clinical success. Localized, sustained delivery of VEGF has been proven necessary to generate blood vessels as demonstrated by implantable, controlled release devices. Ultimately, nanoparticles delivered by intravenous injection may be designed to accumulate in target tissues and sustain the local VEGF concentration; however, injectable nanosuspensions that control the release of stabilized VEGF must first be developed. In this study, we utilize the heparin binding domain of VEGF to bind the polyanion dextran sulfate, resulting in an enhanced thermal stability of VEGF. Coacervation of the VEGF-bound dextran sulfate with selected polycations (chitosan, polyethylenimine, or poly-L-lysine) produced nanoparticles approximately 250 nm in diameter with high VEGF encapsulation efficiency (50-85%). Release of VEGF from these formulations persisted for >10 days and maintained high VEGF activity as determined by ELISA and a mitogenic bioassay. Chitosan-dextran sulfate complexes were preferred because of their biodegradability, desirable particle size ( approximately 250 nm), entrapment efficiency ( approximately 85%), controlled release (near linear for 10 days), and mitogenic activity.

  17. Globular cluster formation with multiple stellar populations from hierarchical star cluster complexes

    NASA Astrophysics Data System (ADS)

    Bekki, Kenji

    2017-01-01

    Most old globular clusters (GCs) in the Galaxy are observed to have internal chemical abundance spreads in light elements. We discuss a new GC formation scenario based on hierarchical star formation within fractal molecular clouds. In the new scenario, a cluster of bound and unbound star clusters (`star cluster complex', SCC) that have a power-law cluster mass function with a slope (β) of 2 is first formed from a massive gas clump developed in a dwarf galaxy. Such cluster complexes and β = 2 are observed and expected from hierarchical star formation. The most massive star cluster (`main cluster'), which is the progenitor of a GC, can accrete gas ejected from asymptotic giant branch (AGB) stars initially in the cluster and other low-mass clusters before the clusters are tidally stripped or destroyed to become field stars in the dwarf. The SCC is initially embedded in a giant gas hole created by numerous supernovae of the SCC so that cold gas outside the hole can be accreted onto the main cluster later. New stars formed from the accreted gas have chemical abundances that are different from those of the original SCC. Using hydrodynamical simulations of GC formation based on this scenario, we show that the main cluster with the initial mass as large as [2 - 5] × 105M⊙ can accrete more than 105M⊙ gas from AGB stars of the SCC. We suggest that merging of hierarchical star cluster complexes can play key roles in stellar halo formation around GCs and self-enrichment processes in the early phase of GC formation.

  18. A QUANTITATIVE KINETIC SCHEME FOR 70S TRANSLATION INITIATION COMPLEX FORMATION

    PubMed Central

    Grigoriadou, Christina; Marzi, Stefano; Kirillov, Stanislas; Gualerzi, Claudio O.; Cooperman, Barry S.

    2007-01-01

    SUMMARY Association of the 30S initiation complex (30SIC) and the 50S ribosomal subunit, leading to formation of the 70S initiation complex (70SIC), is a critical step of the translation initiation pathway. The 70SIC contains initiator tRNA, fMet-tRNAfMet, bound in the P (peptidyl)-site in response to the AUG start codon. We have formulated a quantitative kinetic scheme for the formation of an active 70SIC from 30SIC and 50S subunits on the basis of parallel rapid kinetics measurements of GTP hydrolysis, Pi release, light scattering, and changes in fluorescence intensities of fluorophore-labeled IF2 and fMet-tRNAfMet. According to this scheme, an initially formed labile 70S complex, which promotes rapid IF2-dependent GTP hydrolysis, either dissociates reversibly into 30S and 50S subunits or is converted to a more stable form, leading to 70SIC formation. The latter process takes place with intervening conformational changes of ribosome-bound IF2 and fMet-tRNAfMet, which are monitored by spectral changes of fluorescent derivatives of IF2 and fMet-tRNAfMet. The availability of such a scheme provides a useful framework for precisely elucidating the mechanisms by which substituting the nonhydrolyzable analogue GDPCP for GTP or adding thiostrepton inhibit formation of a productive 70SIC. GDPCP does not affect stable 70S formation, but perturbs fMet-tRNAfMet positioning in the P-site. In contrast, thiostrepton severely retards stable 70S formation, but allows normal binding of fMet-tRNAfMet(prf20) to the P-site. PMID:17868692

  19. Evaluation of bone formation guided by DNA/protamine complex with FGF-2 in an adult rat calvarial defect model.

    PubMed

    Shinozaki, Yosuke; Toda, Masako; Ohno, Jun; Kawaguchi, Minoru; Kido, Hirofumi; Fukushima, Tadao

    2014-11-01

    DNA/protamine complex paste (D/P) and D/P complex paste with Fibroblast Growth Factor-2 (FGF-2) (D/P-FGF) were prepared to investigate their new bone formation abilities using an ∼40-week-old rat calvarial defect model. It was found that D/P could release FGF-2 proportionally in an in vitro experiment with an enzyme-linked immunosorbent assay. It was also found that aging adversely affected self-bone healing of rats by comparison with the results in a previous study using 10-week-old rats. Microcomputed tomography and histopathological examinations showed that new bone formation abilities of D/P and D/P-FGF were superior to that of the control (sham operation). Control, D/P and D/P-FGF showed newly formed bone areas of 6.7, 58.3, and 67.0%, respectively, 3 months after the operation. Moreover, it was found that FGF-2 could support the osteoanagenesis ability of D/P. It was considered that FGF-2 could play an important role in new bone formation at early stages because it induced the genes such as collagen I, CBFA, OSX, and OPN, which are initiated first in the process of osteogenesis. Therefore, D/P-FGF will be a useful injectable biomaterial with biodegradable properties for the repair of bone defects in the elderly.

  20. A Reaction Method for Estimating Gibbs Energy and Enthalpy of Formation of Complex Minerals

    NASA Astrophysics Data System (ADS)

    Li, Ruibing; Zhang, Tingan; Liu, Yan; Kuang, Shibo

    2017-04-01

    New and updated thermodynamic data for simple binary compounds are readily available from both experimental measurements and theoretical calculations. Based on these available data, an approach is proposed to predict Gibbs energies and enthalpies of formation for complex minerals of metallurgical, chemical, and other industrial importance. The approach assumes that complex minerals are formed from binary composite oxides, which in turn, are formed from individual pure oxides. The validity of this approach is examined by comparing the calculated values of Gibbs energies and enthalpies against the experimentally measured ones reported in literature. The results show that for typical complex minerals with available experimental data, the calculated results exhibit an average residual of 0.51 pct for Gibbs energies and 0.52 pct for enthalpies, compared to the experimental results. This new approach thus correlates well with experimental approaches and can be applied to most of the complex minerals.

  1. The formation of molecular aggregates of sulfophthalocyanine in complexes with semiconductor nanocrystals

    NASA Astrophysics Data System (ADS)

    Dadadzhanov, D. R.; Martynenko, I. V.; Orlova, A. O.; Maslov, V. G.; Fedorov, A. V.; Baranov, A. V.

    2015-11-01

    In this study, complexes of CdSe/ZnS quantum dots and quantum rods with sulfophthalocyanine molecules have been formed. Analysis of spectral and luminescent properties of solutions of the complexes has revealed that an increase in the number of molecules per one nanocrystal in a mixed solution results in a noticeable decrease in the intensity of the luminescence of the quantum dots and quantum rods. In addition, it has been found that, upon an increase in the concentration of sulfophthalocyanine molecules, the absorption spectra of the samples in the region of their first absorption band have signs of formation of nonluminiscent aggregates of sulfophthalocyanine molecules. Analysis of the absorption spectra of the mixed solutions has made it possible to demonstrate that the complexes with the quantum rods have a content of the sulfophthalocyanine aggregates significantly lower than the complexes with the quantum dots.

  2. A Reaction Method for Estimating Gibbs Energy and Enthalpy of Formation of Complex Minerals

    NASA Astrophysics Data System (ADS)

    Li, Ruibing; Zhang, Tingan; Liu, Yan; Kuang, Shibo

    2017-01-01

    Abstract New and updated thermodynamic data for simple binary compounds are readily available from both experimental measurements and theoretical calculations. Based on these available data, an approach is proposed to predict Gibbs energies and enthalpies of formation for complex minerals of metallurgical, chemical, and other industrial importance. The approach assumes that complex minerals are formed from binary composite oxides, which in turn, are formed from individual pure oxides. The validity of this approach is examined by comparing the calculated values of Gibbs energies and enthalpies against the experimentally measured ones reported in literature. The results show that for typical complex minerals with available experimental data, the calculated results exhibit an average residual of 0.51 pct for Gibbs energies and 0.52 pct for enthalpies, compared to the experimental results. This new approach thus correlates well with experimental approaches and can be applied to most of the complex minerals.

  3. [Regulation of neurogenesis: factors affecting of new neurons formation in adult mammals brain].

    PubMed

    Respondek, Michalina; Buszman, Ewa

    2015-12-31

    Neurogenesis is a complex and multi-step process of generating completely functional neurons. This process in adult brain is based on pluripotentional neuronal stem cells (NSC), which are able to proliferation and differentiation into mature neurons or glial cells. NSC are located in subgranular zone inside hippocampus and in subventricular zone. The new neurons formation depends on many endo- and exogenous factors which modulate each step of neurogenesis. This article describes the most important regulators of adult neurogenesis, mainly: neurotrophins, growth factors, hormones, neurotransmitters and microenvironment of NSC. Some drugs, especially antipsychotics, antidepressants and normothymics may affect the neurogenic properties of adult brain. Moreover pathological processes such as neuroinflammation, stroke or epilepsy are able to induce proliferation of NSC. The proneurogenic effects of psychotropic drugs and pathological processes are associated with their ability to increase some hormones and neurotrophins level, as well as with rising the expression of antiapoptotic Bcl-2 protein and metalloproteinase MMP-2. Additionaly, some drugs, for example haloperidol, are able to block prolactin and dopaminergic neuroblasts receptors. Down-regulation of adult neurogenesis is associated with alcohol abuse and high stress level. Negative effect of many drugs, such as cytostatics, COX-2 inhibitors and opioides was also observed. The proneurogenic effect of described factors suggest their broad therapeutic potential and gives a new perspective on an effective and modern treatment of many neuropsychiatric disorders. This effect can also help to clarify the pathogenesis of disorders associated with proliferation and degeneration of adult brain cells.

  4. Investigation of Model Sunscreen Formulations Comparing the Sun Protection Factor, the Universal Sun Protection Factor and the Radical Formation Ratio.

    PubMed

    Syring, Felicia; Weigmann, Hans-Jürgen; Schanzer, Sabine; Meinke, Martina C; Knorr, Fanny; Lademann, Jürgen

    2016-01-01

    In view of globally rising skin cancer rates and harmful effects exerted by sunlight throughout the ultraviolet, visible and infrared ranges, an objective, safe and comprehensive method for determining sunscreen efficacy is required in order to warrant safe sun exposure. In this study, the influence of characteristic active ingredients (chemical filters, physical filters and antioxidants) on different sunscreen indicators, including the universal sun protection factor and the radical formation ratio, was determined and compared to their influence on sun protection factor values. Spectroscopic universal sun protection factor measurements were conducted ex vivo by analyzing tape strips taken from human skin, and radical formation ratio determination was performed via electron paramagnetic resonance spectroscopy using porcine ear skin ex vivo. The sun protection factor determination was conducted according to ISO standards (ISO 24444:2010). It was shown that chemical filters provide a protective effect which was measurable by all methods examined (spectroscopy, electron paramagnetic resonance spectroscopy and erythema formation). Physical filters, when used as single active ingredients, increased protective values in universal sun protection factor and sun protection factor measurements but exhibited no significant effect on universal sun protection factor measurements when used in combination with chemical filters or antioxidants. Antioxidants were shown to increase sun protection factor values. Radical formation ratio values were shown to be influenced merely by chemical filters, leading to the conclusion that the universal sun protection factor is the most suitable efficacy indicator for the ultraviolet range.

  5. Rapid-reaction kinetic characterization of the pathway of streptokinase-plasmin catalytic complex formation.

    PubMed

    Verhamme, Ingrid M; Bock, Paul E

    2008-09-19

    Binding of the fibrinolytic proteinase plasmin (Pm) to streptokinase (SK) in a tight stoichiometric complex transforms Pm into a potent proteolytic activator of plasminogen. SK binding to the catalytic domain of Pm, with a dissociation constant of 12 pm, is assisted by SK Lys(414) binding to a Pm kringle, which accounts for a 11-20-fold affinity decrease when Pm lysine binding sites are blocked by 6-aminohexanoic acid (6-AHA) or benzamidine. The pathway of SK.Pm catalytic complex formation was characterized by stopped-flow kinetics of SK and the Lys(414) deletion mutant (SKDeltaK414) binding to Pm labeled at the active site with 5-fluorescein ([5F]FFR-Pm) and the reverse reactions by competitive displacement of [5F]FFR-Pm with active site-blocked Pm. The rate constants for the biexponential fluorescence quenching caused by SK and SKDeltaK414 binding to [5F]FFR-Pm were saturable as a function of SK concentration, reporting encounter complex affinities of 62-110 nm in the absence of lysine analogs and 4900-6500 and 1430-2200 nm in the presence of 6-AHA and benzamidine, respectively. The encounter complex with SKDeltaK414 was approximately 10-fold weaker in the absence of lysine analogs but indistinguishable from that of native SK in the presence of 6-AHA and benzamidine. The studies delineate for the first time the sequence of molecular events in the formation of the SK.Pm catalytic complex and its regulation by kringle ligands. Analysis of the forward and reverse reactions supports a binding mechanism in which SK Lys(414) binding to a Pm kringle accompanies near-diffusion-limited encounter complex formation followed by two slower, tightening conformational changes.

  6. Protein complexing in a methanogen suggests electron bifurcation and electron delivery from formate to heterodisulfide reductase

    PubMed Central

    Costa, Kyle C.; Wong, Phoebe M.; Wang, Tiansong; Lie, Thomas J.; Dodsworth, Jeremy A.; Swanson, Ingrid; Burn, June A.; Hackett, Murray; Leigh, John A.

    2010-01-01

    In methanogenic Archaea, the final step of methanogenesis generates methane and a heterodisulfide of coenzyme M and coenzyme B (CoM-S-S-CoB). Reduction of this heterodisulfide by heterodisulfide reductase to regenerate HS-CoM and HS-CoB is an exergonic process. Thauer et al. [Thauer, et al. 2008 Nat Rev Microbiol 6:579–591] recently suggested that in hydrogenotrophic methanogens the energy of heterodisulfide reduction powers the most endergonic reaction in the pathway, catalyzed by the formylmethanofuran dehydrogenase, via flavin-based electron bifurcation. Here we present evidence that these two steps in methanogenesis are physically linked. We identify a protein complex from the hydrogenotrophic methanogen, Methanococcus maripaludis, that contains heterodisulfide reductase, formylmethanofuran dehydrogenase, F420-nonreducing hydrogenase, and formate dehydrogenase. In addition to establishing a physical basis for the electron-bifurcation model of energy conservation, the composition of the complex also suggests that either H2 or formate (two alternative electron donors for methanogenesis) can donate electrons to the heterodisulfide-H2 via F420-nonreducing hydrogenase or formate via formate dehydrogenase. Electron flow from formate to the heterodisulfide rather than the use of H2 as an intermediate represents a previously unknown path of electron flow in methanogenesis. We further tested whether this path occurs by constructing a mutant lacking F420-nonreducing hydrogenase. The mutant displayed growth equal to wild-type with formate but markedly slower growth with hydrogen. The results support the model of electron bifurcation and suggest that formate, like H2, is closely integrated into the methanogenic pathway. PMID:20534465

  7. Using chemical shifts to determine structural changes in proteins upon complex formation.

    PubMed

    Cavalli, Andrea; Montalvao, Rinaldo W; Vendruscolo, Michele

    2011-08-04

    Methods for determining protein structures using only chemical shift information are progressively becoming more accurate and reliable. A major problem, however, in the use of chemical shifts for the determination of the structures of protein complexes is that the changes in the chemical shifts upon binding tend to be rather limited and indeed often smaller than the standard errors made in the predictions of chemical shifts corresponding to given structures. We present a procedure that, despite this problem, enables one to use of chemical shifts to determine accurately the conformational changes that take place upon complex formation.

  8. Multinuclear complex formation between Ca(II) and gluconate ions in hyperalkaline solutions.

    PubMed

    Pallagi, Attila; Bajnóczi, Éva G; Canton, Sophie E; Bolin, Trudy; Peintler, Gábor; Kutus, Bence; Kele, Zoltán; Pálinkó, István; Sipos, Pál

    2014-06-17

    Alkaline solutions containing polyhydroxy carboxylates and Ca(II) are typical in cementitious radioactive waste repositories. Gluconate (Gluc(-)) is a structural and functional representative of these sugar carboxylates. In the current study, the structure and equilibria of complexes forming in such strongly alkaline solutions containing Ca(2+) and gluconate have been studied. It was found that Gluc(-) significantly increases the solubility of portlandite (Ca(OH)2(s)) under these conditions and Ca(2+) complexes of unexpectedly high stability are formed. The mononuclear (CaGluc(+) and [CaGlucOH](0)) complexes were found to be minor species, and predominant multinuclear complexes were identified. The formation of the neutral [Ca2Gluc(OH)3](0) (log β213 = 8.03) and [Ca3Gluc2(OH)4](0) (log β324 = 12.39) has been proven via H2/Pt-electrode potentiometric measurements and was confirmed via XAS, (1)H NMR, ESI-MS, conductometry, and freezing-point depression experiments. The binding sites of Gluc(-) were identified from multinuclear NMR measurements. Besides the carboxylate group, the O atoms on the second and third carbon atoms were proved to be the most probable sites for Ca(2+) binding. The suggested structure of the trinuclear complex was deduced from ab initio calculations. These observations are of relevance in the thermodynamic modeling of radioactive waste repositories, where the predominance of the binuclear Ca(2+) complex, which is a precursor of various high-stability ternary complexes with actinides, is demonstrated.

  9. Green synthesis of ZnO nanoparticles via complex formation by using Curcuma longa extract

    SciTech Connect

    Fatimah, Is Yudha, Septian P.; Mutiara, Nur Afisa Lintang

    2016-02-08

    Synthesis of ZnO nanoparticles(NPs) were conducted via Zn(II) complex formation by using Curcuma longa extract as template. Curcuma longa extract has the ability to form zinc ions complex with curcumin as ligating agent. Study on synthesis was conducted by monitoring thermal degradation of the material. Successful formation of zinc oxide nanoparticles was confirmed by employing x-ray diffraction, surface area analysis and transmission electron microscopy(TEM) studies. From the XRD analysis it is denoted that ZnO in hexagonal wurtzite phase was formed and particle size was varied as varied temperature. The data are also confirmed by TEM analysis which shows the particle sie at the range 20-80nm. The NPs exhibited excelent photocatalytic activity for methylene blue degradation and also significant antibacterial activity for Eschericia coli. The activity in methylene blue degradation was also confirmed from fast chemical oxygen demand (COD) reduction.

  10. Green synthesis of ZnO nanoparticles via complex formation by using Curcuma longa extract

    NASA Astrophysics Data System (ADS)

    Fatimah, Is; Yudha, Septian P.; Mutiara, Nur Afisa Lintang

    2016-02-01

    Synthesis of ZnO nanoparticles(NPs) were conducted via Zn(II) complex formation by using Curcuma longa extract as template. Curcuma longa extract has the ability to form zinc ions complex with curcumin as ligating agent. Study on synthesis was conducted by monitoring thermal degradation of the material. Successful formation of zinc oxide nanoparticles was confirmed by employing x-ray diffraction, surface area analysis and transmission electron microscopy(TEM) studies. From the XRD analysis it is denoted that ZnO in hexagonal wurtzite phase was formed and particle size was varied as varied temperature. The data are also confirmed by TEM analysis which shows the particle sie at the range 20-80nm. The NPs exhibited excelent photocatalytic activity for methylene blue degradation and also significant antibacterial activity for Eschericia coli. The activity in methylene blue degradation was also confirmed from fast chemical oxygen demand (COD) reduction.

  11. Pattern formation based on complex coupling mechanism in dielectric barrier discharge

    NASA Astrophysics Data System (ADS)

    Liu, Weibo; Dong, Lifang; Wang, Yongjie; Zhang, Hao; Pan, Yuyang

    2016-08-01

    The pattern formation of cinque-dice square superlattice pattern (CDSSP) is investigated based on the complex coupling mechanism in a dielectric barrier discharge (DBD) system. The spatio-temporal structure of CDSSP obtained by using an intensified-charge coupled device indicates that CDSSP is an interleaving of two kinds of subpatterns (mixture of rectangle and square, and dot-line square) which discharge twice in one half voltage, respectively. Selected by the complex coupling of two subpatterns, the CDSSP can be formed and shows good stability. This investigation based on gas discharge theory together with nonlinear theory may provide a deeper understanding for the nonlinear characteristics and even the formation mechanism of patterns in DBD.

  12. Unique behaviour of dinitrogen-bridged dimolybdenum complexes bearing pincer ligand towards catalytic formation of ammonia

    PubMed Central

    Tanaka, Hiromasa; Arashiba, Kazuya; Kuriyama, Shogo; Sasada, Akira; Nakajima, Kazunari; Yoshizawa, Kazunari; Nishibayashi, Yoshiaki

    2014-01-01

    It is vital to design effective nitrogen fixation systems that operate under mild conditions, and to this end we recently reported an example of the catalytic formation of ammonia using a dinitrogen-bridged dimolybdenum complex bearing a pincer ligand, where up to twenty three equivalents of ammonia were produced based on the catalyst. Here we study the origin of the catalytic behaviour of the dinitrogen-bridged dimolybdenum complex bearing the pincer ligand with density functional theory calculations, based on stoichiometric and catalytic formation of ammonia from molecular dinitrogen under ambient conditions. Comparison of di- and mono-molybdenum systems shows that the dinitrogen-bridged dimolybdenum core structure plays a critical role in the protonation of the coordinated molecular dinitrogen in the catalytic cycle. PMID:24769530

  13. [Energetics of complex formation of the DNA hairpin structure d(GCGAAGC) with aromatic ligands].

    PubMed

    Kostiukov, V V

    2011-01-01

    The energy contributions of various physical interactions to the total Gibbs energy of complex formation of the biologically important DNA hairpin d(GCGAAGC) with aromatic antitumor antibiotics daunomycin and novantron and the mutagens ethidium and proflavine have been calculated. It has been shown that the relatively small value of the total energy of binding of the ligands to the hairpin is the sum of components great in absolute value and different in sign. The contributions of van der Waals interactions and both intra- and intermolecular hydrogen bonds and bonds with aqueous environment have been studied. According to the calculations, the hydrophobic and van der Waals components are energetically favorable in complex formation of the ligands with the DNA pairpin d(GCGAAGC), whereas the electrostatic (with consideration of hydrogen bonds) and entropic components are unfavorable.

  14. Engineering Hydrogen Gas Production from Formate in a Hyperthermophile by Heterologous Production of an 18-Subunit Membrane-bound Complex*

    PubMed Central

    Lipscomb, Gina L.; Schut, Gerrit J.; Thorgersen, Michael P.; Nixon, William J.; Kelly, Robert M.; Adams, Michael W. W.

    2014-01-01

    Biohydrogen gas has enormous potential as a source of reductant for the microbial production of biofuels, but its low solubility and poor gas mass transfer rates are limiting factors. These limitations could be circumvented by engineering biofuel production in microorganisms that are also capable of generating H2 from highly soluble chemicals such as formate, which can function as an electron donor. Herein, the model hyperthermophile, Pyrococcus furiosus, which grows optimally near 100 °C by fermenting sugars to produce H2, has been engineered to also efficiently convert formate to H2. Using a bacterial artificial chromosome vector, the 16.9-kb 18-gene cluster encoding the membrane-bound, respiratory formate hydrogen lyase complex of Thermococcus onnurineus was inserted into the P. furiosus chromosome and expressed as a functional unit. This enabled P. furiosus to utilize formate as well as sugars as an H2 source and to do so at both 80° and 95 °C, near the optimum growth temperature of the donor (T. onnurineus) and engineered host (P. furiosus), respectively. This accomplishment also demonstrates the versatility of P. furiosus for metabolic engineering applications. PMID:24318960

  15. Integrin-Associated Complexes Form Hierarchically with Variable Stoichiometry during Nascent Adhesion Formation

    PubMed Central

    Bachir, Alexia I.; Zareno, Jessica; Moissoglu, Konstadinos; Plow, Edward; Gratton, Enrico; Horwitz, Alan R.

    2014-01-01

    Summary Background A complex network of putative molecular interactions underlies the architecture and function of cell-matrix adhesions. Most of these interactions are implicated from co-immunoprecipitation studies using expressed components; but few have been demonstrated or characterized functionally in living cells. Results We introduce fluorescence fluctuation methods to determine, at high spatial and temporal resolution, ‘when’ and ‘where’ molecular complexes form and their stoichiometry in nascent adhesions (NAs). We focus on integrin-associated molecules implicated in integrin-activation and in the integrin-actin linkage in NAs and show that these molecules form integrin containing complexes hierarchically within the adhesion itself. Integrin and kindlin reside in a molecular complex as soon as adhesions are visible; talin, while also present early, associates with the integrin-kindlin complex only after NAs have formed and in response to myosin II activity. Furthermore, talin and vinculin association precedes the formation of the integrin-talin complex. Finally, α-actinin enters NAs periodically and in clusters that transiently associate with integrins. The absolute number and stoichiometry of these molecules varies among the molecules studied and changes as adhesions mature. Conclusions These observations suggest a working model for NA assembly, whereby transient α-actinin- integrin complexes help nucleate NAs within the lamellipodium. Subsequently integrin complexes containing kindlin, but not talin, emerge. Once NAs have formed, myosin II activity promotes talin association with the integrin-kindlin complex in a stoichiometry consistent with each talin molecule linking two integrin-kindlin complexes. PMID:25088556

  16. The standard enthalpies of combustion and formation of crystalline cobalt tetrakis(4-metoxyphenyl)porphin complex

    NASA Astrophysics Data System (ADS)

    Tarasov, R. P.; Volkov, A. V.; Bazanov, M. I.; Semeikin, A. S.

    2009-05-01

    The energy of combustion of cobalt tetrakis(4-metoxyphenyl)porphin was determined in an isothermic-shell liquid calorimeter with a stationary calorimetric bomb. The standard enthalpies of combustion and formation of the complex were calculated, -Δ c H o = 27334.06 ± 50.98 kJ/mol and Δf H o = 3062.90 ± 50.97 kJ/mol.

  17. Display format and highlight validity effects on search performance using complex visual displays

    NASA Technical Reports Server (NTRS)

    Donner, Kimberly A.; Mckay, Tim; O'Brien, Kevin M.; Rudisill, Marianne

    1991-01-01

    Display format and highlight validity were shown to affect visual display search performance; however, these studies were conducted on small, artificial displays of alphanumeric stimuli. A study manipulating these variables was conducted using realistic, complex Space Shuttle information displays. A 2x2x3 within-subjects analysis of variance found that search times were faster for items in reformatted displays than for current displays. The significant format by highlight validity interaction showed that there was little difference in response time to both current and reformatted displays when the highlight validity was applied; however, under the non or invalid highlight conditions, search times were faster with reformatted displays. Benefits of highlighting and reformatting displays to enhance search and the necessity to consider highlight validity and format characteristics in tandem for predicting search performance are discussed.

  18. Microscopic Mechanism and Kinetics of Ice Formation at Complex Interfaces: Zooming in on Kaolinite.

    PubMed

    Sosso, Gabriele C; Li, Tianshu; Donadio, Davide; Tribello, Gareth A; Michaelides, Angelos

    2016-07-07

    Most ice in nature forms because of impurities which boost the exceedingly low nucleation rate of pure supercooled water. However, the microscopic details of ice nucleation on these substances remain largely unknown. Here, we have unraveled the molecular mechanism and the kinetics of ice formation on kaolinite, a clay mineral playing a key role in climate science. We find that the formation of ice at strong supercooling in the presence of this clay is about 20 orders of magnitude faster than homogeneous freezing. The critical nucleus is substantially smaller than that found for homogeneous nucleation and, in contrast to the predictions of classical nucleation theory (CNT), it has a strong two-dimensional character. Nonetheless, we show that CNT describes correctly the formation of ice at this complex interface. Kaolinite also promotes the exclusive nucleation of hexagonal ice, as opposed to homogeneous freezing where a mixture of cubic and hexagonal polytypes is observed.

  19. Microscopic Mechanism and Kinetics of Ice Formation at Complex Interfaces: Zooming in on Kaolinite

    PubMed Central

    2016-01-01

    Most ice in nature forms because of impurities which boost the exceedingly low nucleation rate of pure supercooled water. However, the microscopic details of ice nucleation on these substances remain largely unknown. Here, we have unraveled the molecular mechanism and the kinetics of ice formation on kaolinite, a clay mineral playing a key role in climate science. We find that the formation of ice at strong supercooling in the presence of this clay is about 20 orders of magnitude faster than homogeneous freezing. The critical nucleus is substantially smaller than that found for homogeneous nucleation and, in contrast to the predictions of classical nucleation theory (CNT), it has a strong two-dimensional character. Nonetheless, we show that CNT describes correctly the formation of ice at this complex interface. Kaolinite also promotes the exclusive nucleation of hexagonal ice, as opposed to homogeneous freezing where a mixture of cubic and hexagonal polytypes is observed. PMID:27269363

  20. The LINC complex component Sun4 plays a crucial role in sperm head formation and fertility

    PubMed Central

    Pasch, Elisabeth; Link, Jana; Beck, Carolin; Scheuerle, Stefanie; Alsheimer, Manfred

    2015-01-01

    ABSTRACT LINC complexes are evolutionarily conserved nuclear envelope bridges, physically connecting the nucleus to the peripheral cytoskeleton. They are pivotal for dynamic cellular and developmental processes, like nuclear migration, anchoring and positioning, meiotic chromosome movements and maintenance of cell polarity and nuclear shape. Active nuclear reshaping is a hallmark of mammalian sperm development and, by transducing cytoskeletal forces to the nuclear envelope, LINC complexes could be vital for sperm head formation as well. We here analyzed in detail the behavior and function of Sun4, a bona fide testis-specific LINC component. We demonstrate that Sun4 is solely expressed in spermatids and there localizes to the posterior nuclear envelope, likely interacting with Sun3/Nesprin1 LINC components. Our study revealed that Sun4 deficiency severely impacts the nucleocytoplasmic junction, leads to mislocalization of other LINC components and interferes with the formation of the microtubule manchette, which finally culminates in a globozoospermia-like phenotype. Together, our study provides direct evidence for a critical role of LINC complexes in mammalian sperm head formation and male fertility. PMID:26621829

  1. True boundary for the formation of homoleptic transition-metal hydride complexes.

    PubMed

    Takagi, Shigeyuki; Iijima, Yuki; Sato, Toyoto; Saitoh, Hiroyuki; Ikeda, Kazutaka; Otomo, Toshiya; Miwa, Kazutoshi; Ikeshoji, Tamio; Aoki, Katsutoshi; Orimo, Shin-ichi

    2015-05-04

    Despite many exploratory studies over the past several decades, the presently known transition metals that form homoleptic transition-metal hydride complexes are limited to the Groups 7-12. Here we present evidence for the formation of Mg3 CrH8 , containing the first Group 6 hydride complex [CrH7 ](5-) . Our theoretical calculations reveal that pentagonal-bipyramidal H coordination allows the formation of σ-bonds between H and Cr. The results are strongly supported by neutron diffraction and IR spectroscopic measurements. Given that the Group 3-5 elements favor ionic/metallic bonding with H, along with the current results, the true boundary for the formation of homoleptic transition-metal hydride complexes should be between Group 5 and 6. As the H coordination number generally tends to increase with decreasing atomic number of transition metals, the revised boundary suggests high potential for further discovery of hydrogen-rich materials that are of both technological and fundamental interest.

  2. Rapid formation of cell-particle complexes via dielectrophoretic manipulation for the detection of surface antigens.

    PubMed

    Horii, Takuma; Yamamoto, Masashi; Yasukawa, Tomoyuki; Mizutani, Fumio

    2014-11-15

    A rapid and simple method for the fabrication of the island patterns with particles and cells was applied to detect the presence of specific antigens on the cell surface. An upper interdigitated microband array (IDA) electrode was mounted on a lower substrate with the same design to fabricate a microfluidic-channel device for dielectrophoretic manipulation. The electrode grid structure was fabricated by rotating the upper template IDA by 90° relative to the lower IDA. A suspension of anti-CD33 modified particles and HL-60 cells was introduced into the channel. An AC electrical signal (typically 20 V peak-to-peak, 100 kHz) was then applied to the bands of the upper and lower IDAs, resulting in the formation of island patterns at the intersections with low electric fields. Immunoreactions between the antibodies immobilized on the accumulated particles and the CD33 present on the surface of the cells led to the formation of complexes comprising corresponding antigen-antibody pairs. Non-specific pairs accumulated at the intersection, which did not form complexes, were then dispersed after removal of the applied field. The time required for the detection of the formation/dispersion of the complexes is as short as 6 min in the present procedure. Furthermore, this novel cell binding assay does not require pretreatment such as target labeling or washing of the unbound cells.

  3. Massive Star Formation in the Cygnus-X DR15 Complex

    NASA Astrophysics Data System (ADS)

    Laws, Anna; Hora, Joseph L.; Zhang, Qizhou

    2017-01-01

    To unravel the mysteries of massive star formation it is necessary to observe Young Stellar Objects (YSOs) in a variety of environments and evolutionary stages. The Cygnus-X region, at a distance of 1.4kpc, is one of the closest massive star-forming complexes and so offers an excellent view of the earliest stages of massive stars and clusters. A key area in this complex is DR15, a cluster population with many intriguing objects including a molecular pillar and InfraRed Dark Cloud (IRDC) that is likely to host newly forming massive stars. Previous infrared studies incorporating data from Spitzer and Herschel have built catalogs of YSOs in the DR15 region, revealing its abundance of massive star formation. To improve on these catalogs and to probe the earliest stages of star formation, we have observed the region at high spatial resolution using the Submillimeter Array (SMA). The SMA data are more sensitive to objects in earlier evolutionary phases and provide additional constraints when modeling the Spectral Energy Distribution (SED) of each star, resulting in more accurate values for each star’s mass and accretion rate. The SMA data allow us to trace the particular YSOs that are actively accreting and drive molecular outflows, which influence the ISM and chemical trends across the region. DR15 offers an exciting chance to expand our understanding of the processes behind massive star formation.

  4. Carotenoid-induced cooperative formation of bacterial photosynthetic LH1 complex.

    PubMed

    Fiedor, Leszek; Akahane, Junji; Koyama, Yasushi

    2004-12-28

    A simple reconstitution technique has been developed and then applied to prepare a series of light-harvesting antenna 1 (LH1) complexes with a programmed carotenoid composition, not available from native photosynthetic membranes. The complexes were reconstituted with different C(40) carotenoids, having two structural parameters variable: the functional side groups and the number of conjugated C-C double bonds, systematically increasing from 9 to 13. The complexes, differing only in the type of carotenoid, bound to an otherwise identical bacteriochlorophyll-polypeptide matrix, can serve as a unique model system in which the relationship between the carotenoid character and the functioning of pigment-protein complexes can be investigated. The reconstituted LH1 complexes resemble the native antenna, isolated from wild-type Rhodospirillum rubrum, but their coloration is entirely determined by carotenoid. Along with the increase in its conjugation size, the carotenoid absorption transitions gradually shift to the red. Thus, the extension of the conjugation size of the antenna carotenoids provides a mechanism for the spectral tuning of light harvesting in the visible part of the spectrum. The carotenoids in the reconstitution system promote the LH1 formation and seem to bind and transfer the excitation energy specifically only to a species with characteristically red-shifted absorption and emission maxima, apparently, due to a cooperative effect. Monitoring the LH1 formation by steady-state absorption and fluorescence spectroscopies reveals that in the presence of carotenoids it proceeds without spectrally resolved intermediates, leading directly to B880. The effect of the carotenoid is enhanced when the pigment contains the hydroxy or methoxy side groups, implying that, in parallel to hydrophobic interactions and pi-pi stacking, other interactions are also involved in the formation and stabilization of LH1.

  5. Formylglycinamide Ribonucleotide Amidotransferase from Thermotoga maritima: Structural Insights into Complex Formation

    SciTech Connect

    Morar, Mariya; Hoskins, Aaron A.; Stubbe, JoAnne; Ealick, Steven E.

    2008-10-02

    In the fourth step of the purine biosynthetic pathway, formyl glycinamide ribonucleotide (FGAR) amidotransferase, also known as PurL, catalyzes the conversion of FGAR, ATP, and glutamine to formyl glycinamidine ribonucleotide (FGAM), ADP, P{sub i}, and glutamate. Two forms of PurL have been characterized, large and small. Large PurL, present in most Gram-negative bacteria and eukaryotes, consists of a single polypeptide chain and contains three major domains: the N-terminal domain, the FGAM synthetase domain, and the glutaminase domain, with a putative ammonia channel located between the active sites of the latter two. Small PurL, present in Gram-positive bacteria and archaea, is structurally homologous to the FGAM synthetase domain of large PurL, and forms a complex with two additional gene products, PurQ and PurS. The structure of the PurS dimer is homologous with the N-terminal domain of large PurL, while PurQ, whose structure has not been reported, contains the glutaminase activity. In Bacillus subtilis, the formation of the PurLQS complex is dependent on glutamine and ADP and has been demonstrated by size-exclusion chromatography. In this work, a structure of the PurLQS complex from Thermotoga maritima is described revealing a 2:1:1 stoichiometry of PurS:Q:L, respectively. The conformational changes observed in TmPurL upon complex formation elucidate the mechanism of metabolite-mediated recruitment of PurQ and PurS. The flexibility of the PurS dimer is proposed to play a role in the activation of the complex and the formation of the ammonia channel. A potential path for the ammonia channel is identified.

  6. Evaluation of CO2 migration and formation storage capacity in the Dalders formations, Baltic Sea - Preliminary analysis by means of models of increasing complexity

    NASA Astrophysics Data System (ADS)

    Niemi, Auli; Yang, Zhibing; Tian, Liang; Jung, Byeongju; Fagerlund, Fritjof; Joodaki, Saba; Pasquali, Riccardo; O'Neill, Nick; Vernon, Richard

    2014-05-01

    We present preliminary data analysis and modeling of CO2 injection into selected parts of the Dalders Monocline and Dalders Structure, formations situated under the Baltic Sea and of potential interest for CO2 geological storage. The approach taken is to use models of increasing complexity successively, thereby increasing the confidence and reliability of the predictions. The objective is to get order-of-magnitude estimates of the behavior of the formations during potential industrial scale CO2 injection and subsequent storage periods. The focus has been in regions with best cap-rock characteristics, according to the present knowledge. Data has been compiled from various sources available, such as boreholes within the region. As the first approximation we use analytical solutions, in order to get an initial estimate the CO2 injection rates that can be used without causing unacceptable pressure increases. These preliminary values are then used as basis for more detailed numerical analyses with TOUGH2/TOUGH2-MP (e.g. Zhang et al, 2008) simulator and vertical equilibrium based (e.g. Gasda et al, 2009) models. With the numerical models the variations in material properties, formation thickness etc., as well as more processes such as CO2 dissolution can also be taken into account. The presentation discusses results from these preliminary analyses in terms of estimated storage capacity, CO2 and pressure plume extent caused by various injection scenarios, as well as CO2 travel time after the end of the injection. The effect of factors such as number of injection wells and the positioning of these, the effect of formation properties and the boundary conditions are discussed as are the benefits and disadvantages of the various modeling approaches used. References: Gasda S.E. et al, 2009. Computational Geosciences 13, 469-481. Zhang et al, 2008. Report LBNL-315E, Lawrence Berkeley National Laboratory.

  7. Formation and Recondensation of Complex Organic Molecules during Protostellar Luminosity Outbursts

    NASA Astrophysics Data System (ADS)

    Taquet, Vianney; Wirström, Eva S.; Charnley, Steven B.

    2016-04-01

    During the formation of stars, the accretion of surrounding material toward the central object is thought to undergo strong luminosity outbursts followed by long periods of relative quiescence, even at the early stages of star formation when the protostar is still embedded in a large envelope. We investigated the gas-phase formation and recondensation of the complex organic molecules (COMs) di-methyl ether and methyl formate, induced by sudden ice evaporation processes occurring during luminosity outbursts of different amplitudes in protostellar envelopes. For this purpose, we updated a gas-phase chemical network forming COMs in which ammonia plays a key role. The model calculations presented here demonstrate that ion-molecule reactions alone could account for the observed presence of di-methyl ether and methyl formate in a large fraction of protostellar cores without recourse to grain-surface chemistry, although they depend on uncertain ice abundances and gas-phase reaction branching ratios. In spite of the short outburst timescales of about 100 years, abundance ratios of the considered species higher than 10% with respect to methanol are predicted during outbursts due to their low binding energies relative to water and methanol which delay their recondensation during cooling. Although the current luminosity of most embedded protostars would be too low to produce complex organics in the hot-core regions that are observable with current sub-millimetric interferometers, previous luminosity outburst events would induce the formation of COMs in extended regions of protostellar envelopes with sizes increasing by up to one order of magnitude.

  8. FORMATION AND RECONDENSATION OF COMPLEX ORGANIC MOLECULES DURING PROTOSTELLAR LUMINOSITY OUTBURSTS

    SciTech Connect

    Taquet, Vianney; Wirström, Eva S.; Charnley, Steven B.

    2016-04-10

    During the formation of stars, the accretion of surrounding material toward the central object is thought to undergo strong luminosity outbursts followed by long periods of relative quiescence, even at the early stages of star formation when the protostar is still embedded in a large envelope. We investigated the gas-phase formation and recondensation of the complex organic molecules (COMs) di-methyl ether and methyl formate, induced by sudden ice evaporation processes occurring during luminosity outbursts of different amplitudes in protostellar envelopes. For this purpose, we updated a gas-phase chemical network forming COMs in which ammonia plays a key role. The model calculations presented here demonstrate that ion–molecule reactions alone could account for the observed presence of di-methyl ether and methyl formate in a large fraction of protostellar cores without recourse to grain-surface chemistry, although they depend on uncertain ice abundances and gas-phase reaction branching ratios. In spite of the short outburst timescales of about 100 years, abundance ratios of the considered species higher than 10% with respect to methanol are predicted during outbursts due to their low binding energies relative to water and methanol which delay their recondensation during cooling. Although the current luminosity of most embedded protostars would be too low to produce complex organics in the hot-core regions that are observable with current sub-millimetric interferometers, previous luminosity outburst events would induce the formation of COMs in extended regions of protostellar envelopes with sizes increasing by up to one order of magnitude.

  9. Formation and Recondensation of Complex Organic Molecules During Protostellar Luminosity Outbursts

    NASA Technical Reports Server (NTRS)

    Taquet, Vianney; Wirstrom, Eva S.; Charnley, Steven B.

    2016-01-01

    During the formation of stars, the accretion of surrounding material toward the central object is thought to undergo strong luminosity outbursts followed by long periods of relative quiescence, even at the early stages of star formation when the protostar is still embedded in a large envelope. We investigated the gas-phase formation and recondensation of the complex organic molecules (COMs) di-methyl ether and methyl formate, induced by sudden ice evaporation processes occurring during luminosity outbursts of different amplitudes in protostellar envelopes. For this purpose, we updated a gas-phase chemical network forming COMs in which ammonia plays a key role. The model calculations presented here demonstrate that ion-molecule reactions alone could account for the observed presence of di-methyl ether and methyl formate in a large fraction of protostellar cores without recourse to grain-surface chemistry, although they depend on uncertain ice abundances and gas-phase reaction branching ratios. In spite of the short outburst timescales of about 100 years, abundance ratios of the considered species higher than 10% with respect to methanol are predicted during outbursts due to their low binding energies relative to water and methanol which delay their recondensation during cooling. Although the current luminosity of most embedded protostars would be too low to produce complex organics in the hot-core regions that are observable with current sub-millimetric interferometers, previous luminosity outburst events would induce the formation of COMs in extended regions of protostellar envelopes with sizes increasing by up to one order of magnitude.

  10. Method for determining formation quality factor from seismic data

    DOEpatents

    Taner, M. Turhan; Treitel, Sven

    2005-08-16

    A method is disclosed for calculating the quality factor Q from a seismic data trace. The method includes calculating a first and a second minimum phase inverse wavelet at a first and a second time interval along the seismic data trace, synthetically dividing the first wavelet by the second wavelet, Fourier transforming the result of the synthetic division, calculating the logarithm of this quotient of Fourier transforms and determining the slope of a best fit line to the logarithm of the quotient.

  11. Structure of solvated Fe(CO)5: complex formation during solvation in alcohols.

    PubMed

    Lessing, Joshua; Li, Xiaodi; Lee, Taewoo; Rose-Petruck, Christoph G

    2008-03-20

    The equilibrium structure of iron pentacarbonyl, Fe(CO)5, solvated in various alcohols has been investigated by Fourier transform infrared (FTIR) measurements and density functional theory calculations. This system was studied because it is prototypical of a larger class of monometallic systems, which are electronically saturated but not sterically crowded. Upon solvation, the Fe(CO)5 is not just surrounded by a solvation shell. Instead, solute-solvent complexes are formed with the oxygen of the alcohol oriented toward an axial ligand of the Fe(CO)5 giving a formation energy on the order of -5 kJ/mol. This complexation is not a chemical reaction but rather a "preassembly" of the solute molecules with a single solvent molecule. For instance, at room temperature the interaction between Fe(CO)5 and ethanol results in 87% of all Fe(CO)5 molecules being complexated with a single ethanol molecule. This complexation was found in all the alcohol systems studied in this paper. The stability of these complexes was found to depend on the alcohol chain length and branching. The observed complexation mechanism is accompanied by an electron density shift from the complexed alcohol molecule toward Fe(CO)5 where it induces a dipole moment. The finding that Fe(CO)5 forms a complex with the hydroxyl group of a single solvent molecule might have significant implications for ligand substitution reactions. This implies that ligand substitution reactions do not have to proceed via a dissociative mechanism. Instead, the reaction might proceed through a concerted mechanism with the leaving CO simultaneously being replaced by the incoming alcohol that was complexed to Fe(CO)5 prior to the photoexcitation.

  12. [Regularities of formation of chlorophyll-human serum albumin functionally active complexes in the aqueous medium].

    PubMed

    Semichaevskiĭ, V D

    1975-01-01

    In the system with constant content of the chlorophyll a and increasing amounts of human serum albumin, dependence of pigment incorporation into the complex upon interaction of its aqueous associates with protein solutions was studied by applying the gel filtration on Sephadex G-75 and by measuring light scattering and rate of sensitized photoreduction of the methyl red by ascorbic-acid. The curves were obtained after extraction of the chlorophyll by acetone from dry pigment-protein films formed after desiccation of the aqueous systems. Sigmoid character of the above dependences, their linearization in Hill's coordinates and the value of cooperativity coefficient close to 2 testifies in favour of the cooperative character of the complex formation, two pigment molecules reacting with a single protein molecule. Measurement of adsorption isotherms and their treatment with use of the Brunauer-Emmett-Teller theory of polymolecular adsorption make it possible to evaluate the maximum molar ratio of the pigment to the protein in the complex (close to 2). The pigment-pigment interaction suggests that the chlorophyll molecules adsorbed on the protein are in the state of loosely packed dimers. Deaggregation of aqueus pigment associates by the protein in the course of complex formation results in a considerable increase of the protosensitizing chlorophyll activity.

  13. Modifications of the acyl-d-alanyl-d-alanine terminus affecting complex-formation with vancomycin

    PubMed Central

    Nieto, M.; Perkins, H. R.

    1971-01-01

    Vancomycin forms complexes with peptides terminating in d-alanyl-d-alanine that are analogous to the biosynthetic precursors of bacterial mucopeptides. The specificity of complex-formation has been studied by means of many synthetic peptides, prepared by both solid-phase and conventional methods. The following conclusions can be drawn: (a) three amide linkages are required to form a stable complex; (b) the terminal carboxyl group must be free; (c) the carboxyl terminal and subterminal residues must be either glycine or of the d-configuration; (d) the size of the side chain in these residues greatly influences the affinity for vancomycin, a methyl group being the optimum in each case; (e) the nature of the side chain in the third and fourth residues has a smaller effect on complex-formation, but an l-configuration was somewhat better than a d-configuration in the third position. In addition to acyl-d-alanyl-d-alanine, other peptides that occur in bacterial cell walls will combine with vancomycin, although less strongly, e.g. acyl-d-alanyl-d-α-amino acid (where the terminal d-residue may form the cross-link in mucopeptide structure) and acyl-l-alanyl-d-glutamylglycine (a sequence found in the mucopeptide of Micrococcus lysodeikticus and related organisms). These results throw some light on the specificity of the uptake of vancomycin by living bacteria. PMID:5124386

  14. Actomyosin-dependent formation of the mechanosensitive talin-vinculin complex reinforces actin anchoring

    NASA Astrophysics Data System (ADS)

    Ciobanasu, Corina; Faivre, Bruno; Le Clainche, Christophe

    2014-01-01

    The force generated by the actomyosin cytoskeleton controls focal adhesion dynamics during cell migration. This process is thought to involve the mechanical unfolding of talin to expose cryptic vinculin-binding sites. However, the ability of the actomyosin cytoskeleton to directly control the formation of a talin-vinculin complex and the resulting activity of the complex are not known. Here we develop a microscopy assay with pure proteins in which the self-assembly of actomyosin cables controls the association of vinculin to a talin-micropatterned surface in a reversible manner. Quantifications indicate that talin refolding is limited by vinculin dissociation and modulated by the actomyosin network stability. Finally, we show that the activation of vinculin by stretched talin induces a positive feedback that reinforces the actin-talin-vinculin association. This in vitro reconstitution reveals the mechanism by which a key molecular switch senses and controls the connection between adhesion complexes and the actomyosin cytoskeleton.

  15. Formation and antimicrobial activity of complexes of beta-cyclodextrin and some antimycotic imidazole derivatives.

    PubMed

    Van Doorne, H; Bosch, E H; Lerk, C F

    1988-04-22

    Complex formation between beta-cyclodextrin and six antimycotic imidazole derivatives has been studied. The solubility of all drugs was increased in the presence of beta-cyclodextrin. The smallest increase (approx. 5-fold) was observed for miconazol, and the largest increase (approx. 160-fold) was observed for bifonazol. Apparent 1:1-complex constants were measured and found to decrease in the order: bifonazol greater than ketoconazol greater than tioconazol greater than miconazol greater than itraconazol greater than clotrimazol. The complexes appeared to possess a low, if any, antimicrobial activity. Measurement of inhibition zone sizes, with four test organisms was used to study the release of the antimycotic drugs from topical preparations. The antimycotic drugs were more readily released from topical preparations containing beta-cyclodextrin than from the same vehicles without beta-cyclodextrin. The rationale of beta-cyclodextrin addition to antimycotic topical preparations is discussed.

  16. WRAP53 is essential for Cajal body formation and for targeting the survival of motor neuron complex to Cajal bodies.

    PubMed

    Mahmoudi, Salah; Henriksson, Sofia; Weibrecht, Irene; Smith, Stephen; Söderberg, Ola; Strömblad, Staffan; Wiman, Klas G; Farnebo, Marianne

    2010-11-02

    The WRAP53 gene gives rise to a p53 antisense transcript that regulates p53. This gene also encodes a protein that directs small Cajal body-specific RNAs to Cajal bodies. Cajal bodies are nuclear organelles involved in diverse functions such as processing ribonucleoproteins important for splicing. Here we identify the WRAP53 protein as an essential factor for Cajal body maintenance and for directing the survival of motor neuron (SMN) complex to Cajal bodies. By RNA interference and immunofluorescence we show that Cajal bodies collapse without WRAP53 and that new Cajal bodies cannot be formed. By immunoprecipitation we find that WRAP53 associates with the Cajal body marker coilin, the splicing regulatory protein SMN, and the nuclear import receptor importinβ, and that WRAP53 is essential for complex formation between SMN-coilin and SMN-importinβ. Furthermore, depletion of WRAP53 leads to accumulation of SMN in the cytoplasm and prevents the SMN complex from reaching Cajal bodies. Thus, WRAP53 mediates the interaction between SMN and associated proteins, which is important for nuclear targeting of SMN and the subsequent localization of the SMN complex to Cajal bodies. Moreover, we detect reduced WRAP53-SMN binding in patients with spinal muscular atrophy, which is the leading genetic cause of infant mortality worldwide, caused by mutations in SMN1. This suggests that loss of WRAP53-mediated SMN trafficking contributes to spinal muscular atrophy.

  17. Having excess levels of PCSK9 is not sufficient to induce complex formation between PCSK9 and the LDL receptor.

    PubMed

    Wooten, Catherine J; Adcock, Audrey F; Agina-Obu, DaTonye I; Lopez, Dayami

    2014-03-01

    Proprotein convertase subtilisin/kexin-9 (PCSK9) acts mainly by forming complexes with the LDL receptor at the cell surface, which are then degraded in the lysosome. Studies were performed to determine whether excess levels of PCSK9 was sufficient to induce PCSK9/LDL receptor complex formation in human hepatocyte-like C3A cells. It was demonstrated using ELISA that instead of considering the overall levels of PCSK9 protein that is produced in response to certain treatment, what is critical is how much PCSK9 is actually capable of forming complexes. Despite the high levels, most of the PCSK9 produced as a result of incubating cells with a medium supplemented with BD™ MITO+ serum extender (MITO+ medium) appeared to be inhibited by a secreted factor. Having lower levels of PCSK9/LDL receptor complexes did not prevent an increase in the degradation rate of LDL receptors in MITO+ medium as compared to fetal bovine serum (FBS) containing medium (Regular medium), an effect that did not correlate with an increase in protein levels of the inducible degrader of LDL receptors (IDOL), as demonstrated using Western blotting analysis. Additional studies are required to determine the exact mechanism(s) for the degradation of the LDL receptor and/or to identify the secreted inhibitor of PCSK9.

  18. Effects of formate binding on the quinone-iron electron acceptor complex of photosystem II.

    PubMed

    Sedoud, Arezki; Kastner, Lisa; Cox, Nicholas; El-Alaoui, Sabah; Kirilovsky, Diana; Rutherford, A William

    2011-02-01

    EPR was used to study the influence of formate on the electron acceptor side of photosystem II (PSII) from Thermosynechococcus elongatus. Two new EPR signals were found and characterized. The first is assigned to the semiquinone form of Q(B) interacting magnetically with a high spin, non-heme-iron (Fe²(+), S=2) when the native bicarbonate/carbonate ligand is replaced by formate. This assignment is based on several experimental observations, the most important of which were: (i) its presence in the dark in a significant fraction of centers, and (ii) the period-of-two variations in the concentration expected for Q(B)(•-) when PSII underwent a series of single-electron turnovers. This signal is similar but not identical to the well-know formate-modified EPR signal observed for the Q(A)(•-)Fe²(+) complex (W.F.J. Vermaas and A.W. Rutherford, FEBS Lett. 175 (1984) 243-248). The formate-modified signals from Q(A)(•-)Fe²(+) and Q(B)(•-)Fe²(+) are also similar to native semiquinone-iron signals (Q(A)(•-)Fe²(+)/Q(B)(•-)Fe²(+)) seen in purple bacterial reaction centers where a glutamate provides the carboxylate ligand to the iron. The second new signal was formed when Q(A)(•-) was generated in formate-inhibited PSII when the secondary acceptor was reduced by two electrons. While the signal is reminiscent of the formate-modified semiquinone-iron signals, it is broader and its main turning point has a major sub-peak at higher field. This new signal is attributed to the Q(A)(•-)Fe²(+) with formate bound but which is perturbed when Q(B) is fully reduced, most likely as Q(B)H₂ (or possibly Q(B)H(•-) or Q(B)(²•-)). Flash experiments on formate-inhibited PSII monitoring these new EPR signals indicate that the outcome of charge separation on the first two flashes is not greatly modified by formate. However on the third flash and subsequent flashes, the modified Q(A)(•-)Fe²(+)Q(B)H₂ signal is trapped in the EPR experiment and there is a marked

  19. Serum response factor is essential for mesoderm formation during mouse embryogenesis.

    PubMed Central

    Arsenian, S; Weinhold, B; Oelgeschläger, M; Rüther, U; Nordheim, A

    1998-01-01

    The transcription factor serum response factor (SRF), a phylogenetically conserved nuclear protein, mediates the rapid transcriptional response to extracellular stimuli, e.g. growth and differentiation signals. DNA- protein complexes containing SRF or its homologues function as nuclear targets of the Ras/MAPK signalling network, thereby directing gene activities associated with processes as diverse as pheromone signalling, cell-cycle progression (transitions G0-G1 and G2-M), neuronal synaptic transmission and muscle cell differentiation. So far, the activity of mammalian SRF has been studied exclusively in cultured cells. To study SRF function in a multicellular organism we generated an Srf null allele in mice. SRF-deficient embryos (Srf -/-) have a severe gastrulation defect and do not develop to term. They consist of misfolded ectodermal and endodermal cell layers, do not form a primitive streak or any detectable mesodermal cells and fail to express the developmental marker genes Bra (T), Bmp-2/4 and Shh. Activation of the SRF-regulated immediate early genes Egr-1 and c-fos, as well as the alpha-Actin gene, is severely impaired. Our study identifies SRF as a new and essential regulator of mammalian mesoderm formation. We therefore suggest that in mammals Ras/MAPK signalling contributes to mesoderm induction, as is the case in amphibia. PMID:9799237

  20. Structural Complexities Influencing Biostratigraphic Interpretations of the Permian Nansen Formation type-section, Ellesmere Island, Canada

    NASA Astrophysics Data System (ADS)

    Hill, M.; Guest, B.

    2011-12-01

    The Carboniferous to Permian aged Nansen Formation is a cyclic carbonate shelf deposit and potential hydrocarbon reservoir. This formation is the thickest, most widespread carbonate sequence in the Sverdrup Basin. Deformed during the Eurekan Orogeny, the Nansen Fm. is topographically prominent and responsible for the rugged topography on Axel Heiburg and Ellesmere Island. The type-section for the Nansen Fm. is located on the north side of Hare Fiord, along Girty Creek. At this location there is an estimated stratigraphic thickness of 2 km. Due to easier access most of the stratigraphic work has been completed on nearby glacially exposed sections that traverse parallel to Girty Creek along glacial margins. Extensive biostratigraphy was completed on a glacier section to the west, however, in a glacier section to the east of Girty Creek, structural complexities appear to be repeating sections of the formation. Here, the Nansen formation is bounded by two regional reverse faults. This has produced duplex structures, with clearly exposed stacked horses, footwall synclines, and truncations. By projecting the structures observed along the eastern glacier section to the western glacier section that was used for biostratigraphic studies, it is clear that these structures would affect biostratigraphic interpretations. It was previously noted by biostratigraphers that thrust faults appear to be repeating sections of the Nansen formation. However by correlating all observed faults with the biostratigraphy, we can determine the extent to which the faulting has affected the interpretations, and whether all faults or stratigraphic repetitions are accounted for.

  1. Factors influencing acute thrombus formation on carotid artery vascular grafts

    SciTech Connect

    Torem, S.; Schneider, P.A.; Paxton, L.D.; Yasuda, H.; Hanson, S.R.

    1988-10-01

    Scintillation camera imaging of 111Indium-labeled platelets has been used to measure acute thrombus formation on modified expanded Teflon (ePTFE) vascular grafts placed in the carotid arteries of normal baboons. Platelet deposition plateaued over 2 hr postoperatively and occurred primarily at the graft-vessel anastomoses. A positive correlation was found between the circulating platelet count in individual animals and the extent of early platelet thrombus deposition. Unmodified ePTFE grafts accumulated 4.6 +/- 1.2 x 10(9) platelets per graft, or 2.3 +/- 0.71 x 10(9) platelets per anastomosis. Acutely, platelet accumulation was reduced versus control graft results by coating the graft lumenal surfaces with a smooth layer of silicone rubber polymer (0.60 +/- 0.19 x 10(9) platelets per anastomosis; P less than 0.02) but not by coating the grafts using a plasma polymer based on methane, which did not modify graft texture (8.2 +/- 1.7 x 10(9) platelets per graft; P greater than 0.10). The benefit of the silicone rubber coating persisted for at least 48 hr. However, longer term patency was not preserved because 10 of 12 grafts placed had failed within 1 to 2 months.

  2. Methods for diagnosing the risk factors of stone formation

    PubMed Central

    Robertson, William G.

    2012-01-01

    Objective To compare various systems for assessing the risk of recurrent stones, based on the composition of urine. Methods The relative supersaturation (RSS) of urine, the Tiselius Indices, the Robertson Risk Factor Algorithms (RRFA) and the BONN-Risk Index were compared in terms of the numbers of variables required to be measured, the ease of use of the system and the value of the information obtained. Results The RSS methods require up to 14 analyses in every urine sample but measure the RSS of all the main constituents of kidney stones. The Tiselius Indices and the RRFA require only seven analyses. The Tiselius Indices yield information on the crystallisation potentials (CP) of calcium oxalate and calcium phosphate; the RRFA also provide information on the CP of uric acid. Both methods provide details on the particular urinary abnormalities that lead to the abnormal CP of that urine. The BONN-Risk Index requires two measurements in each urine sample but only provides information on the CP of calcium oxalate. Additional measurements in urine have to be made to identify the cause of any abnormality. Conclusions The methods that are based on measuring RSS are work-intensive and unsuitable for the routine screening of patients. The Tiselius Indices and the RRFA are equally good at predicting the risk of a patient forming further stones. The BONN-Risk Index provides no additional information about the causative factors for any abnormality detected. PMID:26558033

  3. Toward a Reduced Complexity Channel Resolving Model for Sedimentary Delta Formation

    NASA Astrophysics Data System (ADS)

    Liang, M.; Voller, V. R.; Edmonds, D. A.; Paola, C.

    2010-12-01

    Predicting styles of delta growth in restoration areas is a challenge as we try to restore impacted coastlines. Cellular and rule-based reduced complexity models offer a worthwhile means of uncovering key dynamics in delta morphodynamics without the need to fully solve the governing transport equations. In terms of modeling sedimentary delta building processes a critical ingredients is accounting for the formation and bifurcation of channels; phenomena that can be related to the formation of levees and mouth-bars. To that end, we have developed a reduced complexity model that uses a simplified shallow-water solver to study channel formation, mouth bar deposition, and delta development under different forcings. Under the assumption that the flow has a very low Froude Number (Fr2<<1), the inertia term is dropped out and only the gravitational term and friction term remain in the momentum equation. The coupled mass conservation equation becomes a non-linear diffusive equation, which is linearized by a Kirchhoff transformation. Directional diffusivity is added to this system to compensate the loss of inertia and promote spreading of the turbulent jet. We test the reduced model against flow over Gaussian-shaped bumps of various heights. Comparison of results from this model with results from a full scale commercial code (Delft3D) show a satisfactory agreement on the critical mouth bar height needed to divert flow around the bar. Based on the same diffusive equation, we develop a low-Froude water-routing method for reduced complexity morphodynamics models. The preliminary results show that the method is capable of producing reasonable channel forms and mouth bar formation, and provides a good starting point for development of a channel resolving delta building model.

  4. Can proline-rich polypeptide complex mimic the effect of nerve growth factor?

    PubMed

    Zabłocka, Agnieszka; Urbaniak, Anna; Kuropatwa, Marianna; Zyzak, Joanna; Rossowska, Joanna; Janusz, Maria

    2014-01-01

    Naturally occurring compounds that can act as prosurvival factors and neurite formation stimulants in the conditions of reduced neurotrophins production are important both in neuronal protection and therapy of neurodegenerative disorders. Therefore, the role of proline-rich polypeptide complex (PRP) and its nonapeptide fragment (NP) in the promotion of pheochromocytoma cell line (PC12) survival and neurite outgrowth pathway is presented. It was shown that PRP/NP did not affect the neuronal nitric oxide synthase (nNOS) at the transcriptional and protein level. However, the activity of nNOS and intracellular nitric oxide (NO) concentration was markedly increased after treatment of PC12 cells with peptides. This reaction was inhibited by L-NAME-nNOS inhibitor. It was shown that PRP and NP induce the soluble guanylyl cyclase to release higher amount of cyclic GMP (cGMP), and subsequently, the increased phosphorylation of extracellular signal-regulated kinases 1 and 2 (ERK1/2) is observed. This effect was abolished by both U0126 (inhibitor of ERK1/2) and also by L-NAME. Reduction of ERK1/2 activity observed in the presence of nNOS inhibitor suggests that its activation is NO-dependent. The presented results shed some light on the mechanism of action of PRP complex. PRP and NP can activate NO/cGMP/ERK1/2 signaling pathway, similarly to nerve growth factor (NGF). The prosurvival action and short fibers formation suggest the role of PRP and NP in neuroprotection and the initiation of neuritogenesis. They can also participate in the amplification of signals controlling the survival and differentiation of neurons effect when the deficit of NGF takes place.

  5. Ab initio study of the formation of vacancy and hydrogen-vacancy complexes in palladium and its hydride

    NASA Astrophysics Data System (ADS)

    Supryadkina, I. A.; Bazhanov, D. I.; Ilyushin, A. S.

    2014-01-01

    We report on the results of ab initio calculations of vacancy and hydrogen-vacancy complexes in palladium and palladium hydride. Comparative analysis of the energies of the formation of defect complexes in palladium and its hydride has revealed that the formation of vacancy clusters is easier in the palladium hydride structure. Investigation of hydrogen-vacancy complexes in bulk crystalline palladium has shown that a hydrogen atom and a vacancy interact to form a stable hydrogen-vacancy (H-Vac) defect complex with a binding energy of E b = -0.21 eV. To investigate the initial stage in the formation of hydrogen-vacancy complexes (H n -Vac m ), we consider the clusterization of defects into clusters containing H-Vac and H2-Vac complexes as a structural unit. It is found that hydrogen-vacancy complexes form 2D defect structures in palladium in the (100)-type planes.

  6. Internal and External Factors Affecting Teachers' Adoption of Formative Assessment to Support Learning

    ERIC Educational Resources Information Center

    Izci, Kemal

    2016-01-01

    Assessment forms an important part of instruction. Assessment that aims to support learning is known as formative assessment and it contributes student's learning gain and motivation. However, teachers rarely use assessment formatively to aid their students' learning. Thus reviewing the factors that limit or support teachers' practices of…

  7. Complete stereocontrol in the synthesis of macrocyclic lanthanide complexes: direct formation of enantiopure systems for circularly polarised luminescence applications.

    PubMed

    Evans, Nicholas H; Carr, Rachel; Delbianco, Martina; Pal, Robert; Yufit, Dmitry S; Parker, David

    2013-11-28

    Mono-C-substitution of the 1,4,7-triazacyclononane ring induces formation of single enantiomers of Eu(III) complexes with nonadentate N6O3 ligands. The absolute configuration of each complex is determined by the stereogenicity of the C-substituent, revealed by comparison of the sign and sequence of CPL transitions for a series of complexes.

  8. Molybdenum Hydride and Dihydride Complexes Bearing Diphosphine Ligands with a Pendant Amine: Formation of Complexes With Bound Amines

    SciTech Connect

    Zhang, Shaoguang; Bullock, R. Morris

    2015-07-06

    CpMo(CO)(PNP)H complexes (PNP = (R2PCH2)2NMe, R = Et or Ph) were synthesized by displacement of two CO ligands of CpMo(CO)3H by the PNP ligand; these complexes were characterized by IR and variable temperature 1H and 31P NMR spectroscopy. CpMo(CO)(PNP)H complexes are formed as mixture of cis and trans-isomers. Both cis-CpMo(CO)(PEtNMePEt)H and trans-CpMo(CO)(PPhNMePPh)H were analyzed by single crystal X-ray diffraction. Electrochemical oxidation of CpMo(CO)(PEtNMePEt)H and CpMo(CO)(PPhNMePPh)H in CH3CN are both irreversible at slow scan rates and quasi-reversible at higher scan rates, with E1/2 = -0.36 V (vs. Cp2Fe+/0) for CpMo(CO)(PEtNMePEt)H and E1/2 = -0.18 V for CpMo(CO)(PPhNMePPh)H. Hydride abstraction from CpMo(CO)(PNP)H with [Ph3C]+[A]- (A = B(C6F5)4 or BArF4; [ArF = 3,5-bis(trifluoromethyl)phenyl]) afforded “tuck-in” [CpMo(CO)(κ3-PNP)]+ complexes that feature the amine bound to the metal. Displacement of the κ3 Mo-N bond by CD3CN gives [CpMo(CO)(PNP)(CD3CN)]+. The kinetics of this reaction were studied by NMR spectroscopy, providing the activation parameters ΔH‡ = 22.1 kcal/mol, ΔS‡ = 1.89 cal/(mol·K), Ea = 22.7 kcal/mol. Protonation of CpMo(CO)(PEtNMePEt)H affords [CpMo(CO)(κ2-PEtNMePEt)(H)2]+ as a Mo dihydride complex, which loses H2 to generate [CpMo(CO)(κ3-PEtNMePEt)]+ at room temperature. CpMo(CO)(dppp)H (dppp = 1,2-bis(diphenylphosphino)propane) was studied as a Mo diphosphine analogue without a pendant amine, and the product of protonation of this complex gives [CpMo(CO)(dppp)(H)2]+. Our results show that the pendant amine has a strong driving force to form stable “tuck-in” [CpMo(CO)(κ3-PNP)]+ complexes, and also promotes hydrogen elimination from [CpMo(CO)(PNP)(H)2]+ complexes by formation of Mo-N dative bond. We thank the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences and Biosciences for support. Pacific Northwest National Laboratory is operated by

  9. Revised nomenclature and stratigraphic relationships of the Fredericksburg Complex and Quantico Formation of the Virginia Piedmont

    USGS Publications Warehouse

    Pavlides, Louis

    1980-01-01

    The Fredericksburg Complex, in part a migmatitic terrane in northeast Virginia, is subdivided on the basis of lithology, as well as aeromagnetic and aeroradiometric data, into two metamorphic suites. These suites are separated by the northeast-trending Spotsylvania lineament, a rectilinear geophysical feature that is probably the trace of an old fault zone. East of the lineament, the Po River Metamorphic Suite, of Proterozoic Z and (or) early Paleozoic age, consists dominantly of biotite gneiss, generally augen gneiss, and lesser amounts of hornblende gneiss and mica schist. West of the Spotsylvania lineament is the Ta River Metamorphic Suite, composed mostly of amphibolite and amphibole gneiss. However, to the southwest, along its strike belt, the Ta River contains abundant biotite gneiss and mica schist. Both the Ta River and Po River contain abundant foliated granitoid and pegmatoid bodies as concordant tabular masses and as crosscutting dikes; these rocks are considered part of the Ta River and Po River Metamorphic Suites. The amphibolitic Holly Corner Gneiss is interpreted to be a western allochthonous equivalent of the Ta River. Both the Ta River and Holly Corner are considered to be coeval, eastern, distal facies of the Lower Cambrian(?) Chopawamsic Formation. The Paleozoic Falls Run Granite Gneiss intrudes the Ta River Metamorphic Suite and the Holly Corner Gneiss; locally the Falls Run is interpreted to have been transported westward with the Holly Corner after intrusion. The Quantico Formation, in the core of the Quantico-Columbia synclinorium, rests with angular unconformity along its northwest and southeast limbs, respectively, on the Chopawamsic Formation and the Ta River Metamorphic Suite. The Quantico Formation is assigned the same Late Ordovician age and similar stratigraphic position as the Arvonia Slate of the Arvonia syncline. The youngest rocks of the area are the granitoid and pegmatoid bodies of the Falmouth Intrusive Suite. They consist of

  10. Experimental studies of complex crater formation under cluster implantation of solids

    NASA Astrophysics Data System (ADS)

    Prasalovich, S.; Popok, V.; Persson, P.; Campbell, E. E. B.

    2005-10-01

    The results of a systematic study of surface defect formation after energetic Arn+ (n = 12, 22, 32, 54) and Xen+ (n = 4, 16) cluster ion implantation into silicon and sapphire are presented. Implantation energies vary from 3 to 18 keV/ion. Two cases of comparative studies are carried out: the same cluster species are implanted into two different substrates, i.e. Arn+ cluster ions into silicon and sapphire and two different cluster species Arn+ and Xen+ are implanted into the same kind of substrate (silicon). Atomic force, scanning electron and transmission electron microscopies (AFM, SEM and TEM) are used to study the implanted samples. The analysis reveals the formation of two types of surface erosion defects: simple and complex (with centrally positioned hillock) craters. It is found that the ratio of simple to complex crater formation as well as the hillock dimensions depend strongly on the cluster species, size and impact energy as well as on the type of substrate material. Qualitative models describing the two comparative cases of cluster implantation, the case of different cluster species and the case of different substrate materials, are proposed.

  11. CARBON DIOXIDE INFLUENCE ON THE THERMAL FORMATION OF COMPLEX ORGANIC MOLECULES IN INTERSTELLAR ICE ANALOGS

    SciTech Connect

    Vinogradoff, V.; Fray, N.; Bouilloud, M.; Cottin, H.; Duvernay, F.; Chiavassa, T.

    2015-08-20

    Interstellar ices are submitted to energetic processes (thermal, UV, and cosmic-ray radiations) producing complex organic molecules. Laboratory experiments aim to reproduce the evolution of interstellar ices to better understand the chemical changes leading to the reaction, formation, and desorption of molecules. In this context, the thermal evolution of an interstellar ice analogue composed of water, carbon dioxide, ammonia, and formaldehyde is investigated. The ice evolution during the warming has been monitored by IR spectroscopy. The formation of hexamethylenetetramine (HMT) and polymethylenimine (PMI) are observed in the organic refractory residue left after ice sublimation. A better understanding of this result is realized with the study of another ice mixture containing methylenimine (a precursor of HMT) with carbon dioxide and ammonia. It appears that carbamic acid, a reaction product of carbon dioxide and ammonia, plays the role of catalyst, allowing the reactions toward HMT and PMI formation. This is the first time that such complex organic molecules (HMT, PMI) are produced from the warming (without VUV photolysis or irradiation with energetic particles) of abundant molecules observed in interstellar ices (H{sub 2}O, NH{sub 3}, CO{sub 2}, H{sub 2}CO). This result strengthens the importance of thermal reactions in the ices’ evolution. HMT and PMI, likely components of interstellar ices, should be searched for in the pristine objects of our solar system, such as comets and carbonaceous chondrites.

  12. Carbon Dioxide Influence on the Thermal Formation of Complex Organic Molecules in Interstellar Ice Analogs

    NASA Astrophysics Data System (ADS)

    Vinogradoff, V.; Duvernay, F.; Fray, N.; Bouilloud, M.; Chiavassa, T.; Cottin, H.

    2015-08-01

    Interstellar ices are submitted to energetic processes (thermal, UV, and cosmic-ray radiations) producing complex organic molecules. Laboratory experiments aim to reproduce the evolution of interstellar ices to better understand the chemical changes leading to the reaction, formation, and desorption of molecules. In this context, the thermal evolution of an interstellar ice analogue composed of water, carbon dioxide, ammonia, and formaldehyde is investigated. The ice evolution during the warming has been monitored by IR spectroscopy. The formation of hexamethylenetetramine (HMT) and polymethylenimine (PMI) are observed in the organic refractory residue left after ice sublimation. A better understanding of this result is realized with the study of another ice mixture containing methylenimine (a precursor of HMT) with carbon dioxide and ammonia. It appears that carbamic acid, a reaction product of carbon dioxide and ammonia, plays the role of catalyst, allowing the reactions toward HMT and PMI formation. This is the first time that such complex organic molecules (HMT, PMI) are produced from the warming (without VUV photolysis or irradiation with energetic particles) of abundant molecules observed in interstellar ices (H2O, NH3, CO2, H2CO). This result strengthens the importance of thermal reactions in the ices’ evolution. HMT and PMI, likely components of interstellar ices, should be searched for in the pristine objects of our solar system, such as comets and carbonaceous chondrites.

  13. In vivo dynamics of chromatin-associated complex formation in mammalian nucleotide excision repair

    PubMed Central

    Moné, Martijn J.; Bernas, Tytus; Dinant, Christoffel; Goedvree, Feliks A.; Manders, Erik M. M.; Volker, Marcel; Houtsmuller, Adriaan B.; Hoeijmakers, Jan H. J.; Vermeulen, Wim; van Driel, Roel

    2004-01-01

    Chromatin is the substrate for many processes in the cell nucleus, including transcription, replication, and various DNA repair systems, all of which require the formation of multiprotein machineries on the chromatin fiber. We have analyzed the kinetics of in vivo assembly of the protein complex that is responsible for nucleotide excision repair (NER) in mammalian cells. Assembly is initiated by UV irradiation of a small area of the cell nucleus, after which the accumulation of GFP-tagged NER proteins in the DNA-damaged area is measured, reflecting the establishment of the dual-incision complex. The dynamic behavior of two NER proteins, ERCC1-XPF and TFIIH, was studied in detail. Results show that the repair complex is assembled with a rate of ≈30 complexes per second and is not diffusion limited. Furthermore, we provide in vivo evidence that not only binding of TFIIH, but also its helicase activity, is required for the recruitment of ERCC1-XPF. These studies give quantitative insight into the de novo assembly of a chromatin-associated protein complex in living cells. PMID:15520397

  14. Formation mechanism and biological activity of novel thiolated human-like collagen iron complex.

    PubMed

    Zhu, Chenhui; Liu, Lingyun; Deng, Jianjun; Ma, Xiaoxuan; Hui, Junfeng; Fan, Daidi

    2016-03-01

    To develop an iron supplement that is effectively absorbed and utilized, thiolated human-like collagen was created to improve the iron binding capacity of human-like collagen. A thiolated human-like collagen-iron complex was prepared in a phosphate buffer, and one mole of thiolated human-like collagen-iron possessed approximately 28.83 moles of iron. The characteristics of thiolated human-like collagen-iron were investigated by ultraviolet-visible absorption spectroscopy, Fourier transform infrared spectroscopy, circular dichroism, and differential scanning calorimetry. The results showed that the thiolated human-like collagen-iron complex retained the secondary structure of human-like collagen and had greater thermodynamic stability than human-like collagen, although interactions between iron ions and human-like collagen occurred during the formation of the complex. In addition, to evaluate the bioavailability of thiolated human-like collagen-iron, an in vitro Caco-2 cell model and an in vivo iron deficiency anemia mouse model were employed. The data demonstrated that the thiolated human-like collagen-iron complex exhibited greater bioavailability and was more easily utilized than FeSO4, ferric ammonium citrate, or ferrous glycinate. These results indicated that the thiolated human-like collagen-iron complex is a potential iron supplement in the biomedical field.

  15. Interaction and formation mechanism of binary complex between zein and propylene glycol alginate.

    PubMed

    Sun, Cuixia; Dai, Lei; Gao, Yanxiang

    2017-02-10

    The anti-solvent co-precipitation method was used to fabricate the zein-propylene glycol alginate (PGA) binary complex with different mass ratios of zein to PGA (20:1, 10:1, 5:1, 2:1 and 1:1) at pH 4.0. Results showed that attractive electrostatic interaction between zein and PGA occurred and negatively charged binary complex with large size and high turbidity was formed due to the charge neutralization. Hydrogen bonding and hydrophobic effects were involved in the interactions between zein and PGA, leading to the changed secondary structure and improved thermal stability of zein. Aggregates in the irregular shape with large size were obviously observed in the AFM images. PGA alone exhibited a fine filamentous network structure, while zein-PGA binary complex showed a rough branch-like pattern and the surface of "branch" was closely adsorbed by lots of spherical zein particles. Q in zein-PGA binary complex dispersions presented the improved photochemical and thermal stability. The potential mechanism of a two-step process was proposed to explain the formation of zein-PGA binary complexes.

  16. Presenilin and nicastrin regulate each other and determine amyloid β-peptide production via complex formation

    PubMed Central

    Edbauer, Dieter; Winkler, Edith; Haass, Christian; Steiner, Harald

    2002-01-01

    Amyloid β-peptide (Aβ) is generated by the consecutive cuts of two membrane-bound proteases. β-Secretase cuts at the N terminus of the Aβ domain, whereas γ-secretase mediates the C-terminal cut. Recent evidence suggests that the presenilin (PS) proteins, PS1 and PS2, may be γ-secretases. Because PSs principally exist as high molecular weight protein complexes, biologically active γ-secretases likely require other cofactors such as nicastrin (Nct) for their activities. Here we show that preferentially mature Nct forms a stable complex with PSs. Furthermore, we have down-regulated Nct levels by using a highly specific and efficient RNA interference approach. Very similar to a loss of PS function, down-regulation of Nct levels leads to a massive accumulation of the C-terminal fragments of the β-amyloid precursor protein. In addition, Aβ production was markedly reduced. Strikingly, down-regulation of Nct destabilized PS and strongly lowered levels of the high molecular weight PS1 complex. Interestingly, absence of the PS1 complex in PS1−/− cells was associated with a strong down-regulation of the levels of mature Nct, suggesting that binding to PS is required for trafficking of Nct through the secretory pathway. Based on these findings we conclude that Nct and PS regulate each other and determine γ-secretase function via complex formation. PMID:12048259

  17. Factors affecting catalysis of copper corrosion products in NDMA formation from DMA in simulated premise plumbing.

    PubMed

    Zhang, Hong; Andrews, Susan A

    2013-11-01

    This study investigated the effects of corrosion products of copper, a metal commonly employed in household plumbing systems, on N-nitrosodimethylamine (NDMA) formation from a known NDMA precursor, dimethylamine (DMA). Copper-catalyzed NDMA formation increased with increasing copper concentrations, DMA concentrations, alkalinity and hardness, but decreased with increasing natural organic matter (NOM) concentration. pH influenced the speciation of chloramine and the interactions of copper with DMA. The transformation of monochloramine (NH2Cl) to dichloramine and complexation of copper with DMA were involved in elevating the formation of NDMA by copper at pH 7.0. The inhibiting effect of NOM on copper catalysis was attributed to the rapid consumption of NH2Cl by NOM and/or the competitive complexation of NOM with copper to limit the formation of DMA-copper complexes. Hardness ions, as represented by Ca(2+), also competed with copper for binding sites on NOM, thereby weakening the inhibitory effect of NOM on NDMA formation. Common copper corrosion products also participated in these reactions but in different ways. Aqueous copper released from malachite [Cu2CO3(OH)2] was shown to promote NDMA formation while NDMA formation decreased in the presence of CuO, most likely due to the adsorption of DMA.

  18. GTP binding controls complex formation by the human ROCO protein MASL1.

    PubMed

    Dihanich, Sybille; Civiero, Laura; Manzoni, Claudia; Mamais, Adamantios; Bandopadhyay, Rina; Greggio, Elisa; Lewis, Patrick A

    2014-01-01

    The human ROCO proteins are a family of multi-domain proteins sharing a conserved ROC-COR supra-domain. The family has four members: leucine-rich repeat kinase 1 (LRRK1), leucine-rich repeat kinase 2 (LRRK2), death-associated protein kinase 1 (DAPK1) and malignant fibrous histiocytoma amplified sequences with leucine-rich tandem repeats 1 (MASL1). Previous studies of LRRK1/2 and DAPK1 have shown that the ROC (Ras of complex proteins) domain can bind and hydrolyse GTP, but the cellular consequences of this activity are still unclear. Here, the first biochemical characterization of MASL1 and the impact of GTP binding on MASL1 complex formation are reported. The results demonstrate that MASL1, similar to other ROCO proteins, can bind guanosine nucleotides via its ROC domain. Furthermore, MASL1 exists in two distinct cellular complexes associated with heat shock protein 60, and the formation of a low molecular weight pool of MASL1 is modulated by GTP binding. Finally, loss of GTP enhances MASL1 toxicity in cells. Taken together, these data point to a central role for the ROC/GTPase domain of MASL1 in the regulation of its cellular function.

  19. The plant cell cycle: Pre-Replication complex formation and controls.

    PubMed

    Brasil, Juliana Nogueira; Costa, Carinne N Monteiro; Cabral, Luiz Mors; Ferreira, Paulo C G; Hemerly, Adriana S

    2017-03-16

    The multiplication of cells in all living organisms requires a tight regulation of DNA replication. Several mechanisms take place to ensure that the DNA is replicated faithfully and just once per cell cycle in order to originate through mitoses two new daughter cells that contain exactly the same information from the previous one. A key control mechanism that occurs before cells enter S phase is the formation of a pre-replication complex (pre-RC) that is assembled at replication origins by the sequential association of the origin recognition complex, followed by Cdt1, Cdc6 and finally MCMs, licensing DNA to start replication. The identification of pre-RC members in all animal and plant species shows that this complex is conserved in eukaryotes and, more importantly, the differences between kingdoms might reflect their divergence in strategies on cell cycle regulation, as it must be integrated and adapted to the niche, ecosystem, and the organism peculiarities. Here, we provide an overview of the knowledge generated so far on the formation and the developmental controls of the pre-RC mechanism in plants, analyzing some particular aspects in comparison to other eukaryotes.

  20. Gas Phase Uranyl Activation: Formation of a Uranium Nitrosyl Complex from Uranyl Azide

    SciTech Connect

    Gong, Yu; De Jong, Wibe A.; Gibson, John K.

    2015-05-13

    Activation of the oxo bond of uranyl, UO22+, was achieved by collision induced dissociation (CID) of UO2(N3)Cl2– in a quadrupole ion trap mass spectrometer. The gas phase complex UO2(N3)Cl2– was produced by electrospray ionization of solutions of UO2Cl2 and NaN3. CID of UO2(N3)Cl2– resulted in the loss of N2 to form UO(NO)Cl2–, in which the “inert” uranyl oxo bond has been activated. Formation of UO2Cl2– via N3 loss was also observed. Density functional theory computations predict that the UO(NO)Cl2– complex has nonplanar Cs symmetry and a singlet ground state. Analysis of the bonding of the UO(NO)Cl2– complex shows that the side-on bonded NO moiety can be considered as NO3–, suggesting a formal oxidation state of U(VI). Activation of the uranyl oxo bond in UO2(N3)Cl2– to form UO(NO)Cl2– and N2 was computed to be endothermic by 169 kJ/mol, which is energetically more favorable than formation of NUOCl2– and UO2Cl2–. The observation of UO2Cl2– during CID is most likely due to the absence of an energy barrier for neutral ligand loss.

  1. Model of formation of the Khibiny-Lovozero ore-bearing volcanic-plutonic complex

    NASA Astrophysics Data System (ADS)

    Arzamastsev, A. A.; Arzamastseva, L. V.; Zhirova, A. M.; Glaznev, V. N.

    2013-09-01

    The paper presents the results of a study of the large Paleozoic ore-magmatic system in the northeastern Fennoscandian Shield comprising the Khibiny and Lovozero plutons, the Kurga intrusion, volcanic rocks, and numerous alkaline dike swarms. As follows from the results of deep drilling and 3D geophysical simulation, large bodies of rocks pertaining to the ultramafic alkaline complex occur at the lower level of the ore-magmatic system. Peridotite, pyroxenite, melilitolite, melteigite, and ijolite occupy more than 50 vol % of the volcanic-plutonic complex within the upper 15 km accessible to gravity exploration. The proposed model represents the ore-magmatic system as a conjugate network of mantle magmatic sources localized at different depth levels and periodically supplying the melts belonging to the two autonomous groups: (1) ultramafic alkaline rocks with carbonatites and (2) alkali syenites-peralkaline syenites, which were formed synchronously having a common system of outlet conduits. With allowance for the available isotopic datings and new geochronological evidence, the duration of complex formation beginning from supply of the first batches of melt into calderas and up to postmagmatic events, expressed in formation of late pegmatoids, was no less than 25 Ma.

  2. Quantitative serine protease assays based on formation of copper(II)-oligopeptide complexes.

    PubMed

    Ding, Xiaokang; Yang, Kun-Lin

    2015-01-07

    A quantitative protease assay based on the formation of a copper-oligopeptide complex is developed. In this assay, when a tripeptide GGH fragment is cleaved from an oligopeptide chain by serine proteases, the tripeptide quickly forms a pink GGH/Cu(2+) complex whose concentration can be determined quantitatively by using UV-Vis spectroscopy. Therefore, activities of serine proteases can be determined from the formation rate of the GGH/Cu(2+) complex. This principle can be used to detect the presence of serine protease in a real-time manner, or measure proteolytic activities of serine protease cleaving different oligopeptide substrates. For example, by using this assay, we demonstrate that trypsin, a model serine protease, is able to cleave two oligopeptides GGGGKGGH () and GGGGRGGH (). However, the specificity constant (kcat/Km) for is higher than that of (6.4 × 10(3) mM(-1) min(-1)vs. 1.3 × 10(3) mM(-1) min(-1)). This result shows that trypsin is more specific toward arginine (R) than lysine (K) in the oligopeptide sequence.

  3. Gas phase uranyl activation: formation of a uranium nitrosyl complex from uranyl azide.

    PubMed

    Gong, Yu; de Jong, Wibe A; Gibson, John K

    2015-05-13

    Activation of the oxo bond of uranyl, UO2(2+), was achieved by collision induced dissociation (CID) of UO2(N3)Cl2(-) in a quadrupole ion trap mass spectrometer. The gas phase complex UO2(N3)Cl2(-) was produced by electrospray ionization of solutions of UO2Cl2 and NaN3. CID of UO2(N3)Cl2(-) resulted in the loss of N2 to form UO(NO)Cl2(-), in which the "inert" uranyl oxo bond has been activated. Formation of UO2Cl2(-) via N3 loss was also observed. Density functional theory computations predict that the UO(NO)Cl2(-) complex has nonplanar Cs symmetry and a singlet ground state. Analysis of the bonding of the UO(NO)Cl2(-) complex shows that the side-on bonded NO moiety can be considered as NO(3-), suggesting a formal oxidation state of U(VI). Activation of the uranyl oxo bond in UO2(N3)Cl2(-) to form UO(NO)Cl2(-) and N2 was computed to be endothermic by 169 kJ/mol, which is energetically more favorable than formation of NUOCl2(-) and UO2Cl2(-). The observation of UO2Cl2(-) during CID is most likely due to the absence of an energy barrier for neutral ligand loss.

  4. Imprime PGG-Mediated Anti-Cancer Immune Activation Requires Immune Complex Formation

    PubMed Central

    Qiu, Xiaohong; Ottoson, Nadine R.; Walsh, Richard M.; Gorden, Keith B; Harrison, Ben; Maimonis, Peter J.; Leonardo, Steven M.; Ertelt, Kathleen E.; Danielson, Michael E.; Michel, Kyle S.; Nelson, Mariana; Graff, Jeremy R.; Patchen, Myra L.; Bose, Nandita

    2016-01-01

    Imprime PGG (Imprime), an intravenously-administered, soluble β-glucan, has shown compelling efficacy in multiple phase 2 clinical trials with tumor targeting or anti-angiogenic antibodies. Mechanistically, Imprime acts as pathogen-associated molecular pattern (PAMP) directly activating innate immune effector cells, triggering a coordinated anti-cancer immune response. Herein, using whole blood from healthy human subjects, we show that Imprime-induced anti-cancer functionality is dependent on immune complex formation with naturally-occurring, anti-β glucan antibodies (ABA). The formation of Imprime-ABA complexes activates complement, primarily via the classical complement pathway, and is opsonized by iC3b. Immune complex binding depends upon Complement Receptor 3 and Fcg Receptor IIa, eliciting phenotypic activation of, and enhanced chemokine production by, neutrophils and monocytes, enabling these effector cells to kill antibody-opsonized tumor cells via the generation of reactive oxygen species and antibody-dependent cellular phagocytosis. Importantly, these innate immune cell changes were not evident in subjects with low ABA levels but could be rescued with exogenous ABA supplementation. Together, these data indicate that pre-existing ABA are essential for Imprime-mediated anti-cancer immune activation and suggest that pre-treatment ABA levels may provide a plausible patient selection biomarker to delineate patients most likely to benefit from Imprime-based therapy. PMID:27812183

  5. Decay of Activity Complexes, Formation of Unipolar Magnetic Regions, and Coronal Holes in Their Causal Relation

    NASA Astrophysics Data System (ADS)

    Golubeva, E. M.; Mordvinov, A. V.

    2016-12-01

    The peculiar development of solar activity in the current cycle resulted in an asynchronous reversal of the Sun's polar fields. The asymmetry is also observed in the formation of polar coronal holes. A stable coronal hole was first formed at the South Pole, despite the later polar-field reversal there. The aim of this study is to understand the processes making this situation possible. Synoptic magnetic maps from the Global Oscillation Network Group and corresponding coronal-hole maps from the Extreme ultraviolet Imaging Telescope onboard the Solar and Heliospheric Observatory and the Atmospheric Imaging Assembly onboard the Solar Dynamics Observatory are analyzed here to study the causal relationship between the decay of activity complexes, evolution of large-scale magnetic fields, and formation of coronal holes. Ensembles of coronal holes associated with decaying active regions and activity complexes are presented. These ensembles take part in global rearrangements of the Sun's open magnetic flux. In particular, the south polar coronal hole was formed from an ensemble of coronal holes that came into existence after the decay of multiple activity complexes observed during 2014.

  6. Isolation and Characterization of FORMATE/NI(CYCLAM)^{2+} Complexes with Cryogenic Ion Vibrational Predissociation

    NASA Astrophysics Data System (ADS)

    Wolk, Arron B.; Fournier, Joseph A.; Wolke, Conrad T.; Johnson, Mark A.

    2013-06-01

    Transition metal-based organometallic catalysts are a promising means of converting CO_{2} to transportable fuels. Ni(cyclam)^{2+}(cyclam = 1,4,8,11-tetraazacyclotetradecane), a Ni^{II} complex ligated by four nitrogen centers, has shown promise as a catalyst selective for CO_{2} reduction in aqueous solutions. The cyclam ligand has four NH hydrogen bond donors that can adopt five conformations, each offering distinct binding motifs for coordination of CO_{2} close to the metal center. To probe the ligand conformation and the role of hydrogen bonding in adduct binding, we extract Ni(cyclam)^{2+} complexes with the formate anion and some of its analogs from solution using electrospray ionization, and characterize their structures using cryogenic ion vibrational predissociation spectroscopy. Using the signature vibrational features of the embedded carboxylate anion and the NH groups as reporters, we compare the binding motifs of oxalate, benzoate, and formate anions to the Ni(cyclam)^{2+} framework. Finally, we comment on possible routes to generate the singly charged Ni(cyclam)^{+} complex, a key intermediate that has been invoked in the catalytic CO_{2} reduction cycle, but has never been isolated through ion processing techniques.

  7. Influence of structural features of carrageenan on the formation of polyelectrolyte complexes with chitosan.

    PubMed

    Volod'ko, A V; Davydova, V N; Glazunov, V P; Likhatskaya, G N; Yermak, I M

    2016-03-01

    The polyelectrolyte complexes (PEC) of carrageenans (CG)-κ-, κ/β-, λ-and x-CG with chitosan were obtained. The formation of PEC was detected by Fourier-transform infrared (FTIR) spectroscopy and by centrifugation in a Percoll gradient. The influence of the structural peculiarities of CG on its interaction with chitosan was studied. The results of centrifugation showed that x-CG with a high degree of sulphation (SD) was completely bound to chitosan, unlike low SD κ-CG and κ/β-CG. Binding constant values showed there was a high affinity of CG for chitosan. CG with flexible macromolecule conformation and high SD exhibited the greatest binding affinity for chitosan. The full-atomic 3D-structures of the PEC κ-CG: chitosan in solution have been obtained by the experiments in silico for the first time. The amino groups of chitosan make the largest contribution to the energy of the complex formation by means of hydrogen and ionic bonds. The most probable complexes have stoichiometries of 1:1 and 1:1.5.

  8. Dysregulated serum response factor triggers formation of hepatocellular carcinoma

    PubMed Central

    Ohrnberger, Stefan; Thavamani, Abhishek; Braeuning, Albert; Lipka, Daniel B; Kirilov, Milen; Geffers, Robert; Authenrieth, Stella E; Römer, Michael; Zell, Andreas; Bonin, Michael; Schwarz, Michael; Schütz, Günther; Schirmacher, Peter; Plass, Christoph; Longerich, Thomas; Nordheim, Alfred

    2015-01-01

    The ubiquitously expressed transcriptional regulator serum response factor (SRF) is controlled by both Ras/MAPK (mitogen-activated protein kinase) and Rho/actin signaling pathways, which are frequently activated in hepatocellular carcinoma (HCC). We generated SRF-VP16iHep mice, which conditionally express constitutively active SRF-VP16 in hepatocytes, thereby controlling subsets of both Ras/MAPK- and Rho/actin-stimulated target genes. All SRF-VP16iHep mice develop hyperproliferative liver nodules that progresses to lethal HCC. Some murine (m)HCCs acquire Ctnnb1 mutations equivalent to those in human (h)HCC. The resulting transcript signatures mirror those of a distinct subgroup of hHCCs, with shared activation of oncofetal genes including Igf2, correlating with CpG hypomethylation at the imprinted Igf2/H19 locus. Conclusion: SRF-VP16iHep mHCC reveal convergent Ras/MAPK and Rho/actin signaling as a highly oncogenic driver mechanism for hepatocarcinogenesis. This suggests simultaneous inhibition of Ras/MAPK and Rho/actin signaling as a treatment strategy in hHCC therapy. (Hepatology 2015;61:979–989) PMID:25266280

  9. Solid inclusion complexes of vanillin with cyclodextrins: their formation, characterization, and high-temperature stability.

    PubMed

    Kayaci, Fatma; Uyar, Tamer

    2011-11-09

    This study reports the formation of solid vanillin/cyclodextrin inclusion complexes (vanillin/CD ICs) with the aim to enhance the thermal stability and sustained release of vanillin by inclusion complexation. The solid vanillin/CD ICs with three types of CDs (α-CD, β-CD, and γ-CD) were prepared using the freeze-drying method; in addition, a coprecipitation method was also used in the case of γ-CD. The presence of vanillin in CD ICs was confirmed by FTIR and (1)H NMR studies. Moreover, (1)H NMR study elucidated that the complexation stoichiometry for both vanillin/β-CD IC and vanillin/γ-CD IC was a 1:1 molar ratio, whereas it was 0.625:1 for vanillin/α-CD IC. XRD studies have shown channel-type arrangement for CD molecules, and no diffraction peak for free vanillin was observed for vanillin/β-CD IC and vanillin/γ-CD IC, indicating that complete inclusion complexation was successfully achieved for these CD ICs. In the case of vanillin/α-CD IC, the sample was mostly amorphous and some uncomplexed vanillin was present, suggesting that α-CD was not very effective for complexation with vanillin compared to β-CD and γ-CD. Furthermore, DSC studies for vanillin/β-CD IC and vanillin/γ-CD IC have shown no melting point for vanillin, elucidating the true complex formation, whereas a melting point for vanillin was recorded for vanillin/α-CD IC, confirming the presence of some uncomplexed vanillin in this sample. TGA thermograms indicated that thermal evaporation/degradation of vanillin occurred over a much higher temperature range (150-300 °C) for vanillin/CD ICs samples when compared to pure vanillin (80-200 °C) or vanillin/CD physical mixtures, signifying that the thermal stability of vanillin was increased due to the inclusion complexation with CDs. Moreover, headspace GC-MS analyses indicated that the release of vanillin was sustained at higher temperatures in the case of vanillin/CD ICs due to the inclusion complexation when compared to vanillin

  10. Considerable fluorescence enhancement upon supramolecular complex formation between berberine and p-sulfonated calixarenes

    NASA Astrophysics Data System (ADS)

    Megyesi, Mónika; Biczók, László

    2006-06-01

    Remarkably strong binding of berberine to 4-sulfonatocalix[8]arene was found in aqueous solution, which led to fluorescence quantum yield increase of a factor about 40 at pH 2. The hypsochromic shift of the fluorescence maximum implied that berberine sensed less polar microenvironment when confined to SCX8. The stability of the supramolecular complex significantly diminished when sulfocalixarenes of smaller ring size served as host compounds but the pH affected the association strength to a much lesser extent. All berberine complexes proved to be barely fluorescent at pH 12.2 because of excited state quenching by the hosts via electron transfer.

  11. Diversity of potential pathogenicity and biofilm formation among Burkholderia cepacia complex water, clinical, and agricultural isolates in China.

    PubMed

    Ibrahim, Muhammad; Tang, Qiaomei; Shi, Yu; Almoneafy, Abdulwareth; Fang, Yuan; Xu, Liuhu; Li, Wen; Li, Bin; Xie, Guan-Lin

    2012-05-01

    A collection of 70 Burkholderia cepacia complex isolates, recovered from clinical, water, and agricultural resources in China in our previous studies, were tested to assess their potential pathogenicity and association of biofilm formation with pathogenicity. The pathogenicity was tested in the alternative infection models alfalfa, detached lettuce midrib, Galleria mellonella (wax moth), rat agar bead, and lettuce intact leaves. Severe to moderate pathogenicity were observed for isolates of clinical and water origin compared to agricultural isolates, with the exception of a few clinical isolates exhibiting reduced pathogenicity. Virulent isolates persisted in rat lungs until 21 days post infection causing histopathological changes like inflammation, while in lettuce midrib tissues invasion, localization, and replication of bacteria were observed. Biofilm formation ability was also documented in high frequency among water and clinical virulent isolates compared to agricultural isolates. Although variations in pathogenicity were observed for a few isolates, results obtained from different model systems including lettuce were consistent. Our studies indicate that water and clinical isolates showed severe virulence and strong biofilm formation ability compared to agricultural isolates. The results also show lettuce as a promising infection model not only to study the pathogenicity factors used by Bcc bacteria but also for characterization the in vivo transcriptional profile for different niches adaptation of this opportunistic pathogen.

  12. Calcium l-tartrate complex formation in neutral and in hyperalkaline aqueous solutions.

    PubMed

    Gácsi, Attila; Kutus, Bence; Csendes, Zita; Faragó, Tünde; Peintler, Gábor; Pálinkó, István; Sipos, Pál

    2016-11-01

    The complex formation reaction between the l-tartrate (Tar(2-)) and calcium ions taking place in neutral and in hyperalkaline (pH > 13) aqueous solutions has been investigated. It was demonstrated that upon NaOH addition the solubility of the CaTar(s) precipitate significantly increases. Conductometric and freezing point depression measurements further confirmed that in this process water soluble species are formed as a result of a reaction between the CaTar(s) and the hydroxide ion (or, conversely, between Ca(OH)2(s) and the Tar(2-) ion). (13)C NMR spectroscopic measurements yielded the value of pK3 = 15.4 ± 0.2 for the proton dissociation of one of the alcoholic OH groups of Tar(2-) (at 25.0 °C and 4 M Na(Cl) ionic strength). Upon addition of calcium ions to an alkaline Tar(2-) solution, the (1)H NMR signal gradually broadened and the (13)C-satellite peaks split to two components, which also indicate complexation. From H2/Pt potentiometric titrations performed with solutions in the 13.6 ≤ pH ≤ 14.4 range, it was observed, that this complex formation is accompanied by a hydroxide ion consuming process. The titration curves can be best described via assuming the formation of the CaTarH-1(-)(aq) (lg β11-1 = -11.2 ± 0.1) and CaTarH-2(2-)(aq) (lg β11-2 = -25.3 ± 0.1) complexes. In hyperalkaline solutions, these two species account for more than 90-99% of the calcium ions present and the contribution of the other reasonable and well-established calcium-containing solution species is rather small. The possible structures of the above complexes have been modeled via ab initio calculations. The stoichiometries are consistent both with species containing coordinated alcoholate group(s) and with mixed Ca(ii)-hydroxo-tartrato complexes. From the data available at present, both types of structures can be considered as chemically reasonable.

  13. The Catabolite Repressor Protein-Cyclic AMP Complex Regulates csgD and Biofilm Formation in Uropathogenic Escherichia coli.

    PubMed

    Hufnagel, David A; Evans, Margery L; Greene, Sarah E; Pinkner, Jerome S; Hultgren, Scott J; Chapman, Matthew R

    2016-12-15

    The extracellular matrix protects Escherichia coli from immune cells, oxidative stress, predation, and other environmental stresses. Production of the E. coli extracellular matrix is regulated by transcription factors that are tuned to environmental conditions. The biofilm master regulator protein CsgD upregulates curli and cellulose, the two major polymers in the extracellular matrix of uropathogenic E. coli (UPEC) biofilms. We found that cyclic AMP (cAMP) regulates curli, cellulose, and UPEC biofilms through csgD The alarmone cAMP is produced by adenylate cyclase (CyaA), and deletion of cyaA resulted in reduced extracellular matrix production and biofilm formation. The catabolite repressor protein (CRP) positively regulated csgD transcription, leading to curli and cellulose production in the UPEC isolate, UTI89. Glucose, a known inhibitor of CyaA activity, blocked extracellular matrix formation when added to the growth medium. The mutant strains ΔcyaA and Δcrp did not produce rugose biofilms, pellicles, curli, cellulose, or CsgD. Three putative CRP binding sites were identified within the csgD-csgB intergenic region, and purified CRP could gel shift the csgD-csgB intergenic region. Additionally, we found that CRP binded upstream of kpsMT, which encodes machinery for K1 capsule production. Together our work shows that cAMP and CRP influence E. coli biofilms through transcriptional regulation of csgD IMPORTANCE The catabolite repressor protein (CRP)-cyclic AMP (cAMP) complex influences the transcription of ∼7% of genes on the Escherichia coli chromosome (D. Zheng, C. Constantinidou, J. L. Hobman, and S. D. Minchin, Nucleic Acids Res 32:5874-5893, 2004, https://dx.doi.org/10.1093/nar/gkh908). Glucose inhibits E. coli biofilm formation, and ΔcyaA and Δcrp mutants show impaired biofilm formation (D. W. Jackson, J.W. Simecka, and T. Romeo, J Bacteriol 184:3406-3410, 2002, https://dx.doi.org/10.1128/JB.184.12.3406-3410.2002). We determined that the c

  14. Role of G protein signaling in the formation of the fibrin(ogen)-integrin αIIbβ3-actin cytoskeleton complex in platelets.

    PubMed

    Budnik, Ivan; Shenkman, Boris; Savion, Naphtali

    2016-09-01

    Effective platelet function requires formation of a physical link between fibrin(ogen), integrin αIIbβ3, and cytoplasmic actin filaments. We investigated the role of the Gαq, Gαi, and Gα12/13 families of heterotrimeric GTP-binding proteins (G proteins) in the assembly of a ligand-αIIbβ3-actin cytoskeleton complex. Selective and combined activation of the G proteins was achieved by using combinations of various platelet agonists and inhibitors. Formation and stability of fibrinogen-αIIbβ3 interaction were evaluated by the extent of platelet aggregation and the rate of eptifibatide-induced platelet disaggregation; association of αIIbβ3 with the cytoskeleton was analyzed by western blot. Formation of the fibrin-αIIbβ3-actin cytoskeleton complex was evaluated by rotational thromboelastometry assay in which clot formation was induced by the mixture of reptilase and factor XIIIa. We demonstrated that involvement of heterotrimeric G proteins in the formation of the ligand-αIIbβ3-cytoskeleton complex depends on whether fibrinogen or fibrin serves as the integrin ligand. Formation of the fibrinogen-αIIbβ3-cytoskeleton complex requires combined activation of at least two G protein pathways while the maximal αIIbβ3-cytoskeleton association and the strongest αIIbβ3-fibrinogen binding supporting irreversible platelet aggregation require combined activation of all three-Gαq, Gαi, and Gα12/13-G protein families. In contrast, formation of the fibrin-αIIbβ3-cytoskeleton complex mediating clot retraction is critically dependent on the activation of the Gαi family, especially on the activation of Gαz.

  15. Complex Organic Molecules Formation in Space Through Gas Phase Reactions: A Theoretical Approach

    NASA Astrophysics Data System (ADS)

    Redondo, Pilar; Barrientos, Carmen; Largo, Antonio

    2017-02-01

    Chemistry in the interstellar medium (ISM) is capable of producing complex organic molecules (COMs) of great importance to astrobiology. Gas phase and grain surface chemistry almost certainly both contribute to COM formation. Amino acids as building blocks of proteins are some of the most interesting COMs. The simplest one, glycine, has been characterized in meteorites and comets and, its conclusive detection in the ISM seems to be highly plausible. In this work, we analyze the gas phase reaction of glycine and {{{CH}}5}+ to establish the role of this process in the formation of alanine or other COMs in the ISM. Formation of protonated α- and β-alanine in spite of being exothermic processes is not viable under interstellar conditions because the different paths leading to these isomers present net activation energies. Nevertheless, glycine can evolve to protonated 1-imide-2, 2-propanediol, protonated amino acetone, protonated hydroxyacetone, and protonated propionic acid. However, formation of acetic acid and protonated methylamine is also a favorable process and therefore will be a competitive channel with the evolution of glycine to COMs.

  16. New spectroscopic studies of plutonium (IV) nitrate complex formation in solution

    SciTech Connect

    Berg, J.M.; Veirs, D.K.; Vaughn, R.B.

    1997-06-01

    Spectrophotometric titrations of Pu(IV) with HNO{sub 3} were conducted in a series of aqueous HClO{sub 4} solutions ranging ionic strength from 2 to 19 mol/kg on the molality scale. The Pu f-f absorption spectra in the visible and near IR range were deconvoluted into spectra of Pu{sup 4+}(aq), Pu(NO{sub 3}){sup 3+} and Pu(NO{sub 3}){sub 2}{sup 2+} complexes and their formation constants as functions of ionic strength. When corrected for the incomplete dissociation of nitric acid, these formation constants exhibit smooth increases with ionic strength from 5 to 19 mol/kg.

  17. Struvite crystal growth inhibition by trisodium citrate and the formation of chemical complexes in growth solution

    NASA Astrophysics Data System (ADS)

    Prywer, Jolanta; Mielniczek-Brzóska, Ewa; Olszynski, Marcin

    2015-05-01

    Effect of trisodium citrate on the crystallization of struvite was studied. To evaluate such an effect an experiment of struvite growth from artificial urine was performed. The investigations are related to infectious urinary stones formation. The crystallization process was induced by the addition of aqueous ammonia solution to mimic the bacterial activity. The spectrophotometric results demonstrate that trisodium citrate increases induction time with respect to struvite formation and decreases the growth efficiency of struvite. The inhibitory effect of trisodium citrate on the nucleation and growth of struvite is explained in base of chemical speciation analysis. Such an analysis demonstrates that the inhibitory effect is related with the fact that trisodium citrate binds NH4 + and Mg2+ ions in the range of pH from 7 to 9.5 characteristic for struvite precipitation. The most important is the MgCit- complex whose concentration strongly depends on an increase in pH rather than on an increase in citrate concentrations.

  18. Chiral symmetry breaking in complex chemical systems during formation of life on earth

    NASA Astrophysics Data System (ADS)

    Konstantinova, A. F.; Konstantinov, K. K.

    2015-09-01

    The chiral symmetry in complex chemical systems containing many amino acids and characterized by many similar chemical reactions (a situation corresponding to the formation of life on Earth) is considered. It is shown that effective averaging over similar reaction channels may lead to very weak effective enantioselectivity, which does not allow for chiral symmetry breaking in most known models. A class of models with simple and catalytic synthesis of one amino acid, the formation of peptides with a length reaching three, and the precipitation of one insoluble pair of materials is analyzed. It is proven that chiral symmetry breaking may occur in one possible version from an insoluble pair of materials even in the complete absence of catalytic synthesis of amino acid. It is shown that the presence of weakly enantioselective catalytic synthesis in a model significantly increases the number of possible versions in which chiral symmetry breaks.

  19. Formation of polyelectrolyte complexes with diethylaminoethyl dextran: charge ratio and molar mass effect.

    PubMed

    Le Cerf, Didier; Pepin, Anne Sophie; Niang, Pape Momar; Cristea, Mariana; Karakasyan-Dia, Carole; Picton, Luc

    2014-11-26

    The formation of polyelectrolyte complexes (PECs) between carboxymethyl pullulan and DEAE Dextran, was investigated, in dilute solution, with emphasis on the effect of charge density (molar ratio or pH) and molar masses. Electrophoretic mobility measurements have evidenced that insoluble PECs (neutral electrophoretic mobility) occurs for charge ratio between 0.6 (excess of polycation) and 1 (stoichiometry usual value) according to the pH. This atypical result is explained by the inaccessibility of some permanent cationic charge when screened by pH dependant cationic ones (due to the Hoffman alkylation). Isothermal titration calorimetry (ITC) indicates an endothermic formation of PEC with a binding constant around 10(5) L mol(-1). Finally asymmetrical flow field flow fractionation coupled on line with static multi angle light scattering (AF4/MALS) evidences soluble PECs with very large average molar masses and size around 100 nm, in agreement with scrambled eggs multi-association between various polyelectrolyte chains.

  20. Interaction of ortho-Phospho-l-serine with Hydroxyapatite: Formation of a Surface Complex

    PubMed

    Misra

    1997-10-01

    ortho-Phospho-l-serine (H2Psi, where Psi represents the serinephosphato ion), a constituent of salivary proteins, seems to play an important role in the mineralization of teeth. To understand the basic mechanism of this interaction, the uptake of o-phospho-l-serine from relatively concentrated aqueous solutions (up to 100 mmol/L) onto synthetic hydroxyapatite was studied. Previous studies have shown that in the dilute concentration range (<12.5 mmol/L) the uptake followed a regular Langmuirian adsorption plot. At higher concentrations the uptake curve increased steeply, but no formation of a separate phase in the reacted apatite was discernible, either by optical or by scanning electron microscopy. The dissolution of apatite released phosphate and calcium ions into the solution in amounts linearly related to the uptake of serine with P/Psi = 1 and Ca/Psi = 2. The charge and mass balance of the reaction can be reconciled with the formation of the surface complex (shown within brackets):Ca10(OH)2(PO4)6 + 6H2Psi --> [Ca6(HPsi)2(HPO4)2(PO4)2] + 4Ca2+ + 2HPsi1- + 2Psi2- + 2H2PO1-4 + 2H2O.The formation of two other surface complexes is possible; however, the complex shown above probably disrupts the apatite lattice the least. Traces of CaPsi·H2O precipitate out from the filtrates of highly concentrated solutions after 6 days. Copyright 1997 Academic Press. Copyright 1997Academic Press

  1. Effect of fat type in baked bread on amylose-lipid complex formation and glycaemic response.

    PubMed

    Lau, Evelyn; Zhou, Weibiao; Henry, Christiani Jeyakumar

    2016-06-01

    The formation of amylose-lipid complexes (ALC) had been associated with reduced starch digestibility. A few studies have directly characterised the extent of ALC formation with glycaemic response. The objectives of this study were to investigate the effect of using fats with varying degree of saturation and chain length on ALC formation as well as glycaemic and insulinaemic responses after consumption of bread. Healthy men consumed five test breads in a random order: control bread without any added fats (CTR) and breads baked with butter (BTR), coconut oil (COC), grapeseed oil (GRP) or olive oil (OLV). There was a significant difference in glycaemic response between the different test breads (P=0·002), primarily due to COC having a lower response than CTR (P=0·016), but no significant differences between fat types were observed. Insulinaemic response was not altered by the addition of fats/oils. Although BTR was more insulinotropic than GRP (P<0·05), postprandial β-cell function did not differ significantly. The complexing index (CI), a measure of ALC formation, was significantly higher for COC and OLV compared with BTR and GRP (P<0·05). CI was significantly negatively correlated with incremental AUC (IAUC) of change in blood glucose concentrations over time (IAUCglucose) (r -0·365, P=0·001). Linear regression analysis showed that CI explained 13·3 % of the variance and was a significant predictor of IAUCglucose (β=-1·265, P=0·001), but IAUCinsulin did not predict IAUCglucose. Our study indicated that a simple way to modulate glycaemic response in bread could lie in the choice of fats/oils, with coconut oil showing the greatest attenuation of glycaemic response.

  2. Algebraic approach to form factors in the complex sinh-Gordon theory

    NASA Astrophysics Data System (ADS)

    Lashkevich, Michael; Pugai, Yaroslav

    2017-01-01

    We study form factors of the quantum complex sinh-Gordon theory in the algebraic approach. In the case of exponential fields the form factors can be obtained from the known form factors of the ZN-symmetric Ising model. The algebraic construction also provides an Ansatz for form factors of descendant operators. We obtain generating functions of such form factors and establish their main properties: the cluster factorization and reflection equations.

  3. Formation of charge-transfer-complex in organic:metal oxides systems

    NASA Astrophysics Data System (ADS)

    Wu, S. P.; Kang, Y.; Liu, T. L.; Jin, Z. H.; Jiang, N.; Lu, Z. H.

    2013-04-01

    It is found that composite systems consisting of 4,4'-bis(carbazol-9-yl)biphenyl (CBP) and molybdenum trioxide (MoO3) form an IR absorption band around 847 nm. It is also found that the vibrational modes of the CBP, as measured by Fourier Transform Infrared Spectroscopy, are quenched upon the formation of charge-transfer-complex (CTC) between CBP and MoO3. By examining several sets of organic:metal oxides systems, we discovered that the IR absorption band of the CTCs follow two distinct mechanisms depending on the nature and location of the HOMOs in the organic molecules.

  4. Peculiarities of latent inhibition formation in SHR rats in conditioned task of different complexity.

    PubMed

    Kostyunina, N V; Loskutova, L V

    2012-05-01

    Inhibition of attention to irrelevant stimuli was studied in SHR rats using latent inhibition test. Latent inhibition was formed in two types of conditioned tasks with different levels of complexity and stress. Passive and active avoidance conditioning was preceded by preexposure to conditioned stimulus consisting of 20 and 100 non-reinforced presentations, respectively. Control Wistar rats demonstrated successful formation of latent inhibition in both tasks. SHR rats showed different degree of disruption of latent inhibition depending on the type of behavioral task. We assume that learning defect in these animals in respect to both novel and preexposed conditioned stimuli is associated with the lack of behavioral inhibition.

  5. Speciation of phytate ion in aqueous solution. Alkali metal complex formation in different ionic media.

    PubMed

    De Stefano, Concetta; Milea, Demetrio; Pettignano, Alberto; Sammartano, Silvio

    2003-08-01

    The acid-base properties of phytic acid [ myo-inositol 1,2,3,4,5,6-hexakis(dihydrogen phosphate)] (H(12)Phy; Phy(12-)=phytate anion) were studied in aqueous solution by potentiometric measurements ([H+]-glass electrode) in lithium and potassium chloride aqueous media at different ionic strengths (0< I mol L(-1)< or =3) and at t=25 degrees C. The protonation of phytate proved strongly dependent on both ionic medium and ionic strength. The protonation constants obtained in alkali metal chlorides are considerably lower than the corresponding ones obtained in a previous paper in tetraethylammonium iodide (Et(4)NI; e.g., at I=0.5 mol L(-1), log K(3)(H)=11.7, 8.0, 9.1, and 9.1 in Et(4)NI, LiCl, NaCl and KCl, respectively; the protonation constants in Et(4)NI and NaCl were already reported), owing to the strong interactions occurring between the phytate and alkaline cations present in the background salt. We explained this in terms of complex formation between phytate and alkali metal ions. Experimental evidence allows us to consider the formation of 13 mixed proton-metal-ligand complexes, M(j)H(i)Phy((12-i-j)-), (M+ =Li+, Na+, K+), with j< or =7 and i< or =6, in the range 2.5< or =pH< or =10 (some measurements, at low ionic strength, were extended to pH=11). In particular, all the species formed are negatively charged: i+j-12=-5, -6. Very high formation percentages of M+-phytate species are observed in all the pH ranges investigated. The stability of alkali metal complexes follows the trend Li+ > or =Na+K+. Some measurements were also performed at constant ionic strength (I=0.5 mol L(-1)), using different mixtures of Et(4)NI and alkali metal chlorides, in order to confirm the formation of hypothesized and calculated metal-proton-ligand complex species and to obtain conditional protonation constants in these multi-component ionic media.

  6. Preferential formation of the different hydrogen bonds and their effects in tetrahydrofuran and tetrahydropyran microhydrated complexes.

    PubMed

    Vallejos, Margarita M; Peruchena, Nélida M

    2012-04-26

    The role of cycloether-water (c-w) and water-water (w-w) hydrogen bonds (H-bonds) on the stability of the tetrahydrofuran THF/(H(2)O)(n) and the tetrahydropyran THP/(H(2)O)(n) complexes with n = 1-4 was investigated herein using the density functional and ab initio methods and the atoms in molecules theory. Geometry optimizations for these complexes were carried out with various possible initial guess structures. It was revealed that the major contributions of the mono and dihydrated complexes came from c-w H-bonds. A competition between c-w and w-w H-bonds contribution was observed for trihydrated complexes. For most of tetrahydrated complexes, the inter-water H-bonds provided the greatest contribution, whereas the c-w contributions were small but not negligible. It was confirmed that to produce a hydrophobic hydration of cycloethers, the C-H···O(w) H-bond should be associated with a network of H-bonds that connects both portions of the solute, through the formation of a bifunctional H-bond. A linear correlation is obtained for the sum of electron density at the bond critical points (ρ(b)) with the interaction energy (ΔE) and with the solute-solvent interaction energy (ΔE(s-w)) of the microhydrated complexes. In addition, a new way to estimate the energetic contribution as well as the preferential formation of the different H-bonds based completely on ρ(b) was found. Even more, it allows to differentiate the contribution from c-w interactions in both hydrophilic and hydrophobic contributions, it is therefore a useful tool for studying the hydration of large biomolecules. The analysis of the modifications in the atomic and group properties brought about by successive addition of H(2)O molecules allowed to pinpoint the atoms or molecular groups that undergo the greatest changes in electron population and energetic stabilization. It was identified that the remarkable stabilization of the water oxygen atoms is crucial for the stabilization of the complexes.

  7. Influence of Exciplex formation on the electroluminescent properties of dimeric Zn (II) bis-2-(2'-hydroxyphenyl) benzoxazole complex and monomeric Zn (II) 2-(1'-hydroxynaphthyl) benzothiazole complex

    NASA Astrophysics Data System (ADS)

    Prakash, Sattey; Anand, R. S.; Manoharan, S. Sundar

    2011-10-01

    In this paper we present the factors affecting electroluminescent properties of Zinc complexes of oxazole & thiazole derivatives. Electroluminescent spectra of the Zinc (II) complex of bis-[2-(2'-hydroxyphenyl) benzoxazole], [Zn (HPBO)2]2 and 2-(1'-hydroxynaphthyl) benzothiazole [Zn (HNBT)2] show unusual broadening and shows structural and photophysical similarity with [Zn (HPBT)2]2, a dimeric complex. The [Zn (HPBO)2]2 complex as an emissive layer in the device structure ITO /PEDOT:PSS /TPD (30nm) /[Zn (HPBO)2]2 (60nm) /BCP (6nm) /Ca (3nm) /Al (200nm) shows a broad bluish green emission, with a full width at half maxima (FWHM1˜70nm). The EL spectra is much broader compared to the PL spectra because of exciplex formation at the interfacial region between the emissive layer (EML) & hole transport layer (HTL). We also show the device performance of Zinc 2-(1'-hydroxynaphthyl) benzothiazole [Zn (HNBT)2] complex as emissive layer. Distinctly this device shows a broad greenish yellow emission with a peak maxima at 535nm and 690nm, owing to the exciplex formation between electron transport layer (ETL) and emissive layer (EML), which is in sharp contrast to the exciplex formation across the HTL-EML interface observed for the [Zn (HPBO)2]2 complex.

  8. Determination of absorptivity and formation constant of a chalcone association complex.

    PubMed

    Blanco, S E; Ferretti, F H

    1998-04-01

    A UV spectrometric method was developed to determine the molar absorptivity (epsilon(C)) and formation constant (K(c)) of the association complex of unsubstituted chalcone in cyclohexane, in the concentration range from 4.00.10(-4) to 2.00.10(-2) mol dm(-3). The thermodynamic and spectroscopic magnitudes such as K(c) and epsilon(C) contribute to the understanding of the physicochemical behavior of several alpha,beta-unsaturated carbonylic compounds, of low solubility in water, as it is the case of numerous flavonoids of chemical and biological importance. The studied association complex, formed by two chalcone molecules, is characterized by the constants epsilon(C) (300.8 nm)=4.98.10(4) dm(3) mol(-1) cm(-1) and K(c)=5.58.10(3). The method proposed is convenient for the study of solute-solute molecular associations particularly those due to dipole-dipole interactions.

  9. Time-resolved fluorescence spectroscopic investigation of cationic polymer/DNA complex formation

    NASA Astrophysics Data System (ADS)

    D'Andrea, Cosimo; Bassi, Andrea; Taroni, Paola; Pezzoli, Daniele; Volonterio, Alessandro; Candiani, Gabriele

    2011-07-01

    Since DNA is not internalized efficiently by cells, the success of gene therapy depends on the availability of carriers to efficiently deliver genetic material into target cells. Gene delivery vectors can be broadly categorized into viral and non-viral ones. Non-viral gene delivery systems are represented by cationic lipids and polymers rely on the basics of supramolecular chemistry termed "self-assembling": at physiological pH, they are cations and spontaneously form lipoplexes (for lipids) and polyplexes (for polymers) complexing nucleic acids. In this scenario, cationic polymers are commonly used as non-viral vehicles. Their effectiveness is strongly related to key parameters including DNA binding ability and stability in different environments. Time-resolved fluorescence spectroscopy of SYBR Green I (DNA dye) was carried out to characterize cationic polymer/DNA complex (polyplex) formation dispersed in aqueous solution. Both fluorescence amplitude and lifetime proved to be very sensitive to the polymer/DNA ratio (N/P ratio, +/-).

  10. Formation and dynamics of "waterproof" photoluminescent complexes of rare earth ions in crowded environment.

    PubMed

    Ignatova, Tetyana; Blades, Michael; Duque, Juan G; Doorn, Stephen K; Biaggio, Ivan; Rotkin, Slava V

    2014-12-28

    Understanding behavior of rare-earth ions (REI) in crowded environments is crucial for several nano- and bio-technological applications. Evolution of REI photoluminescence (PL) in small compartments inside a silica hydrogel, mimic to a soft matter bio-environment, has been studied and explained within a solvation model. The model uncovered the origin of high PL efficiency to be the formation of REI complexes, surrounded by bile salt (DOC) molecules. Comparative study of these REI-DOC complexes in bulk water solution and those enclosed inside the hydrogel revealed a strong correlation between an up to 5×-longer lifetime of REIs and appearance of the DOC ordered phase, further confirmed by dynamics of REI solvation shells, REI diffusion experiments and morphological characterization of microstructure of the hydrogel.

  11. Formation and properties of organo-phosphatase complexes by abiotic and biotic polymerization of pyrogallol-phosphatase mixtures.

    PubMed

    Rao, Maria A; Del Gaudio, Stefania; Scelza, Rosalia; Gianfreda, Liliana

    2010-04-28

    In this paper, the catalytic efficacy of peroxidase and manganese oxide, both commonly present in soil, to catalyze the formation of pyrogallol-phosphatase complexes was compared. The influence of several factors (e.g., the concentration of pyrogallol, the amount of catalysts, the nature of manganese oxide, birnessite, or pyrolusite, the incubation time, and the pH) on the transformation of pyrogallol and the characteristics and properties of the pyrogallol-phosphatase interaction products were investigated. The pyrogallol transformation mediated by both catalysts was very fast and increased by increasing the catalyst concentration. The nature of the catalyst also influenced the size and the molecular mass of the formed complexes. When polymerization of pyrogallol occurred with high intensity, a loss of phosphatase activity occurred, and it strongly depended on the pH at which the process was carried out and the catalyst. In particular, with peroxidase, the phosphatase activity was much lower in either suspensions or supernatants and not measurable in the insoluble complexes as compared to that measured in the presence of manganese oxides.

  12. C3b deposition on human erythrocytes induces the formation of a membrane skeleton–linked protein complex

    PubMed Central

    Karnchanaphanurach, Pallop; Mirchev, Rossen; Ghiran, Ionita; Asara, John M.; Papahadjopoulos-Sternberg, Brigitte; Nicholson-Weller, Anne; Golan, David E.

    2009-01-01

    Decay-accelerating factor (DAF, also known as CD55), a glycosylphosphatidylinositol-linked (GPI-linked) plasma membrane protein, protects autologous cells from complement-mediated damage by inhibiting complement component 3 (C3) activation. An important physical property of GPI-anchored complement regulatory proteins such as DAF is their ability to translate laterally in the plasma membrane. Here, we used single-particle tracking and tether-pulling experiments to measure DAF lateral diffusion, lateral confinement, and membrane skeletal associations in human erythrocyte membranes. In native membranes, most DAF molecules exhibited Brownian lateral diffusion. Fluid-phase complement activation caused deposition of C3b, one of the products of C3 cleavage, onto erythrocyte glycophorin A (GPA). We then determined that DAF, C3b, GPA, and band 3 molecules were laterally immobilized in the membranes of complement-treated cells, and GPA was physically associated with the membrane skeleton. Mass spectrometry analysis further showed that band 3, α-spectrin, β-spectrin, and ankyrin were present in a complex with C3b and GPA in complement-treated cells. C3b deposition was also associated with a substantial increase in erythrocyte membrane stiffness and/or viscosity. We therefore suggest that complement activation stimulates the formation of a membrane skeleton–linked DAF-C3b-GPA–band 3 complex on the erythrocyte surface. This complex may promote the removal of senescent erythrocytes from the circulation. PMID:19258706

  13. Probabilistic Multi-Factor Interaction Model for Complex Material Behavior

    NASA Technical Reports Server (NTRS)

    Chamis, Christos C.; Abumeri, Galib H.

    2008-01-01

    The Multi-Factor Interaction Model (MFIM) is used to evaluate the divot weight (foam weight ejected) from the launch external tanks. The multi-factor has sufficient degrees of freedom to evaluate a large number of factors that may contribute to the divot ejection. It also accommodates all interactions by its product form. Each factor has an exponent that satisfies only two points the initial and final points. The exponent describes a monotonic path from the initial condition to the final. The exponent values are selected so that the described path makes sense in the absence of experimental data. In the present investigation, the data used was obtained by testing simulated specimens in launching conditions. Results show that the MFIM is an effective method of describing the divot weight ejected under the conditions investigated.

  14. Probabilistic Multi-Factor Interaction Model for Complex Material Behavior

    NASA Technical Reports Server (NTRS)

    Chamis, Christos C.; Abumeri, Galib H.

    2008-01-01

    The Multi-Factor Interaction Model (MFIM) is used to evaluate the divot weight (foam weight ejected) from the launch external tanks. The multi-factor has sufficient degrees of freedom to evaluate a large number of factors that may contribute to the divot ejection. It also accommodates all interactions by its product form. Each factor has an exponent that satisfies only two points, the initial and final points. The exponent describes a monotonic path from the initial condition to the final. The exponent values are selected so that the described path makes sense in the absence of experimental data. In the present investigation the data used was obtained by testing simulated specimens in launching conditions. Results show that the MFIM is an effective method of describing the divot weight ejected under the conditions investigated.

  15. A Novel High Throughput Biochemical Assay to Evaluate the HuR Protein-RNA Complex Formation

    PubMed Central

    D’Agostino, Vito G.; Adami, Valentina; Provenzani, Alessandro

    2013-01-01

    The RNA binding protein HuR/ELAVL1 binds to AU-rich elements (AREs) promoting the stabilization and translation of a number of mRNAs into the cytoplasm, dictating their fate. We applied the AlphaScreen technology using purified human HuR protein, expressed in a mammalian cell-based system, to characterize in vitro its binding performance towards a ssRNA probe whose sequence corresponds to the are present in TNFα 3’ untranslated region. We optimized the method to titrate ligands and analyzed the kinetic in saturation binding and time course experiments, including competition assays. The method revealed to be a successful tool for determination of HuR binding kinetic parameters in the nanomolar range, with calculated Kd of 2.5±0.60 nM, kon of 2.76±0.56*106 M-1 min-1, and koff of 0.007±0.005 min-1. We also tested the HuR-RNA complex formation by fluorescent probe-based RNA-EMSA. Moreover, in a 384-well plate format we obtained a Z-factor of 0.84 and an averaged coefficient of variation between controls of 8%, indicating that this biochemical assay fulfills criteria of robustness for a targeted screening approach. After a screening with 2000 small molecules and secondary verification with RNA-EMSA we identified mitoxantrone as an interfering compound with rHuR and TNFα probe complex formation. Notably, this tool has a large versatility and could be applied to other RNA Binding Proteins recognizing different RNA, DNA, or protein species. In addition, it opens new perspectives in the identification of small-molecule modulators of RNA binding proteins activity. PMID:23951323

  16. Ubiquitination of p27 is regulated by Cdk-dependent phosphorylation and trimeric complex formation

    PubMed Central

    Montagnoli, Alessia; Fiore, Francesca; Eytan, Esther; Carrano, Andrea C.; Draetta, Giulio F.; Hershko, Avram; Pagano, Michele

    1999-01-01

    The cellular abundance of the cyclin-dependent kinase (Cdk) inhibitor p27 is regulated by the ubiquitin–proteasome system. Activation of p27 degradation is seen in proliferating cells and in many types of aggressive human carcinomas. p27 can be phosphorylated on threonine 187 by Cdks, and cyclin E/Cdk2 overexpression can stimulate the degradation of wild-type p27, but not of a threonine 187-to-alanine p27 mutant [p27(T187A)]. However, whether threonine 187 phosphorylation stimulates p27 degradation through the ubiquitin–proteasome system or an alternative pathway is still not known. Here, we demonstrate that p27 ubiquitination (as assayed in vivo and in an in vitro reconstituted system) is cell-cycle regulated and that Cdk activity is required for the in vitro ubiquitination of p27. Furthermore, ubiquitination of wild-type p27, but not of p27(T187A), can occur in G1-enriched extracts only upon addition of cyclin E/Cdk2 or cyclin A/Cdk2. Using a phosphothreonine 187 site-specific antibody for p27, we show that threonine 187 phosphorylation of p27 is also cell-cycle dependent, being present in proliferating cells but undetectable in G1 cells. Finally, we show that in addition to threonine 187 phosphorylation, efficient p27 ubiquitination requires formation of a trimeric complex with the cyclin and Cdk subunits. In fact, cyclin B/Cdk1 which can phosphorylate p27 efficiently, but cannot form a stable complex with it, is unable to stimulate p27 ubiquitination by G1 extracts. Furthermore, another p27 mutant [p27(CK−)] that can be phosphorylated by cyclin E/Cdk2 but cannot bind this kinase complex, is refractory to ubiquitination. Thus throughout the cell cycle, both phosphorylation and trimeric complex formation act as signals for the ubiquitination of a Cdk inhibitor. PMID:10323868

  17. Radiation increases the cellular uptake of exosomes through CD29/CD81 complex formation

    SciTech Connect

    Hazawa, Masaharu; Tomiyama, Kenichi; Saotome-Nakamura, Ai; Obara, Chizuka; Yasuda, Takeshi; Gotoh, Takaya; Tanaka, Izumi; Yakumaru, Haruko; Ishihara, Hiroshi; Tajima, Katsushi

    2014-04-18

    Highlights: • Radiation increases cellular uptake of exosomes. • Radiation induces colocalization of CD29 and CD81. • Exosomes selectively bind the CD29/CD81 complex. • Radiation increases the cellular uptake of exosomes through CD29/CD81 complex formation. - Abstract: Exosomes mediate intercellular communication, and mesenchymal stem cells (MSC) or their secreted exosomes affect a number of pathophysiologic states. Clinical applications of MSC and exosomes are increasingly anticipated. Radiation therapy is the main therapeutic tool for a number of various conditions. The cellular uptake mechanisms of exosomes and the effects of radiation on exosome–cell interactions are crucial, but they are not well understood. Here we examined the basic mechanisms and effects of radiation on exosome uptake processes in MSC. Radiation increased the cellular uptake of exosomes. Radiation markedly enhanced the initial cellular attachment to exosomes and induced the colocalization of integrin CD29 and tetraspanin CD81 on the cell surface without affecting their expression levels. Exosomes dominantly bound to the CD29/CD81 complex. Knockdown of CD29 completely inhibited the radiation-induced uptake, and additional or single knockdown of CD81 inhibited basal uptake as well as the increase in radiation-induced uptake. We also examined possible exosome uptake processes affected by radiation. Radiation-induced changes did not involve dynamin2, reactive oxygen species, or their evoked p38 mitogen-activated protein kinase-dependent endocytic or pinocytic pathways. Radiation increased the cellular uptake of exosomes through CD29/CD81 complex formation. These findings provide essential basic insights for potential therapeutic applications of exosomes or MSC in combination with radiation.

  18. Fluids circulations during the formation of the Naxos Metamorphic Core Complex (Greece)

    NASA Astrophysics Data System (ADS)

    Vanderhaeghe, Olivier; Boiron, Marie-Christine; Siebenaller, Luc

    2015-04-01

    The island of Naxos, in the central part of the Cycladic Metamorphic Core Complex (Greece) represents a perfect example to address the evolution of fluid circulations during collapse of an orogenic belt. It displays a complex detachment system characterized by mylonites, cataclasites and high-angle normal faults which geometric relationships reflect rheological layering of the orogenic crust and its evolution during collapse. The chemistry of fluid inclusions determined by microthermometry, RAMAN spectroscopy, LA-ICPMS, and crush-leach combined with C and H isotopic signatures point to three distinct types of fluids, namely (i) a H2O-dominated fluid, (ii) a composite H2O-CO2 fluid, and (iii) a NaCl-rich fluid concentrated in metals. These different types of fluids are interpreted to reflect mixtures to various degrees among fluids generated by (i) condensation of clouds (meteoric aqueous fluid), (ii) dehydration and decarbonatation of metasedimentary rocks during metamorphism (metamorphic aqueous-carbonic fluid), and (iii) crystallization of granitic magmas (magmatic saline fluid with high metal contents). The distribution of fluids with respect to microstructures evidences the close link between deformation and fluid circulations at the mineral scale from intracristalline deformation to fracturing. The orientation of fluid inclusion planes, veins and alteration zones allows to identify the scale and geometry of the reservoir into which fluids are circulating and their evolution during the formation of the Metamorphic Core Complex. These data indicate that the orogenic crust is subdivided in two reservoirs separated by the ductile/fragile transition. Meteoric fluids circulate in the upper crust affected by brittle deformation whereas metamorphic and magmatic fluids circulate in relation to intracristalline ductile deformation affecting the lower crust. The geometry of these reservoirs evolves during the formation of the Naxos Metamorphic Core Complex as the

  19. Hormad1 mutation disrupts synaptonemal complex formation, recombination, and chromosome segregation in mammalian meiosis.

    PubMed

    Shin, Yong-Hyun; Choi, Youngsok; Erdin, Serpil Uckac; Yatsenko, Svetlana A; Kloc, Malgorzata; Yang, Fang; Wang, P Jeremy; Meistrich, Marvin L; Rajkovic, Aleksandar

    2010-11-04

    Meiosis is unique to germ cells and essential for reproduction. During the first meiotic division, homologous chromosomes pair, recombine, and form chiasmata. The homologues connect via axial elements and numerous transverse filaments to form the synaptonemal complex. The synaptonemal complex is a critical component for chromosome pairing, segregation, and recombination. We previously identified a novel germ cell-specific HORMA domain encoding gene, Hormad1, a member of the synaptonemal complex and a mammalian counterpart to the yeast meiotic HORMA domain protein Hop1. Hormad1 is essential for mammalian gametogenesis as knockout male and female mice are infertile. Hormad1 deficient (Hormad1(-/) (-)) testes exhibit meiotic arrest in the early pachytene stage, and synaptonemal complexes cannot be visualized by electron microscopy. Hormad1 deficiency does not affect localization of other synaptonemal complex proteins, SYCP2 and SYCP3, but disrupts homologous chromosome pairing. Double stranded break formation and early recombination events are disrupted in Hormad1(-/) (-) testes and ovaries as shown by the drastic decrease in the γH2AX, DMC1, RAD51, and RPA foci. HORMAD1 co-localizes with γH2AX to the sex body during pachytene. BRCA1, ATR, and γH2AX co-localize to the sex body and participate in meiotic sex chromosome inactivation and transcriptional silencing. Hormad1 deficiency abolishes γH2AX, ATR, and BRCA1 localization to the sex chromosomes and causes transcriptional de-repression on the X chromosome. Unlike testes, Hormad1(-/) (-) ovaries have seemingly normal ovarian folliculogenesis after puberty. However, embryos generated from Hormad1(-/) (-) oocytes are hyper- and hypodiploid at the 2 cell and 8 cell stage, and they arrest at the blastocyst stage. HORMAD1 is therefore a critical component of the synaptonemal complex that affects synapsis, recombination, and meiotic sex chromosome inactivation and transcriptional silencing.

  20. Mutations in the rpoS gene are the major limiting factor for biofilm formation in Escherichia coli serotype O157:H7 clinical isolates

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Background: Biofilm formation is a complex process that is highly regulated through a battery of transcriptional regulators, small regulatory RNAs, and environmental conditions. RpoS sigma factor along with MlrA protein directly regulate the expression of the curli key regulator CsgD. In most serot...

  1. E-ring conformation has a key role in cleavable complex formation: homocamptothecin versus camptothecins

    NASA Astrophysics Data System (ADS)

    Chauvier, D.; Chourpa, I.; Maizieres, M.; Riou, J.-F.; Dauchez, M.; Alix, A. J. P.; Manfait, M.

    2003-06-01

    Homocamptothecin (hCPT) is a new camptothecin (CPT) derivative with a seven-membered β-hydroxylactone E-ring. This modification provides higher lactone stability and did not impair its activity against topoisomerase I (top1), but rather appears to improve it compared to CPT. Such lactone modification was unexpected regarding the previous structure-activity relationship data inside the CPT series, and may have crucial mechanistic implications in the ternary cleavable complex formation. In this study, the detailed characterization of the E-ring homologation and lactone/carboxylate conversion, self-aggregation, influence of pH and polarity of the molecular environment have been performed for hCPT by frequency-domain fluorescence. The real-time spectrofluorometry confirmed the enhanced stability of hCPT. We have also investigated the E-ring status of hCPT within the top1 ternary complex with DNA, and with top1 or DNA binary complexes. Unlike CPT, no modification of the (β-hydroxy-) lactone-carboxylate conversion rates was observed, suggesting that E-ring opening is not required for cleavable complex stabilization in presence of hCPT. Comparison of the two structures by molecular modeling revealed similar conformation and steric volumes between the β-hydroxylactone ring conformation of hCPT and the opened ring of CPT. The lack of hCPT E-ring opening was discussed in the light of these molecular modeling results.

  2. Formation of novel transition metal hydride complexes with ninefold hydrogen coordination

    PubMed Central

    Takagi, Shigeyuki; Iijima, Yuki; Sato, Toyoto; Saitoh, Hiroyuki; Ikeda, Kazutaka; Otomo, Toshiya; Miwa, Kazutoshi; Ikeshoji, Tamio; Orimo, Shin-ichi

    2017-01-01

    Ninefold coordination of hydrogen is very rare, and has been observed in two different hydride complexes comprising rhenium and technetium. Herein, based on a theoretical/experimental approach, we present evidence for the formation of ninefold H- coordination hydride complexes of molybdenum ([MoH9]3−), tungsten ([WH9]3−), niobium ([NbH9]4−) and tantalum ([TaH9]4−) in novel complex transition-metal hydrides, Li5MoH11, Li5WH11, Li6NbH11 and Li6TaH11, respectively. All of the synthesized materials are insulated with band gaps of approximately 4 eV, but contain a sufficient amount of hydrogen to cause the H 1s-derived states to reach the Fermi level. Such hydrogen-rich materials might be of interest for high-critical-temperature superconductivity if the gaps close under compression. Furthermore, the hydride complexes exhibit significant rotational motions associated with anharmonic librations at room temperature, which are often discussed in relation to the translational diffusion of cations in alkali-metal dodecahydro-closo-dodecaborates and strongly point to the emergence of a fast lithium conduction even at room temperature. PMID:28287143

  3. Formation of novel transition metal hydride complexes with ninefold hydrogen coordination

    NASA Astrophysics Data System (ADS)

    Takagi, Shigeyuki; Iijima, Yuki; Sato, Toyoto; Saitoh, Hiroyuki; Ikeda, Kazutaka; Otomo, Toshiya; Miwa, Kazutoshi; Ikeshoji, Tamio; Orimo, Shin-Ichi

    2017-03-01

    Ninefold coordination of hydrogen is very rare, and has been observed in two different hydride complexes comprising rhenium and technetium. Herein, based on a theoretical/experimental approach, we present evidence for the formation of ninefold H- coordination hydride complexes of molybdenum ([MoH9]3‑), tungsten ([WH9]3‑), niobium ([NbH9]4‑) and tantalum ([TaH9]4‑) in novel complex transition-metal hydrides, Li5MoH11, Li5WH11, Li6NbH11 and Li6TaH11, respectively. All of the synthesized materials are insulated with band gaps of approximately 4 eV, but contain a sufficient amount of hydrogen to cause the H 1s-derived states to reach the Fermi level. Such hydrogen-rich materials might be of interest for high-critical-temperature superconductivity if the gaps close under compression. Furthermore, the hydride complexes exhibit significant rotational motions associated with anharmonic librations at room temperature, which are often discussed in relation to the translational diffusion of cations in alkali-metal dodecahydro-closo-dodecaborates and strongly point to the emergence of a fast lithium conduction even at room temperature.

  4. Formation of novel transition metal hydride complexes with ninefold hydrogen coordination.

    PubMed

    Takagi, Shigeyuki; Iijima, Yuki; Sato, Toyoto; Saitoh, Hiroyuki; Ikeda, Kazutaka; Otomo, Toshiya; Miwa, Kazutoshi; Ikeshoji, Tamio; Orimo, Shin-Ichi

    2017-03-13

    Ninefold coordination of hydrogen is very rare, and has been observed in two different hydride complexes comprising rhenium and technetium. Herein, based on a theoretical/experimental approach, we present evidence for the formation of ninefold H- coordination hydride complexes of molybdenum ([MoH9](3-)), tungsten ([WH9](3-)), niobium ([NbH9](4-)) and tantalum ([TaH9](4-)) in novel complex transition-metal hydrides, Li5MoH11, Li5WH11, Li6NbH11 and Li6TaH11, respectively. All of the synthesized materials are insulated with band gaps of approximately 4 eV, but contain a sufficient amount of hydrogen to cause the H 1s-derived states to reach the Fermi level. Such hydrogen-rich materials might be of interest for high-critical-temperature superconductivity if the gaps close under compression. Furthermore, the hydride complexes exhibit significant rotational motions associated with anharmonic librations at room temperature, which are often discussed in relation to the translational diffusion of cations in alkali-metal dodecahydro-closo-dodecaborates and strongly point to the emergence of a fast lithium conduction even at room temperature.

  5. Ice Complex formation in arctic East Siberia during the MIS3 Interstadial

    NASA Astrophysics Data System (ADS)

    Wetterich, Sebastian; Tumskoy, Vladimir; Rudaya, Natalia; Andreev, Andrei A.; Opel, Thomas; Meyer, Hanno; Schirrmeister, Lutz; Hüls, Matthias

    2014-01-01

    A continuous 15 m long sequence of Ice Complex permafrost (Yedoma) exposed in a thermo-cirque at the southern coast of Bol'shoy Lyakhovsky Island (New Siberian Archipelago, Dmitry Laptev Strait) was studied to reconstruct past landscape and environmental dynamics. The sequence accumulated during the Marine Isotope Stage 3 (MIS3) Interstadial between >49 and 29 ka BP in an ice-wedge polygon. The frozen deposits were cryolithologically described and sampled on a vertical bluff between two ice wedges. According to sedimentological and geochronological data, the section is subdivided into three units which correlate with environmental conditions of the early, middle, and late MIS3 period. Palynological data support this stratification. The stable isotope signature of texture ice in the polygon structure reflects fractionation due to local freeze-thaw processes, while the signature of an approximately 5 m wide and more than 17 m high ice wedge fits very well into the regional stable-water isotope record. Regional climate dynamics during the MIS3 Interstadial and local landscape conditions of the polygonal patterned ground controlled the Ice Complex formation. The sequence presented here completes previously published MIS3 permafrost records in Northeast Siberia. Late Quaternary stadial-interstadial climate variability in arctic West Beringia is preserved at millennial resolution in the Ice Complex. A MIS3 climate optimum was revealed between 48 and 38 ka BP from the Ice Complex on Bol'shoy Lyakhovsky Island.

  6. Zeaxanthin Radical Cation Formation in Minor Light-Harvesting Complexes of Higher Plant Antenna

    SciTech Connect

    Avenson, Thomas H.; Ahn, Tae Kyu; Zigmantas, Donatas; Niyogi, Krishna K.; Li, Zhirong; Ballottari, Matteo; Bassi, Roberto; Fleming, Graham R.

    2008-01-31

    Previous work on intact thylakoid membranes showed that transient formation of a zeaxanthin radical cation was correlated with regulation of photosynthetic light-harvesting via energy-dependent quenching. A molecular mechanism for such quenching was proposed to involve charge transfer within a chlorophyll-zeaxanthin heterodimer. Using near infrared (880-1100 nm) transient absorption spectroscopy, we demonstrate that carotenoid (mainly zeaxanthin) radical cation generation occurs solely in isolated minor light-harvesting complexes that bind zeaxanthin, consistent with the engagement of charge transfer quenching therein. We estimated that less than 0.5percent of the isolated minor complexes undergo charge transfer quenching in vitro, whereas the fraction of minor complexes estimated to be engaged in charge transfer quenching in isolated thylakoids was more than 80 times higher. We conclude that minor complexes which bind zeaxanthin are sites of charge transfer quenching in vivo and that they can assume Non-quenching and Quenching conformations, the equilibrium LHC(N)<--> LHC(Q) of which is modulated by the transthylakoid pH gradient, the PsbS protein, and protein-protein interactions.

  7. Ternary complex formation facilitates a redox mechanism for iron release from a siderophore.

    PubMed

    Mies, Kassy A; Wirgau, Joseph I; Crumbliss, Alvin L

    2006-04-01

    While the naturally occurring reducing agents glutathione (GSH) and ascorbate (H2A) alone are ineffective at reducing iron(III) sequestered by the siderophore ferrioxamine B, the addition of an iron(II) chelator, sulfonated bathophenanthroline (BPDS), facilitates reduction by either reducing agent. A mechanism is described in which a ternary complex is formed between ferrioxamine B and BPDS in a rapidly established pre-equilibrium step, which is followed by rate limiting reduction of the ternary complex by glutathione or ascorbate. Spectral, thermodynamic, and kinetic evidence are given for ternary complex formation. Ascorbate was found to be slightly more efficient at reducing the ternary complex than glutathione (k4=2.1 x 10(-3) M(-1) s(-1) and k4=6.3 x 10(-4) M(-1) s(-1), respectively) at pH 7. Reduction is followed by a rapid ligand exchange step where iron is released from ferrioxamine B to form tris-(BPDS)iron(II). The implications of these results for siderophore mediated iron transport and release are discussed.

  8. Cas1-Cas2 complex formation mediates spacer acquisition during CRISPR-Cas adaptive immunity.

    PubMed

    Nuñez, James K; Kranzusch, Philip J; Noeske, Jonas; Wright, Addison V; Davies, Christopher W; Doudna, Jennifer A

    2014-06-01

    The initial stage of CRISPR-Cas immunity involves the integration of foreign DNA spacer segments into the host genomic CRISPR locus. The nucleases Cas1 and Cas2 are the only proteins conserved among all CRISPR-Cas systems, yet the molecular functions of these proteins during immunity are unknown. Here we show that Cas1 and Cas2 from Escherichia coli form a stable complex that is essential for spacer acquisition and determine the 2.3-Å-resolution crystal structure of the Cas1-Cas2 complex. Mutations that perturb Cas1-Cas2 complex formation disrupt CRISPR DNA recognition and spacer acquisition in vivo. Active site mutants of Cas2, unlike those of Cas1, can still acquire new spacers, thus indicating a nonenzymatic role of Cas2 during immunity. These results reveal the universal roles of Cas1 and Cas2 and suggest a mechanism by which Cas1-Cas2 complexes specify sites of CRISPR spacer integration.

  9. Investigating the Effect of Complexity Factors in Stoichiometry Problems Using Logistic Regression and Eye Tracking

    ERIC Educational Resources Information Center

    Tang, Hui; Kirk, John; Pienta, Norbert J.

    2014-01-01

    This paper includes two experiments, one investigating complexity factors in stoichiometry word problems, and the other identifying students' problem-solving protocols by using eye-tracking technology. The word problems used in this study had five different complexity factors, which were randomly assigned by a Web-based tool that we developed. The…

  10. Equilibrium and Formation/Dissociation Kinetics of some Lanthanide(III)-PCTA complexes

    PubMed Central

    Tircsó, Gyula; Kovács, Zoltán; Sherry, A. Dean

    2008-01-01

    The protonation constants (KiH) of 3,6,9,15-tetraazabicyclo[9.3.1]pentadeca-1(15),11,13-triene-3,6,9,-triacetic acid (PCTA) and stability constants of complexes formed between this pyridine containing macrocycle and several different metal ions have been determined in 1.0 M KCl, 25°C and compared to previous literature values. The first protonation constant was found to be 0.5-0.6 log units higher than the value reported previously and a total five protonation steps were detected (log KiH = 11.36, 7.35, 3.83, 2.12 and 1.29). The stability constants of complexes formed between PCTA and Mg2+, Ca2+, Cu2+ and Zn2+ were also somewhat higher than those previously reported but this difference could be largely attributed to the higher first protonation constant of the ligand. Stability constants of complexes formed between PCTA and the Ln3+ series of ions and Y3+ were determined by using an “out-of-cell” potentiometric method. These values ranged from log K = 18.15 for Ce(PCTA) to log K = 20.63 for Yb(PCTA), increasing along the lanthanide series in proportion to decreasing Ln3+ cation size. The rates of complex formation for Ce(PCTA), Eu(PCTA), Y(PCTA) and Yb(PCTA) were followed by conventional UV-VIS spectroscopy in the pH range pH=3.5 - 4.4. First order rate constants (saturation kinetics) obtained for different ligand / metal ion ratios were consistent with rapid formation of a diprotonated intermediate, Ln(H2PCTA)2+. The stabilities of the intermediates as determined from the kinetic data were 2.81, 3.12, 2.97 and 2.69 log K units for Ce(H2PCTA), Eu(H2PCTA), Y(H2PCTA) and Yb(H2PCTA), respectively. Rearrangement of these intermediates to the fully chelated complexes was the rate determining step and the rate constant (kr) for this process was found to be inversely proportional to the proton concentration. The formation rates (kOH) increased with a decrease in lanthanide ion size (9.68×107 M-1s-1, 1.74×108 M-1s-1, 1.13×108 M-1s-1 and 1.11×109 M-1s-1 for Ce

  11. Equilibrium and formation/dissociation kinetics of some Ln(III)PCTA complexes.

    PubMed

    Tircsó, Gyula; Kovacs, Zoltan; Sherry, A Dean

    2006-11-13

    The protonation constants () of 3,6,9,15-tetraazabicyclo[9.3.1]pentadeca-1(15),11,13-triene-3,6,9-triacetic acid (PCTA) and stability constants of complexes formed between this pyridine-containing macrocycle and several different metal ions have been determined in 1.0 M KCl at 25 degrees C and compared to previous literature values. The first protonation constant was found to be 0.5-0.6 log units higher than the value reported previously, and a total of five protonation steps were detected (log = 11.36, 7.35, 3.83, 2.12, and 1.29). The stability constants of complexes formed between PCTA and Mg2+, Ca2+, Cu2+, and Zn2+ were also somewhat higher than those previously reported, but this difference could be largely attributed to the higher first protonation constant of the ligand. Stability constants of complexes formed between PCTA and the Ln3+ series of ions and Y3+ were determined by using an "out-of-cell" potentiometric method. These values ranged from log K = 18.15 for Ce(PCTA) to log K = 20.63 for Yb(PCTA), increasing along the Ln series in proportion to decreasing Ln3+ cation size. The rates of complex formation for Ce(PCTA), Eu(PCTA), Y(PCTA), and Yb(PCTA) were followed by conventional UV-vis spectroscopy in the pH range 3.5-4.4. First-order rate constants (saturation kinetics) obtained for different ligand-to-metal ion ratios were consistent with the rapid formation of a diprotonated intermediate, Ln(H(2)PCTA)(2+). The stabilities of the intermediates as determined from the kinetic data were 2.81, 3.12, 2.97, and 2.69 log K units for Ce(H(2)PCTA), Eu(H(2)PCTA), Y(H(2)PCTA), and Yb(H(2)PCTA), respectively. Rearrangement of these intermediates to the fully chelated complexes was the rate-determining step, and the rate constant (k(r)) for this process was found to be inversely proportional to the proton concentration. The formation rates (k(OH)) increased with a decrease in the lanthanide ion size [9.68 x 10(7), 1.74 x 10(8), 1.13 x 10(8), and 1.11 x 10(9) M(-1

  12. Structure of a bacterial quorum-sensing transcription factor complexed with pheromone and DNA.

    SciTech Connect

    Zhang, R.; Pappas, T.; Brace, J.; Miller, P.; Oulmassov, T.; Molyneaux, J.; Anderson, J.; Bashkin, J.; Winans, S.; Joachimiak, A.; Biosciences Division; Cornell Univ.; Monsanto Co.

    2002-06-27

    Many proteobacteria are able to monitor their population densities through the release of pheromones known as N-acylhomoserine lactones. At high population densities, these pheromones elicit diverse responses that include bioluminescence, biofilm formation, production of antimicrobials, DNA exchange, pathogenesis and symbiosis1. Many of these regulatory systems require a pheromone-dependent transcription factor similar to the LuxR protein of Vibrio fischeri. Here we present the structure of a LuxR-type protein. TraR of Agrobacterium tumefaciens was solved at 1.66 A as a complex with the pheromone N-3-oxooctanoyl-l-homoserine lactone (OOHL) and its TraR DNA-binding site. The amino-terminal domain of TraR is an {alpha}/{beta}/{alpha} sandwich that binds OOHL, whereas the carboxy-terminal domain contains a helix-turn-helix DNA-binding motif. The TraR dimer displays a two-fold symmetry axis in each domain; however, these two axes of symmetry are at an approximately 90 degree angle, resulting in a pronounced overall asymmetry of the complex. The pheromone lies fully embedded within the protein with virtually no solvent contact, and makes numerous hydrophobic contacts with the protein as well as four hydrogen bonds: three direct and one water-mediated.

  13. NUTRITIONAL FACTORS STIMULATING THE FORMATION OF LYSINE DECARBOXYLASE IN ESCHERICHIA COLI

    PubMed Central

    Maretzki, Andrew; Mallette, M. F.

    1962-01-01

    Maretzki, Andrew (Pennsylvania State University, University Park) and M. F. Mallette. Nutritional factors stimulating the formation of lysine decarboxylase in Escherichia coli. J. Bacteriol. 83:720–726. 1962 — Inclusion of complex nitrogen sources in the induction medium was shown to be necessary for the synthesis of appreciable amounts of l-lysine decarboxylase by Escherichia coli B. Hy-case, a commercial acid hydrolyzate of casein, was especially effective in enzyme production, which was assayed manometrically after lysis of the bacteria from without by bacteriophage. Partial fractionation of the Hy-case, identification of the free amino acids, and addition of these amino acids to test media revealed stimulatory effects by methionine, threonine, proline, leucine, and tyrosine. A full complement of amino acids did not match the enzyme levels reached in the presence of Hy-case. Certain peptide fractions obtained from this mixture supplemented the effects of the amino acids in such a way as to suggest direct incorporation of peptide rather than transport or protective roles. Added purines, pyrimidines, iron, and water-soluble vitamins were without effect. Neither carbohydrates nor phosphorylated materials could be detected in the stimulatory fractions. PMID:14469751

  14. Improving the aqueous solubility of triclosan by solubilization, complexation, and in situ salt formation.

    PubMed

    Grove, Christine; Liebenberg, Wilna; du Preez, Jan L; Yang, Wenzhan; de Villiers, Melgardt M

    2003-01-01

    Triclosan, an antimicrobial, although widely incorporated into many skin care products, toothpastes, and liquid soaps, presents formulation difficulties because it is practically insoluble in water. The objective of this study was to improve the aqueous solubility of triclosan through solubilization, complexation, and salt formation. The solubility of triclosan in distilled water and in phosphate buffers (pH 7.4) was determined at 30 degrees C. The order of solubilizing performance of the solubilizers was: N-methylglucamine> or =L-arginine>sodium lauryl sulfate>beta-cyclodextrin> or =hydroxypropyl-beta-cyclodextrin>ethanolamine>sodium benzoate>sodium methyl 4-hydroxybenzoate>triethanolamine> or =diethanolamine. These solubilizers increased the solubility of triclosan from 80- to 6000-fold. Micellar solubilization and the formation of either salts or complexes are postulated as possible mechanisms for the increase in the solubility of triclosan by the surfactant sodium lauryl sulphate, the cyclic sugar derivatives beta-cyclodextrin and 2-hydropropyl-beta-cyclodextrin, the amino acid L-arginine, and the amino sugar alcohol N-methylglucamine. Furthermore, although the bacteriostatic efficacy of triclosan was significantly increased when solubilized with N-methylglucamine, L-arginine, and ethanolamine, increased solubilization did not increase the effectiveness of triclosan for all solubilizers tested.

  15. Interaction and complex formation between catalase and cationic polyelectrolytes: chitosan and Eudragit E100.

    PubMed

    Boeris, Valeria; Romanini, Diana; Farruggia, Beatriz; Picó, Guillemo

    2009-08-01

    Interactions between catalase and the cationic polyelectrolytes: chitosan and Eudragit E100 have been investigated owing to their scientific and technological importance. These interactions have been characterized by turbidimetry, circular dichroism and fluorescence spectroscopy. It was found that the catalase conformation does not change significantly during the chain entanglements between the protein and the polyelectrolytes. The effects of pH, ionic strength and anions which modify the water structure were evaluated on the polymer-protein complex formation. A net coulombic interaction force between them was found since the insoluble complex formation decreased after the NaCl addition. Both polymers were found to precipitate around 80% of the protein in solution. No modification of the tertiary and secondary protein structure or the enzymatic activity was observed when the precipitate was dissolved by changing the pH of the medium. Chitosan and Eudragit E100 proved to be a useful framework to isolate catalase or proteins with a slightly acid isoelectrical pH by means of precipitation.

  16. Paleobiology of a Neoproterozoic tidal flat/lagoonal complex: the Draken Conglomerate Formation, Spitsbergen.

    PubMed

    Knoll, A H; Swett, K; Mark, J

    1991-01-01

    Carbonates and rare shales of the ca 700-800 Ma old Draken Conglomerate Formation, northeastern Spitsbergen, preserve a record of environmental variation within a Neoproterozoic tidal flat/lagoon complex. Forty-two microfossil taxa have been recognized in Draken rocks, and of these, 39 can be characterized in terms of their paleoenvironmental distributions along a gradient from the supratidal zone to permanently submerged lagoons. Supratidal to subtidal trends include: increasing microbenthic diversity, increasing abundance and diversity of included allochthonous (presumably planktonic) elements, decreasing sheath thickness of mat-building organisms (with significant taphonomic consequences), and an increasing sediment/fossil ratio in fossiliferous rocks. Five principal and several minor biofacies can be distinguished. The paleoecological resolution obtainable in the Draken Conglomerate Formation rivals that achieved for most Phanerozoic fossil deposits. It documents the complexity and diversity of Proterozoic coastal ecosystems and indicates that both environment and taphonomy need to be taken into explicit consideration in attempts to understand evolutionary trends in early fossil record. Three species, Coniunctiophycus majorinum, Myxococcoides distola, and M. chlorelloidea, are described as new; Siphonophycus robustum, Siphonophycus septatum, and Gorgonisphaeridium maximum are proposed as new combinations.

  17. Paleobiology of a Neoproterozoic tidal flat/lagoonal complex: the Draken Conglomerate Formation, Spitsbergen

    NASA Technical Reports Server (NTRS)

    Knoll, A. H.; Swett, K.; Mark, J.

    1991-01-01

    Carbonates and rare shales of the ca 700-800 Ma old Draken Conglomerate Formation, northeastern Spitsbergen, preserve a record of environmental variation within a Neoproterozoic tidal flat/lagoon complex. Forty-two microfossil taxa have been recognized in Draken rocks, and of these, 39 can be characterized in terms of their paleoenvironmental distributions along a gradient from the supratidal zone to permanently submerged lagoons. Supratidal to subtidal trends include: increasing microbenthic diversity, increasing abundance and diversity of included allochthonous (presumably planktonic) elements, decreasing sheath thickness of mat-building organisms (with significant taphonomic consequences), and an increasing sediment/fossil ratio in fossiliferous rocks. Five principal and several minor biofacies can be distinguished. The paleoecological resolution obtainable in the Draken Conglomerate Formation rivals that achieved for most Phanerozoic fossil deposits. It documents the complexity and diversity of Proterozoic coastal ecosystems and indicates that both environment and taphonomy need to be taken into explicit consideration in attempts to understand evolutionary trends in early fossil record. Three species, Coniunctiophycus majorinum, Myxococcoides distola, and M. chlorelloidea, are described as new; Siphonophycus robustum, Siphonophycus septatum, and Gorgonisphaeridium maximum are proposed as new combinations.

  18. The Scaling Relations and Star Formation Laws of Mini-starburst Complexes

    NASA Astrophysics Data System (ADS)

    Nguyen-Luong, Quang; Nguyen, Hans V. V.; Motte, Fredérique; Schneider, Nicola; Fujii, Michiko; Louvet, Fabien; Hill, Tracey; Sanhueza, Patricio; Chibueze, James O.; Didelon, Pierre

    2016-12-01

    The scaling relations and star formation laws for molecular cloud complexes (MCCs) in the Milky Way are investigated. MCCs are mostly large (R > 50 pc), massive (˜106 {\\text{}}{M}⊙ ) gravitationally unbound cloud structures. We compare their masses {M}{gas}, mass surface densities {{{Σ }}}{M{gas}}, radii R, velocity dispersions σ, star formation rates (SFRs), and SFR densities {{{Σ }}}{SFR} with those of structures ranging from cores, clumps, and giant molecular clouds, to MCCs, and galaxies, spanning eight orders of magnitudes in size and 13 orders of magnitudes in mass. This results in the following universal relations:σ ˜ {R}0.5,{M}{gas}˜ {R}2,{{{Σ }}}{SFR}˜ {{{Σ }}}{M{gas}}1.5, {SFR}˜ {{M}{gas}}0.9, {and} {SFR}˜ {σ }2.7. Variations in the slopes and coefficients of these relations are found at individual scales, signifying different physics acting at different scales. Additionally, there are breaks at the MCC scale in the σ {--}R relation and between starburst and normal star-forming objects in the {SFR}{--}{M}{gas} and {{{Σ }}}{SFR}-{{{Σ }}}{{{M}}{gas}} relations. Therefore, we propose to use the Schmidt-Kennicutt diagram to distinguish starburst from normal star-forming structures by applying a {{{Σ }}}{M{gas}} threshold of ˜100 {\\text{}}{M}⊙ pc-2 and a {{{Σ }}}{SFR} threshold of 1 {\\text{}}{M}⊙ yr-1 kpc-2. Mini-starburst complexes are gravitationally unbound MCCs that have enhanced {{{Σ }}}{SFR} (>1 {\\text{}}{M}⊙ yr-1 kpc-2), probably caused by dynamic events such as radiation pressure, colliding flows, or spiral arm gravitational instability. Because of dynamical evolution, gravitational boundedness does not play a significant role in regulating the star formation activity of MCCs, especially the mini-starburst complexes, which leads to the dynamical formation of massive stars and clusters. We emphasize the importance of understanding mini-starbursts in investigating the physics of starburst galaxies.

  19. Interaction between the antibiotic spiramycin and a ribosomal complex active in peptide bond formation.

    PubMed

    Dinos, G; Synetos, D; Coutsogeorgopoulos, C

    1993-10-12

    The inhibition of peptide bond formation by spiramycin was studied in an in vitro system derived from Escherichia coli. Peptide bonds are formed between puromycin (S) and Ac-Phe-tRNA, which is a component of complex C, i.e., of the [Ac-Phe-tRNA-70S ribosome-poly(U)] complex, according to the puromycin reaction: C+S (Ks)<==>CS (k3)==>C'+P [Synetos, D., & Coutsogeorgopoulos, C. (1987) Biochim. Biophys. Acta 923, 275-285]. It is shown that spiramycin (A) reacts with complex C and forms the spiramycin complex C*A, which is inactive toward puromycin. C*A is the tightest complex formed between complex C and any of a number of antibiotics, such as chloramphenicol, blasticidin S, lincomycin, or sparsomycin. C*A remains stable following gel chromatography on Sephadex G-200 and sucrose gradient ultracentrifugation. Detailed kinetic study suggests that C*A is formed in a variation of a two-step mechanism in which the initial encounter complex CA is kinetically insignificant and C*A is the product of a conformational change of complex CA according to the equation, C+A (kassoc)<==>(kdissoc) C*A. The rate constants of this reaction (spiramycin reaction) are kassoc = 3.0 x 10(4) M-1 s-1 and kdissoc = 5.0 x 10(-5) s-1. Such values allow the classification of spiramycin as a slow-binding, slowly reversible inhibitor; they also lead to the calculation of an apparent overall dissociation constant equal to 1.8 nM for the C*A complex. Furthermore, they render spiramycin a useful tool in the study of antibiotic action on protein synthesis in vitro. Thus, the spiramycin reaction, in conjunction with the puromycin reaction, is applied (i) to detect a strong preincubation effect exerted by chloramphenicol and lincomycin (this effect constitutes further evidence that these two antibiotics combine with complex C as slow-binding inhibitors) and (ii) to determine the rate constant for the regeneration (k7 = 2.0 x 10(-3) s-1) of complex C from the sparsomycin complex C*I [Theocharis, D. A

  20. Probing the Formation of Complex Organic Molecules in Interstellar Ices - Beyond the FTIR - RGA Limitation

    NASA Astrophysics Data System (ADS)

    Kaiser, Ralf I.

    2015-08-01

    An understanding of the formation of key classes of complex organic molecules (COMs) within interstellar ices is of core value to the laboratory astrophysics community with structural isomers - molecules with the same molecular formula but different connectivities of atoms - serving as a molecular clock and tracers in defining the evolutionary stage of cold molecular clouds and star forming regions. Here, the lack of data on products, branching ratios, and rate constants of their formation and how they depend on the ice temperature and composition limits the understanding how COMs are synthesized. Classically, infrared spectroscopy combined with mass spectrometry of the irradiated and subliming ices have been exploited for the last decades, but the usefulness of these methods has reached the limits when it comes to the identification of CMS in those ices. Here, infrared spectroscopy can only untangle the functional groups of COMs; mass spectrometry coupled with electron impact ionization cannot discriminate structural isomers and suffers from extensive fragmentation. This talk presents a novel approach to elucidate the formation of COMs by exploiting - besides classical infrared, Raman, and ultraviolet-visual spectroscopy - reflectron time-of-flight mass spectrometry (ReTOF) coupled with tunable vacuum ultraviolet (VUV) soft photoionization (ReTOF-PI). This technique has the unique power to identify the molecules based on a cross correlation of their mass-to-charge ratios, their ionization energies (IE), and their sublimation temperatures ultimately unraveling an inventory of individual COMs molecules formed upon interaction of ionizing radiation with interstellar analog ices.

  1. Quantum chemical insights in energy dissipation and carotenoid radical cation formation in light harvesting complexes.

    PubMed

    Wormit, Michael; Dreuw, Andreas

    2007-06-21

    Light harvesting complexes (LHCs) have been identified in all photosynthetic organisms. To understand their function in light harvesting and energy dissipation, detailed knowledge about possible excitation energy transfer (EET) and electron transfer (ET) processes in these pigment proteins is of prime importance. This again requires the study of electronically excited states of the involved pigment molecules, in LHCs of chlorophylls and carotenoids. This paper represents a critical review of recent quantum chemical calculations on EET and ET processes between pigment pairs relevant for the major LHCs of green plants (LHC-II) and of purple bacteria (LH2). The theoretical methodology for a meaningful investigation of such processes is described in detail, and benefits and limitations of standard methods are discussed. The current status of excited state calculations on chlorophylls and carotenoids is outlined. It is focused on the possibility of EET and ET in the context of chlorophyll fluorescence quenching in LHC-II and carotenoid radical cation formation in LH2. In the context of non-photochemical quenching of green plants, it is shown that replacement of the carotenoid violaxanthin by zeaxanthin in its binding pocket of LHC-II can not result in efficient quenching. In LH2, our computational results give strong evidence that the S(1) states of the carotenoids are involved in carotenoid cation formation. By comparison of theoretical findings with recent experimental data, a general mechanism for carotenoid radical cation formation is suggested.

  2. Formation of complex organic molecules in cold objects: the role of gas-phase reactions

    NASA Astrophysics Data System (ADS)

    Balucani, Nadia; Ceccarelli, Cecilia; Taquet, Vianney

    2015-04-01

    While astrochemical models are successful in reproducing many of the observed interstellar species, they have been struggling to explain the observed abundances of complex organic molecules. Current models tend to privilege grain surface over gas-phase chemistry in their formation. One key assumption of those models is that radicals trapped in the grain mantles gain mobility and react on lukewarm ( ≳ 30 K) dust grains. Thus, the recent detections of methyl formate (MF) and dimethyl ether (DME) in cold objects represent a challenge and may clarify the respective role of grain-surface and gas-phase chemistry. We propose here a new model to form DME and MF with gas-phase reactions in cold environments, where DME is the precursor of MF via an efficient reaction overlooked by previous models. Furthermore, methoxy, a precursor of DME, is also synthesized in the gas phase from methanol, which is desorbed by a non-thermal process from the ices. Our new model reproduces fairly well the observations towards L1544. It also explains, in a natural way, the observed correlation between DME and MF. We conclude that gas-phase reactions are major actors in the formation of MF, DME and methoxy in cold gas. This challenges the exclusive role of grain-surface chemistry and favours a combined grain-gas chemistry.

  3. Effect of exciplex formation on organic light emitting diodes based on rare-earth complex

    NASA Astrophysics Data System (ADS)

    Wang, D. Y.; Li, W. L.; Chu, B.; Liang, C. J.; Hong, Z. R.; Li, M. T.; Wei, H. Z.; Xin, Q.; Niu, J. H.; Xu, J. B.

    2006-07-01

    An exciplex can be formed due to the charge transfer between the lowest unoccupied molecular orbital (LUMO) of the acceptor and the highest occupied molecular orbital (HOMO) of the donor. By introducing a mixing layer composed of [N ,N'-diphenyl-N ,N'bis (3-methylphenyl)-1,1'-diphenyl-4,4'-diamine] (TPD) and europium(dibenzoylmethanato)3(bathophenanthroline) [Eu(DBM)3bath] and a graded interface, elimination of light emission from the exciplex and significant luminescence enhancement of trivalent europium ions (Eu3+) in organic light emitting devices have been achieved. The elimination mechanism of exciplex emission based on the concept that an exciplex can be formed between LUMO of the acceptor (Eu complex) and HOMO of donor (TPD) was investigated. To comprehensively understand the mechanism, devices consisting of a Eu(DBM)3bath as the emitting material and the devices using other rare-earth (RE) complex [RE(DBM)3bath] as the emitting material were fabricated with the same device configuration. As a reference, four spin-coated films with the blend composed of TPD and the gadolinium complex [Gd(DBM)3bath] were also fabricated. The electroluminescence (EL) spectra from the devices and photoluminescence spectra from the spin-coating films were fully investigated. The results show that the exciplex was formed by the charge transfer from the donor TPD to the acceptor RE complex, the exciplex state that acted as a transient excited state can be controlled by altering the molecular ratio in the mixing films. The relation of the exciplex formation based on EL devices with the RE complex versus the variety of the RE ions is also discussed by manipulating the energy level of the excited state.

  4. A defined peptide that inhibits the formation of the glycoprotein IIb and IIIa complex.

    PubMed

    Chiang, Thomas M; Zhu, Jiaqian

    2005-01-01

    Collagen-platelet interaction plays an important role in hemostasis and pathological thrombosis. The proposed mechanism of the interaction was the activation of platelets-->releasing of contents from granules-->aggregation. The common end point is the platelets and fibrin aggregates. Platelet glycoprotein (GP) IIb/IIIa (the alphaIIbbeta3 integrin) complexes serve as a receptor for the binding of fibrinogen to form firmed aggregates. Blockading of GP IIb/IIIa has been proposed to prevent platelet aggregation independent of the substance(s) responsible for activating the platelets. The development of various forms of GP IIb/IIIa inhibitor has resulted in the inhibition of platelet aggregation, although studies of alphaIIbbeta3 receptor function and various GP IIb/IIIa inhibitors have demonstrated the potential for these agents to produce effects on other aspects of platelet function as well as having nonplatelet effects. This study investigated platelet inhibition provided by blocking the GP IIb/IIIa complex formation by using a peptide derived from the GP IIIa molecule. The peptide inhibits both types I and III collagen-induced platelet aggregation in a dose-dependent manner. The defined peptide interferes with the formation of the GP IIb/IIIa complex by inhibiting the binding of FITC-PAC-1 onto ADP-, type I collagen-, and type III collagen-activated platelets. However, P-selectin secretion is not affected by the peptide. In addition, the peptide is not interfering with the binding of FITC-PAC-1 to platelets that were preincubated with indomethacin. Results from this study may suggest that the defined peptide is an effective agent to block the interaction of types I and III collagen with platelets.

  5. A Multi-wavelength Study of Star Formation Activity in the S235 Complex

    NASA Astrophysics Data System (ADS)

    Dewangan, L. K.; Ojha, D. K.; Luna, A.; Anandarao, B. G.; Ninan, J. P.; Mallick, K. K.; Mayya, Y. D.

    2016-03-01

    We have carried out an extensive multi-wavelength study to investigate the star formation process in the S235 complex. The S235 complex has a spherelike shell appearance at wavelengths longer than 2 μm and harbors an O9.5V type star approximately at its center. A near-infrared extinction map of the complex traces eight subregions (having AV > 8 mag), and five of them appear to be distributed in an almost regularly spaced manner along the spherelike shell surrounding the ionized emission. This picture is also supported by the integrated 12CO and 13CO intensity maps and by Bolocam 1.1 mm continuum emission. The position-velocity analysis of CO reveals an almost semi-ringlike structure, suggesting an expanding H ii region. We find that the Bolocam clump masses increase as we move away from the location of the ionizing star. This correlation is seen only for those clumps that are distributed near the edges of the shell. Photometric analysis reveals 435 young stellar objects (YSOs), 59% of which are found in clusters. Six subregions (including five located near the edges of the shell) are very well correlated with the dust clumps, CO gas, and YSOs. The average values of Mach numbers derived using NH3 data for three (East 1, East 2, and Central E) out of these six subregions are 2.9, 2.3, and 2.9, indicating these subregions are supersonic. The molecular outflows are detected in these three subregions, further confirming the ongoing star formation activity. Together, all these results are interpreted as observational evidence of positive feedback of a massive star.

  6. A MULTI-WAVELENGTH STUDY OF STAR FORMATION ACTIVITY IN THE S235 COMPLEX

    SciTech Connect

    Dewangan, L. K.; Luna, A.; Mayya, Y. D.; Ojha, D. K.; Ninan, J. P.; Mallick, K. K.; Anandarao, B. G.

    2016-03-01

    We have carried out an extensive multi-wavelength study to investigate the star formation process in the S235 complex. The S235 complex has a spherelike shell appearance at wavelengths longer than 2 μm and harbors an O9.5V type star approximately at its center. A near-infrared extinction map of the complex traces eight subregions (having A{sub V} > 8 mag), and five of them appear to be distributed in an almost regularly spaced manner along the spherelike shell surrounding the ionized emission. This picture is also supported by the integrated {sup 12}CO and {sup 13}CO intensity maps and by Bolocam 1.1 mm continuum emission. The position–velocity analysis of CO reveals an almost semi-ringlike structure, suggesting an expanding H ii region. We find that the Bolocam clump masses increase as we move away from the location of the ionizing star. This correlation is seen only for those clumps that are distributed near the edges of the shell. Photometric analysis reveals 435 young stellar objects (YSOs), 59% of which are found in clusters. Six subregions (including five located near the edges of the shell) are very well correlated with the dust clumps, CO gas, and YSOs. The average values of Mach numbers derived using NH{sub 3} data for three (East 1, East 2, and Central E) out of these six subregions are 2.9, 2.3, and 2.9, indicating these subregions are supersonic. The molecular outflows are detected in these three subregions, further confirming the ongoing star formation activity. Together, all these results are interpreted as observational evidence of positive feedback of a massive star.

  7. Molecular factors that determine Curie spin relaxation in dysprosium complexes.

    PubMed

    Caravan, P; Greenfield, M T; Bulte, J W

    2001-11-01

    Dysprosium complexes can serve as transverse relaxation (T(2)) agents for water protons through chemical exchange and the Curie spin relaxation mechanism. Using a pair of matched dysprosium(III) complexes, Dy-L1 (contains one inner-sphere water) and Dy-L2 (no inner-sphere water), it is shown that the transverse relaxation of bulk water is predominantly an inner-sphere effect. The kinetics of water exchange at Dy-L1 were determined by (17)O NMR. Proton transverse relaxation by Dy-L1 at high fields is governed primarily through a large chemical shift difference between free and bound water. Dy-L1 forms a noncovalent adduct with human serum albumin which dramatically lengthens the rotational correlation time, tau(R), causing the dipole-dipole component of the Curie spin mechanism to become significant and transverse relaxivity to increase by 3-8 times that of the unbound chelate. These findings aid in the design of new molecular species as efficient r(2) agents.

  8. Influence of glyco-oxidation on complexes between fibrin(ogen) and insulin-like growth factor-binding protein-1 in patients with diabetes mellitus type 2.

    PubMed

    Gligorijević, Nikola; Penezić, Ana; Nedić, Olgica

    2017-01-01

    Fibrinogen and insulin-like growth factor-binding protein-1 (IGFBP-1) are tightly connected to metabolic changes and complications in patients with diabetes mellitus (DM), and since they mutually interact to form complexes in plasma, we investigated whether and to what extent IGFBP-1/fibrinogen complexes change due to glyco-oxidative processes in DM and whether they participate in fibrin clot formation. These complexes were determined by immunoblotting in plasma samples from healthy adults and patients with DM type 2 (DM2). The influence of glyco-oxidation in vitro on the complexes was also investigated. Amounts of IGFBP-1/fibrinogen complexes in plasma from patients with DM2 were slightly but not significantly lower than in healthy persons. Such complexes in patients' samples participated in fibrin clot formation to a significantly decreased extent. In vitro experiments with glucose or methylglyoxal (MGO) as reactive agents demonstrated that the complexes underwent glyco-oxidative modification leading to reduced formation and/or stability. Extensively oxidized fibrinogen almost completely lost its ability to bind IGFBP-1. The reduced affinity of fibrinogen for IGFBP-1 accompanying diabetes may potentially shift the equilibrium to liberate more IGFBP-1 (and possibly insulin-like growth factor (IGF)-I) able to activate platelets during coagulation, so contributing to the hypercoagulation state together with other factors. This hypothesis, however, needs further examination.

  9. A Natural Mutation Involving both Pathogenicity and Perithecium Formation in the Fusarium graminearum Species Complex

    PubMed Central

    Suga, Haruhisha; Kageyama, Koji; Shimizu, Masafumi; Hyakumachi, Misturo

    2016-01-01

    Members of the Fusarium graminearum species complex (Fg complex or FGSC) are the primary pathogens causing Fusarium head blight in wheat and barley worldwide. A natural pathogenicity mutant (strain 0225022) was found in a sample of the Fg complex collected in Japan. The mutant strain did not induce symptoms in wheat spikes beyond the point of inoculation, and did not form perithecia. No segregation of phenotypic deficiencies occurred in the progenies of a cross between the mutant and a fully pathogenic wild-type strain, which suggested that a single genetic locus controlled both traits. The locus was mapped to chromosome 2 by using sequence-tagged markers; and a deletion of ∼3 kb was detected in the mapped region of the mutant strain. The wild-type strain contains the FGSG_02810 gene, encoding a putative glycosylphosphatidylinositol anchor protein, in this region. The contribution of FGSG_02810 to pathogenicity and perithecium formation was confirmed by complementation in the mutant strain using gene transfer, and by gene disruption in the wild-type strain. PMID:27678518

  10. Formation of coronene:water complexes: FTIR study in argon matrices and theoretical characterisation.

    PubMed

    Simon, A; Noble, J A; Rouaut, G; Moudens, A; Aupetit, C; Iftner, C; Mascetti, J

    2017-03-13

    In this paper, we report a combined theoretical and experimental study of coronene:water interactions in low temperature argon matrices. The theoretical calculations were performed using the mixed density functional-based tight binding/force field approach. The results are discussed in the light of experimental matrix isolation FTIR spectroscopic data. We show that, in the solid phase, (C24H12)(H2O)n (n ≤ 6) σ-type complexes, i.e. with water molecules coordinated on the edge of coronene, are formed, whereas in the gas phase, π-interaction is preferred. These σ-complexes are characterised by small shifts in water absorption bands and a larger blue shift of the out-of-plane γ(CH) deformation of coronene, with the shift increasing with the number of complexed water molecules. Such σ interaction is expected to favour photochemical reaction between water and coronene at the edges of the coronene molecule, leading to the formation of oxidation products at low temperature, even in the presence of only a few water molecules and at radiation energies below the ionisation potential of coronene.

  11. Incorporation of polyoxotungstate complexes in silica spheres and in situ formation of tungsten trioxide nanoparticles.

    PubMed

    Zhao, Yuanyuan; Fan, Haimei; Li, Wen; Bi, Lihua; Wang, Dejun; Wu, Lixin

    2010-09-21

    In this paper, we demonstrated a new convenient route for in situ fabrication of well separated small sized WO(3) nanoparticles in silica spheres, through a predeposition of surfactant encapsulated polyoxotungates as tungsten source, and followed by a calcination process. In a typical procedure, selected polyoxotungates with different charges were enwrapped with dioctadecyldimethylammonium cations through electrostatic interaction. Elemental analysis, thermogravimetric analysis, and spectral characterization confirmed the formation of prepared complexes with the anticipated chemical structure. The complexes were then phase-transferred into aqueous solution that predissolved surfactant cetyltrimethylammonium bromide, and finally incorporated into silica spheres through a joint sol-gel reaction with tetraethyl orthosilicate in a well dispersed state under the protection of organic layer for polyoxotungates from the alkaline reaction condition. Transmission electron microscopic images illustrated the well dispersed WO(3) nanoparticles in the size range of ca. 2.2 nm in the silica spheres after the calcination at 465 °C. The sizes of both the silica spheres and WO(3) nanoparticles could be adjusted independently through changing the doping content to a large extent. Meanwhile, the doped polyoxotungate complexes acted as the template for the mesoporous structure in silica spheres after the calcination. Along with the increase of doping content and surfactant, the mesopore size changed little (2.0-2.9 nm), but the specific surface areas increased quite a lot. Importantly, the WO(3)-nanoparticle-doped silica spheres displayed an interesting photovoltaic property, which is favorable for the funtionalization of these nanomaterials.

  12. STAR FORMATION ACTIVITY IN THE GALACTIC H II COMPLEX S255-S257

    SciTech Connect

    Ojha, D. K.; Ghosh, S. K.; Samal, M. R.; Pandey, A. K.; Sharma, Saurabh; Bhatt, B. C.; Tamura, M.; Mohan, V.; Zinchenko, I.

    2011-09-10

    We present results on the star formation activity of an optically obscured region containing an embedded cluster (S255-IR) and molecular gas between two evolved H II regions, S255 and S257. We have studied the complex using optical and near-infrared (NIR) imaging, optical spectroscopy, and radio continuum mapping at 15 GHz, along with Spitzer-IRAC results. We found that the main exciting sources of the evolved H II regions S255 and S257 and the compact H II regions associated with S255-IR are of O9.5-B3 V nature, consistent with previous observations. Our NIR observations reveal 109 likely young stellar object (YSO) candidates in an area of {approx}4.'9 x 4.'9 centered on S255-IR, which include 69 new YSO candidates. To see the global star formation, we constructed the V - I/V diagram for 51 optically identified IRAC YSOs in an area of {approx}13' x 13' centered on S255-IR. We suggest that these YSOs have an approximate age between 0.1 and 4 Myr, indicating a non-coeval star formation. Using spectral energy distribution models, we constrained physical properties and evolutionary status of 31 and 16 YSO candidates outside and inside the gas ridge, respectively. The models suggest that the sources associated with the gas ridge are younger (mean age {approx}1.2 Myr) than the sources outside the gas ridge (mean age {approx}2.5 Myr). The positions of the young sources inside the gas ridge at the interface of the H II regions S255 and S257 favor a site of induced star formation.

  13. Factors Controlling the Formation of Oxidized Root Channels: A Review and Annotated Bibliography

    DTIC Science & Technology

    1993-08-01

    phenanthroline or bathophenanthroline disulfonic acid), results in little iron plaque formation compared with that occurring in the presence of ferrous...plaque formation are the availability of soil iron and the oxidizing capacity of the plant root, In spite of the importance of wetland hydrology...persistence of root iron about the environmental and biotic factors that plaques, and the role of soil chemistry, the ab- cause oxidized root channels to form

  14. Factors Affecting Timely Completion of a PhD: A Complex Systems Approach

    ERIC Educational Resources Information Center

    Pitchforth, Jegar; Beames, Stephanie; Thomas, Aleysha; Falk, Matthew; Farr, Charisse; Gasson, Susan; Thamrin, Sri Astuti; Mengersen, Kerrie

    2012-01-01

    Completing a PhD on time is a complex process, influenced by many interacting factors. In this paper we take a Bayesian Network approach to analyzing the factors perceived to be important in achieving this aim. Focusing on a single research group in Mathematical Sciences, we develop a conceptual model to describe the factors considered to be…

  15. Factors Affecting Grammatical and Lexical Complexity of Long-Term L2 Speakers' Oral Proficiency

    ERIC Educational Resources Information Center

    Lahmann, Cornelia; Steinkrauss, Rasmus; Schmid, Monika S.

    2016-01-01

    There remains considerable disagreement about which factors drive second language (L2) ultimate attainment. Age of onset (AO) appears to be a robust factor, lending support to theories of maturational constraints on L2 acquisition. The present study is an investigation of factors that influence grammatical and lexical complexity at the stage of L2…

  16. Chlorination and chloramination of tetracycline antibiotics: disinfection by-products formation and influential factors.

    PubMed

    Zhou, Shiqing; Shao, Yisheng; Gao, Naiyun; Zhu, Shumin; Ma, Yan; Deng, Jing

    2014-09-01

    Formation of disinfection by-products (DBPs) from chlorination and chloramination of tetracycline antibiotics (TCs) was comprehensively investigated. It was demonstrated that a connection existed between the transformation of TCs and the formation of chloroform (CHCl3), carbon tetrachloride (CCl4), dichloroacetonitrile (DCAN) and dichloroacetone (DCAce). Factors evaluated included chlorine (Cl2) and chloramine(NH2Cl) dosage, reaction time, solution pH and disinfection modes. Increased Cl2/NH2Cl dosage and reaction time improved the formation of CHCl3 and DCAce. Formation of DCAN followed an increasing and then decreasing pattern with increasing Cl2 dosage and prolonged reaction time. pH affected DBPs formation differently, with CHCl3 and DCAN decreasing in chlorination, and having maximum concentrations at pH 7 in chloramination. The total concentrations of DBPs obeyed the following order: chlorination>chloramination>pre-chlorination (0.5h)>pre-chlorination (1h)>pre-chlorination (2h).

  17. Formation of tissue factor activity following incubation of recombinant human tissue factor apoprotein with plasma lipoproteins

    SciTech Connect

    Sakai, T.; Kisiel, W. )

    1990-11-01

    Incubation of recombinant human tissue factor apoprotein (Apo-TF) with human plasma decreased the recalcified clotting time of this plasma in a time-and dose-dependent manner suggesting relipidation of the Apo-TF by plasma lipoproteins. Incubation of Apo-TF with purified preparations of human very low density, low density and high density lipoproteins resulted in tissue factor activity in a clotting assay. The order of effectiveness was VLDL greater than LDL much greater than HDL. Tissue factor activity generated by incubation of a fixed amount of Apo-TF with plasma lipoproteins was lipoprotein concentration-dependent and saturable. The association of Apo-TF with lipoprotein particles was supported by gel filtration studies in which {sup 125}I-Apo-TF coeluted with the plasma lipoprotein in the void volume of a Superose 6 column in the presence and absence of calcium ions. In addition, void-volume Apo-TF-lipoprotein fractions exhibited tissue factor activity. These results suggest that the factor VIII-bypassing activity of bovine Apo-TF observed in a canine hemophilic model may be due, in part, to its association with plasma lipoproteins and expression of functional tissue factor activity.

  18. Platelet-derived growth factor receptors form complexes with neuropilin-1 during megakaryocytic differentiation of thrombopoietin-dependent UT-7/TPO cells.

    PubMed

    Ohsaka, Akimichi; Hirota-Komatsu, Satoko; Araki, Marito; Komatsu, Norio

    2015-04-10

    Neuropilin-1 (NRP-1) is involved in angiogenesis, but the role of NRP-1 in megakaryocytopoiesis is not yet fully understood. In this study, we investigated whether thrombopoietin (TPO) regulates the expression of platelet-derived growth factor (PDGF) and its receptors (PDGFRs) on TPO-dependent UT-7/TPO cells and whether PDGFRs and NRP-1 on UT-7/TPO cells form complexes during megakaryocytic differentiation. When UT-7/TPO cells were starved of TPO for 24 h and then stimulated with 5 ng/ml TPO, the expression of PDGF-B, PDGFRα, and PDGFRβ were significantly up-regulated after the addition of TPO. TPO also induced tyrosine phosphorylation of PDGFRα but not PDGFRβ, and promoted the formation of PDGFRαβ heterodimer complexes. Furthermore, megakaryocytic differentiation of UT-7/TPO cells on treatment with phorbol myristate acetate (PMA) was accompanied by a marked up-regulation of PDGFRβ and NRP-1 protein expression, complex formation between PDGFRs and NRP-1, PDGFRαβ heterodimer complexes, and an increase in PDGF-BB-binding activity. Immunocytochemistry confirmed complex formation between PDGFRs and NRP-1 and PDGFRαβ heterodimer complexes in PMA-differentiated UT-7/TPO cells. Our observations suggest that NRP-1 is involved in megakaryocytopoiesis through complex formation with PDGFRs, and that NRP-1-PDGFR-complexes may contribute to effective cellular functions mediated by TPO and PDGF in megakaryocytic cells.

  19. Energetic Mechanism of Cytochrome c-Cytochrome c Oxidase Electron Transfer Complex Formation under Turnover Conditions Revealed by Mutational Effects and Docking Simulation.

    PubMed

    Sato, Wataru; Hitaoka, Seiji; Inoue, Kaoru; Imai, Mizue; Saio, Tomohide; Uchida, Takeshi; Shinzawa-Itoh, Kyoko; Yoshikawa, Shinya; Yoshizawa, Kazunari; Ishimori, Koichiro

    2016-07-15

    Based on the mutational effects on the steady-state kinetics of the electron transfer reaction and our NMR analysis of the interaction site (Sakamoto, K., Kamiya, M., Imai, M., Shinzawa-Itoh, K., Uchida, T., Kawano, K., Yoshikawa, S., and Ishimori, K. (2011) Proc. Natl. Acad. Sci. U.S.A. 108, 12271-12276), we determined the structure of the electron transfer complex between cytochrome c (Cyt c) and cytochrome c oxidase (CcO) under turnover conditions and energetically characterized the interactions essential for complex formation. The complex structures predicted by the protein docking simulation were computationally selected and validated by the experimental kinetic data for mutant Cyt c in the electron transfer reaction to CcO. The interaction analysis using the selected Cyt c-CcO complex structure revealed the electrostatic and hydrophobic contributions of each amino acid residue to the free energy required for complex formation. Several charged residues showed large unfavorable (desolvation) electrostatic interactions that were almost cancelled out by large favorable (Columbic) electrostatic interactions but resulted in the destabilization of the complex. The residual destabilizing free energy is compensated by the van der Waals interactions mediated by hydrophobic amino acid residues to give the stabilized complex. Thus, hydrophobic interactions are the primary factors that promote complex formation between Cyt c and CcO under turnover conditions, whereas the change in the electrostatic destabilization free energy provides the variance of the binding free energy in the mutants. The distribution of favorable and unfavorable electrostatic interactions in the interaction site determines the orientation of the binding of Cyt c on CcO.

  20. Neuropilin-1 forms complexes with vascular endothelial growth factor receptor-2 during megakaryocytic differentiation of UT-7/TPO cells

    SciTech Connect

    Ohsaka, Akimichi; Hirota-Komatsu, Satoko; Shibata, Miki; Komatsu, Norio

    2009-12-25

    We investigated whether the gene expression of vascular endothelial growth factor (VEGF) and its receptors (VEGFR and neuropilin-1 [NRP-1]) could be specifically regulated during the megakaryocytic differentiation of human thrombopoietin (TPO)-dependent UT-7/TPO cells. Undifferentiated UT-7/TPO cells expressed a functional VEGFR-2, leading to VEGF binding and VEGF{sub 165}-induced tyrosine phosphorylation, cell proliferation, and apoptosis inhibition. The megakaryocytic differentiation of UT-7/TPO cells on treatment with phorbol myristate acetate (PMA) was accompanied by a marked up-regulation of NRP-1 mRNA and protein expression and by an increase in VEGF-binding activity, which was mainly mediated by VEGFR-2. VEGF{sub 165} promoted the formation of complexes containing NRP-1 and VEGFR-2 in undifferentiated UT-7/TPO cells in a dose-dependent manner. Unlike human umbilical vein endothelial cells, PMA-differentiated UT-7/TPO cells exhibited complex formation between NRP-1 and VEGFR-2 even in the absence of VEGF{sub 165}. These findings suggest that NRP-1-VEGFR-2-complex formation may contribute to effective cellular functions mediated by VEGF{sub 165} in megakaryocytic cells.

  1. Higher platelet reactivity and platelet-monocyte complex formation in Gram-positive sepsis compared to Gram-negative sepsis.

    PubMed

    Tunjungputri, Rahajeng N; van de Heijden, Wouter; Urbanus, Rolf T; de Groot, Philip G; van der Ven, Andre; de Mast, Quirijn

    2016-12-29

    Platelets may play a role in the high risk for vascular complications in Gram-positive sepsis. We compared the platelet reactivity of 15 patients with Gram-positive sepsis, 17 with Gram-negative sepsis and 20 healthy controls using a whole blood flow cytometry-based assay. Patients with Gram-positive sepsis had the highest median fluorescence intensity (MFI) of the platelet membrane expression of P-selectin upon stimulation with high dose adenosine diphosphate (ADP; P = 0.002 vs. Gram-negative and P = 0.005 vs. control groups) and cross-linked collagen-related peptide (CRP-XL; P = 0.02 vs. Gram-negative and P = 0.0001 vs. control groups). The Gram-positive group also demonstrated significantly higher ADP-induced fibrinogen binding (P = 0.001), as wll as platelet-monocyte complex formation (P = 0.02), compared to the Gram-negative group and had the highest plasma levels of platelet factor 4, β-thromboglobulin and soluble P-selectin. In contrast, thrombin-antithrombin complex and C-reactive protein levels were comparable in both patient groups. In conclusion, common Gram-positive pathogens induce platelet hyperreactivity, which may contribute to a higher risk for vascular complications.

  2. Formation of a Complex between Nucleolin and Replication Protein a after Cell Stress Prevents Initiation of DNA Replication

    PubMed Central

    Daniely, Yaron; Borowiec, James A.

    2000-01-01

    We used a biochemical screen to identify nucleolin, a key factor in ribosome biogenesis, as a high-affinity binding partner for the heterotrimeric human replication protein A (hRPA). Binding studies in vitro demonstrated that the two proteins physically interact, with nucleolin using an unusual contact with the small hRPA subunit. Nucleolin significantly inhibited both simian virus 40 (SV-40) origin unwinding and SV-40 DNA replication in vitro, likely by nucleolin preventing hRPA from productive interaction with the SV-40 initiation complex. In vivo, use of epifluorescence and confocal microscopy showed that heat shock caused a dramatic redistribution of nucleolin from the nucleolus to the nucleoplasm. Nucleolin relocalization was concomitant with a tenfold increase in nucleolin–hRPA complex formation. The relocalized nucleolin significantly overlapped with the position of hRPA, but only poorly with sites of ongoing DNA synthesis. We suggest that the induced nucleolin–hRPA interaction signifies a novel mechanism that represses chromosomal replication after cell stress. PMID:10811822

  3. Structure of von Willebrand factor and its function in platelet adhesion and thrombus formation.

    PubMed

    Ruggeri, Z M

    2001-06-01

    The adhesive protein von Willebrand factor mediates the initiation and progression of thrombus formation at sites of vascular injury. von Willebrand factor is synthesized in endothelial cells and megakaryocytes as a very large polymer composed of identical subunits. In the plasma, it appears as a series of multimers of regularly decreasing molecular mass, from several thousand to 500 kDa. The size of circulating von Willebrand factor multimers is controlled by proteolytic cleavage carried out by a specific protease. The biological functions of von Willebrand factor are exerted through specific domains that interact with extracellular matrix components and cell membrane receptors to promote the initial tethering and adhesion of platelets to subendothelial surfaces, as well as platelet aggregation. Moreover, von Willebrand factor binds the procoagulant co-enzyme, factor VIII, contributing to its stability and, indirectly, to its function in the generation of fibrin. This chapter presents a review of current knowledge on the structure, biosynthesis and functions of von Willebrand factor.

  4. Dimerisation, rhodium complex formation and rearrangements of N-heterocyclic carbenes of indazoles

    PubMed Central

    Guan, Zong; Namyslo, Jan C; Drafz, Martin H H; Nieger, Martin

    2014-01-01

    Summary Deprotonation of indazolium salts at low temperatures gives N-heterocyclic carbenes of indazoles (indazol-3-ylidenes) which can be trapped as rhodium complexes (X-ray analysis). In the absence of Rh, the indazol-3-ylidenes spontaneously dimerize under ring cleavage of one of the N,N-bonds and ring closure to an indazole–indole spiro compound which possesses an exocyclic imine group. The E/Z isomers of the imines can be separated by column chromatography when methanol is used as eluent. We present results of a single crystal X-ray analysis of one of the E-isomers, which equilibrate in solution as well as in the solid state. Heating of the indazole–indole spiro compounds results in the formation of quinazolines by a ring-cleavage/ring-closure sequence (X-ray analysis). Results of DFT calculations are presented. PMID:24778738

  5. Spontaneous formation of complex structures made from elastic membranes in an aluminum-hydroxide-carbonate system

    NASA Astrophysics Data System (ADS)

    Kiehl, Micah; Kaminker, Vitaliy; Pantaleone, James; Nowak, Piotr; Dyonizy, Agnieszka; Maselko, Jerzy

    2015-06-01

    A popular playground for studying chemo-hydrodynamic patterns and instabilities is chemical gardens, also known as silicate gardens. In these systems, complex structures spontaneously form, driven by buoyant forces and either osmotic or mechanical pumps. Here, we report on systems that differ somewhat from classical chemical gardens in that the membranes are much more deformable and soluble. These properties lead to structures that self-construct and evolve in new ways. For example, they exhibit the formation of chemical balloons, a new growth mechanism for tubes, and also the homologous shrinking of these tubes. The stretching mechanism for the membranes is probably different than for other systems by involving membrane "self-healing." Other unusual properties are osmosis that sometimes occurs out of the structure and also small plumes that flow away from the structure, sometimes upwards, and sometimes downwards. Mathematical models are given that explain some of the observed phenomena.

  6. Formation of complexes of antimicrobial agent norfloxacin with antitumor antibiotics of anthracycline series

    NASA Astrophysics Data System (ADS)

    Evstigneev, M. P.; Rybakova, K. A.; Davies, D. B.

    2007-05-01

    The formation of complexes in solutions of the norfloxacin antimicrobial agent (NOR) with daunomycin (DAU) and nogalamycin (NOG), antitumor anthracycline antibiotics, was studied using 1H NMR spectroscopy. Based on the concentration and temperature dependences of the chemical shifts of the protons of interacting molecules, the equilibrium constants and thermodynamic parameters (enthalpy and entropy) of heteroassociation of the antibiotics were calculated. It was shown that NOR interacts with DAU (NOG) in aqueous solutions forming stacked heterocomplexes with parallel orientation of the molecular chromophores. The conclusion was drawn that such interactions should be taken into account when anthracyclines and quinolones are jointly administered during combined chemotherapy, since they can contribute to the medico-biological synergistic effect of these antibiotics.

  7. Thermodynamics of Complex Sulfide Inclusion Formation in Ca-Treated Al-Killed Structural Steel

    NASA Astrophysics Data System (ADS)

    Guo, Yin-tao; He, Sheng-ping; Chen, Gu-jun; Wang, Qian

    2016-08-01

    Controlling the morphology of the sulfide inclusion is of vital importance in enhancing the properties of structural steel. Long strip-shaped sulfides in hot-rolled steel can spherize when, instead of the inclusion of pure single-phase MnS, the guest is a complex sulfide, such as an oxide-sulfide duplex and a solid-solution sulfide particle. In this study, the inclusions in a commercial rolled structural steel were investigated. Spherical and elongated oxide-sulfide duplex as well as single-phase (Mn,Ca)S solid solution inclusions were observed in the steel. A thermodynamic equilibrium between the oxide and sulfide inclusions was proposed to understand the oxide-sulfide duplex inclusion formation. Based on the equilibrium solidification principle, thermodynamic discussions on inclusion precipitation during the solidification process were performed for both general and resulfurized structural steel. The predicted results of the present study agreed well with the experimental ones.

  8. Probing formation of cargo/importin-α transport complexes in plant cells using a pathogen effector

    PubMed Central

    Wirthmueller, Lennart; Roth, Charlotte; Fabro, Georgina; Caillaud, Marie-Cécile; Rallapalli, Ghanasyam; Asai, Shuta; Sklenar, Jan; Jones, Alexandra M E; Wiermer, Marcel; Jones, Jonathan D G; Banfield, Mark J

    2015-01-01

    Importin-αs are essential adapter proteins that recruit cytoplasmic proteins destined for active nuclear import to the nuclear transport machinery. Cargo proteins interact with the importin-α armadillo repeat domain via nuclear localization sequences (NLSs), short amino acids motifs enriched in Lys and Arg residues. Plant genomes typically encode several importin-α paralogs that can have both specific and partially redundant functions. Although some cargos are preferentially imported by a distinct importin-α it remains unknown how this specificity is generated and to what extent cargos compete for binding to nuclear transport receptors. Here we report that the effector protein HaRxL106 from the oomycete pathogen Hyaloperonospora arabidopsidis co-opts the host cell's nuclear import machinery. We use HaRxL106 as a probe to determine redundant and specific functions of importin-α paralogs from Arabidopsis thaliana. A crystal structure of the importin-α3/MOS6 armadillo repeat domain suggests that five of the six Arabidopsis importin-αs expressed in rosette leaves have an almost identical NLS-binding site. Comparison of the importin-α binding affinities of HaRxL106 and other cargos in vitro and in plant cells suggests that relatively small affinity differences in vitro affect the rate of transport complex formation in vivo. Our results suggest that cargo affinity for importin-α, sequence variation at the importin-α NLS-binding sites and tissue-specific expression levels of importin-αs determine formation of cargo/importin-α transport complexes in plant cells. PMID:25284001

  9. The late Quaternary Diego Hernandez Formation, Tenerife: Volcanology of a complex cycle of voluminous explosive phonolitic eruptions

    NASA Astrophysics Data System (ADS)

    Edgar, C. J.; Wolff, J. A.; Olin, P. H.; Nichols, H. J.; Pittari, A.; Cas, R. A. F.; Reiners, P. W.; Spell, T. L.; Martí, J.

    2007-02-01

    The Diego Hernandez Formation (DHF; 600-ca. 180 ka) represents the products of the most recent complete cycle of phonolitic explosive volcanism on Tenerife (Canary Islands, Spain). We provide a revised and detailed stratigraphy, new 40Ar/ 39Ar and (U-Th)/He age determinations for major eruptive units, a summary of new chemical data and an overview of the key characteristics of the cycle, including volume estimates, dispersal patterns, eruption styles, phreatomagmatic influences and caldera collapse episodes. The complex stratigraphy of the DHF is divided into 20 named members, each representing a major eruption, as well as numerous unnamed members of limited present-day exposure. The major eruptions are represented by the Fortaleza (370 ka), Roque (347 ka, 3 km 3), Aldea (319 ka, 3 km 3), Fasnia (309 ka, 13 km 3), Poris (268 ka, 3.5 km 3), Arafo (4 km 3), Caleta (223 ka, 3.5 km 3) and Abrigo (between 196 and 171 ka, 20 km 3) Members. The Aldea, Fasnia and Poris Members consist of highly complex successions of plinian fall, surge and flow deposits and several of the eruptions produced widespread and internally complex ignimbrite sheets. Phreatomagmatism occurred most frequently in the opening phase of the eruptions but also recurred repeatedly throughout many of the sequences. Inferred sources of water include a shallow caldera lake and groundwater, and intermittent phreatomagmatic activity was an important influence on eruption style. Another important factor was conduit and vent instability, which frequently loaded the eruption column with dense lithic debris and occasionally triggered column collapse and ignimbrite formation. Most of the major DHF eruptions were triggered by injection of mafic magma into existing phonolitic magma bodies. Two phonolitic magma types were available for eruption during the lifetime of the DHF, but each was dominant at different times. The results presented here support a caldera collapse rather than a landslide model for the origin

  10. Merging Worlds of Nanomaterials and Biological Environment: Factors Governing Protein Corona Formation on Nanoparticles and Its Biological Consequences

    NASA Astrophysics Data System (ADS)

    Foroozandeh, Parisa; Aziz, Azlan Abdul

    2015-05-01

    Protein corona has became a prevalent subject in the field of nanomedicine owing to its diverse role in determining the efficiency, efficacy, and the ultimate biological fate of the nanomaterials used as a tool to treat and diagnose various diseases. For instance, protein corona formation on the surface of nanoparticles can modify its physicochemical properties and interfere with its intended functionalities in the biological microenvironments. As such, much emphasis should be placed in understanding these complex phenomena that occur at the bio-nano interface. The main aim of this review is to present different factors that are influencing protein-nanoparticle interaction such as physicochemical properties of nanoparticle ( i.e., size and size distribution, shape, composition, surface chemistry, and coatings) and the effect of biological microenvironments. Apart from that, the effect of ignored factors at the bio-nano interface such as temperature, plasma concentration, plasma gradient effect, administration route, and cell observer were also addressed.

  11. Formation of Large Polysulfide Complexes during the Lithium-Sulfur Battery Discharge

    NASA Astrophysics Data System (ADS)

    Wang, Bin; Alhassan, Saeed M.; Pantelides, Sokrates T.

    2014-09-01

    Sulfur cathodes have much larger capacities than transition-metal-oxide cathodes used in commercial lithium-ion batteries but suffer from unsatisfactory capacity retention and long-term cyclability. Capacity degradation originates from soluble lithium polysulfides gradually diffusing into the electrolyte. Understanding of the formation and dynamics of soluble polysulfides during the discharging process at the atomic level remains elusive, which limits further development of lithium-sulfur (Li-S) batteries. Here we report first-principles molecular dynamics simulations and density functional calculations, through which the discharging products of Li-S batteries are studied. We find that, in addition to simple Li2Sn (1≤n ≤8) clusters generated from single cyclooctasulfur (S8) rings, large Li-S clusters form by collectively coupling several different rings to minimize the total energy. At high lithium concentration, a Li-S network forms at the sulfur surfaces. The results can explain the formation of the soluble Li-S complex, such as Li2S8, Li2S6, and Li2S4, and the insoluble Li2S2 and Li2S structures. In addition, we show that the presence of oxygen impurities in graphene, particularly oxygen atoms bonded to vacancies and edges, may stabilize the lithium polysulfides that may otherwise diffuse into the electrolyte.

  12. P31comet, a member of the synaptonemal complex, participates in meiotic DSB formation in rice.

    PubMed

    Ji, Jianhui; Tang, Ding; Shen, Yi; Xue, Zhihui; Wang, Hongjun; Shi, Wenqing; Zhang, Chao; Du, Guijie; Li, Yafei; Cheng, Zhukuan

    2016-09-20

    The human mitotic arrest-deficient 2 (Mad2) binding protein p31(comet) participates in the spindle checkpoint and coordinates cell cycle events in mitosis although its function in meiosis remains unknown in all organisms. Here, we reveal P31(comet) as a synaptonemal complex (SC) protein in rice (Oryza sativa L.). In p31(comet), homologous pairing and synapsis are eliminated, leading to the homologous nondisjunction and complete sterility. The failure in loading of histone H2AX phosphorylation (γH2AX) in p31(comet), together with the suppressed chromosome fragmentation in rice completion of meiotic recombination 1 (com1) p31(comet) and radiation sensitive 51c (rad51c) p31(comet) double mutants, indicates that P31(comet) plays an essential role in double-strand break (DSB) formation. Interestingly, the dynamic colocalization pattern between P31(comet) and ZEP1 (a transverse filament protein of SC) by immunostaining, as well as the interaction between P31(comet) and CENTRAL REGION COMPONENT 1 (CRC1) in yeast two-hybrid assays, suggests possible involvement of P31(comet) in SC installation. Together, these data indicate that P31(comet) plays a key role in DSB formation and SC installation, mainly through its cooperation with CRC1.

  13. Complex organic molecules during low-mass star formation: Pilot survey results

    SciTech Connect

    Öberg, Karin I.; Graninger, Dawn; Lauck, Trish

    2014-06-10

    Complex organic molecules (COMs) are known to be abundant toward some low-mass young stellar objects (YSOs), but how these detections relate to typical COM abundance are not yet understood. We aim to constrain the frequency distribution of COMs during low-mass star formation, beginning with this pilot survey of COM lines toward six embedded YSOs using the IRAM 30 m Telescope. The sample was selected from the Spitzer c2d ice sample and covers a range of ice abundances. We detect multiple COMs, including CH{sub 3}CN, toward two of the YSOs, and tentatively toward a third. Abundances with respect to CH{sub 3}OH vary between 0.7% and 10%. This sample is combined with previous COM observations and upper limits to obtain a frequency distributions of CH{sub 3}CN, HCOOCH{sub 3}, CH{sub 3}OCH{sub 3}, and CH{sub 3}CHO. We find that for all molecules more than 50% of the sample have detections or upper limits of 1%-10% with respect to CH{sub 3}OH. Moderate abundances of COMs thus appear common during the early stages of low-mass star formation. A larger sample is required, however, to quantify the COM distributions, as well as to constrain the origins of observed variations across the sample.

  14. P31comet, a member of the synaptonemal complex, participates in meiotic DSB formation in rice

    PubMed Central

    Ji, Jianhui; Tang, Ding; Shen, Yi; Xue, Zhihui; Wang, Hongjun; Shi, Wenqing; Zhang, Chao; Du, Guijie; Li, Yafei; Cheng, Zhukuan

    2016-01-01

    The human mitotic arrest-deficient 2 (Mad2) binding protein p31comet participates in the spindle checkpoint and coordinates cell cycle events in mitosis although its function in meiosis remains unknown in all organisms. Here, we reveal P31comet as a synaptonemal complex (SC) protein in rice (Oryza sativa L.). In p31comet, homologous pairing and synapsis are eliminated, leading to the homologous nondisjunction and complete sterility. The failure in loading of histone H2AX phosphorylation (γH2AX) in p31comet, together with the suppressed chromosome fragmentation in rice completion of meiotic recombination 1 (com1) p31comet and radiation sensitive 51c (rad51c) p31comet double mutants, indicates that P31comet plays an essential role in double-strand break (DSB) formation. Interestingly, the dynamic colocalization pattern between P31comet and ZEP1 (a transverse filament protein of SC) by immunostaining, as well as the interaction between P31comet and CENTRAL REGION COMPONENT 1 (CRC1) in yeast two-hybrid assays, suggests possible involvement of P31comet in SC installation. Together, these data indicate that P31comet plays a key role in DSB formation and SC installation, mainly through its cooperation with CRC1. PMID:27601671

  15. Unraveling the complexities of circadian and sleep interactions with memory formation through invertebrate research

    PubMed Central

    Michel, Maximilian; Lyons, Lisa C.

    2014-01-01

    Across phylogeny, the endogenous biological clock has been recognized as providing adaptive advantages to organisms through coordination of physiological and behavioral processes. Recent research has emphasized the role of circadian modulation of memory in generating peaks and troughs in cognitive performance. The circadian clock along with homeostatic processes also regulates sleep, which itself impacts the formation and consolidation of memory. Thus, the circadian clock, sleep and memory form a triad with ongoing dynamic interactions. With technological advances and the development of a global 24/7 society, understanding the mechanisms underlying these connections becomes pivotal for development of therapeutic treatments for memory disorders and to address issues in cognitive performance arising from non-traditional work schedules. Invertebrate models, such as Drosophila melanogaster and the mollusks Aplysia and Lymnaea, have proven invaluable tools for identification of highly conserved molecular processes in memory. Recent research from invertebrate systems has outlined the influence of sleep and the circadian clock upon synaptic plasticity. In this review, we discuss the effects of the circadian clock and sleep on memory formation in invertebrates drawing attention to the potential of in vivo and in vitro approaches that harness the power of simple invertebrate systems to correlate individual cellular processes with complex behaviors. In conclusion, this review highlights how studies in invertebrates with relatively simple nervous systems can provide mechanistic insights into corresponding behaviors in higher organisms and can be used to outline possible therapeutic options to guide further targeted inquiry. PMID:25136297

  16. Generalized additive models reveal the intrinsic complexity of wood formation dynamics.

    PubMed

    Cuny, Henri E; Rathgeber, Cyrille B K; Kiessé, Tristan Senga; Hartmann, Felix P; Barbeito, Ignacio; Fournier, Meriem

    2013-04-01

    The intra-annual dynamics of wood formation, which involves the passage of newly produced cells through three successive differentiation phases (division, enlargement, and wall thickening) to reach the final functional mature state, has traditionally been described in conifers as three delayed bell-shaped curves followed by an S-shaped curve. Here the classical view represented by the 'Gompertz function (GF) approach' was challenged using two novel approaches based on parametric generalized linear models (GLMs) and 'data-driven' generalized additive models (GAMs). These three approaches (GFs, GLMs, and GAMs) were used to describe seasonal changes in cell numbers in each of the xylem differentiation phases and to calculate the timing of cell development in three conifer species [Picea abies (L.), Pinus sylvestris L., and Abies alba Mill.]. GAMs outperformed GFs and GLMs in describing intra-annual wood formation dynamics, showing two left-skewed bell-shaped curves for division and enlargement, and a right-skewed bimodal curve for thickening. Cell residence times progressively decreased through the season for enlargement, whilst increasing late but rapidly for thickening. These patterns match changes in cell anatomical features within a tree ring, which allows the separation of earlywood and latewood into two distinct cell populations. A novel statistical approach is presented which renews our understanding of xylogenesis, a dynamic biological process in which the rate of cell production interplays with cell residence times in each developmental phase to create complex seasonal patterns.

  17. Functional properties of an isolated. cap alpha beta. heterodimeric human placenta insulin-like growth factor 1 receptor complex

    SciTech Connect

    Feltz, S.M.; Swanson, M.L.; Wemmie, J.A.; Pessin, J.E.

    1988-05-03

    Treatment of human placenta membranes at pH 8.5 in the presence of 2.0 mM dithiothreitol (DTT) for 5 min, followed by the simultaneous removal of the DTT and pH adjustment of pH 7.6, resulted in the formation of a functional ..cap alpha beta.. heterodimeric insulin-like growth factor 1 (IGF-1) receptor complex from the native ..cap alpha../sub 2/..beta../sub 2/ heterotetrameric disulfide-linked state. The membrane-bound ..cap alpha beta.. heterodimeric complex displayed similar curvilinear /sup 125/I-IGF-1 equilibrium binding compared to the ..cap alpha../sub 2/..beta../sub 2/ heterotetrameric complex. /sup 125/I-IGF-1 binding to both the isolated ..cap alpha../sub 2/..beta../sub 2/ heterotetrameric and ..cap alpha beta.. heterodimeric complexes demonstrated a marked straightening of the Scatchard plots, compared to the placenta membrane-bound IGF-1 receptors, with a 2-fold increase in the high-affinity binding component. IGF-1 stimulation of IGF-1 receptor autophosphorylation indicated that the ligand-dependent activation of ..cap alpha beta.. heterodimeric protein kinase activity occurred concomitant with the reassociation into a covalent ..cap alpha../sub 2/..beta../sub 2/ heterotetrameric state. These data demonstrate that (i) a combination of alkaline pH and DTT treatment of human placenta membranes results in the formation of an ..cap alpha beta.. heterodimeric IGF-1 receptor complex, (ii) unlike the insulin receptor, high-affinity homogeneous IGF-1 binding occurs in both the ..cap alpha../sub 2/..beta../sub 2/ heterotetrameric and ..cap alpha beta.. heterodimeric complexes, and (iii) IGF-1-dependent autophosphorylation of the ..cap alpha beta.. heterodimeric IGF-1 receptor complex correlates wit an IGF-1 dependent covalent reassociation into an ..cap alpha../sub 2/..beta../sub 2/ heterotetrameric disulfide-linked state.

  18. Distinct Growth Factor Families Are Recruited in Unique Spatiotemporal Domains during Long-Term Memory Formation in Aplysia californica.

    PubMed

    Kopec, Ashley M; Philips, Gary T; Carew, Thomas J

    2015-06-03

    Several growth factors (GFs) have been implicated in long-term memory (LTM), but no single GF can support all of the plastic changes that occur during memory formation. Because GFs engage highly convergent signaling cascades that often mediate similar functional outcomes, the relative contribution of any particular GF to LTM is difficult to ascertain. To explore this question, we determined the unique contribution of distinct GF families (signaling via TrkB and TGF-βr-II) to LTM formation in Aplysia. We demonstrate that TrkB and TGF-βr-II signaling are differentially recruited during two-trial training in both time (by trial 1 or 2, respectively) and space (in distinct subcellular compartments). These GFs independently regulate MAPK activation and synergistically regulate gene expression. We also show that trial 1 TrkB and trial 2 TGF-βr-II signaling are required for LTM formation. These data support the view that GFs engaged in LTM formation are interactive components of a complex molecular network.

  19. Hepatocyte Growth Factor Modulates MET Receptor Tyrosine Kinase and β-Catenin Functional Interactions to Enhance Synapse Formation

    PubMed Central

    Xie, Zhihui; Eagleson, Kathie L.

    2016-01-01

    MET, a pleiotropic receptor tyrosine kinase implicated in autism risk, influences multiple neurodevelopmental processes. There is a knowledge gap, however, in the molecular mechanism through which MET mediates developmental events related to disorder risk. In the neocortex, MET is expressed transiently during periods of peak dendritic outgrowth and synaptogenesis, with expression enriched at developing synapses, consistent with demonstrated roles in dendritic morphogenesis, modulation of spine volume, and excitatory synapse development. In a recent coimmunoprecipitation/mass spectrometry screen, β-catenin was identified as part of the MET interactome in developing neocortical synaptosomes. Here, we investigated the influence of the MET/β-catenin complex in mouse neocortical synaptogenesis. Western blot analysis confirms that MET and β-catenin coimmunoprecipitate, but N-cadherin is not associated with the MET complex. Following stimulation with hepatocyte growth factor (HGF), β-catenin is phosphorylated at tyrosine142 (Y142) and dissociates from MET, accompanied by an increase in β-catenin/N-cadherin and MET/synapsin 1 protein complexes. In neocortical neurons in vitro, proximity ligation assays confirmed the close proximity of these proteins. Moreover, in neurons transfected with synaptophysin-GFP, HGF stimulation increases the density of synaptophysin/bassoon (a presynaptic marker) and synaptophysin/PSD-95 (a postsynaptic marker) clusters. Mutation of β-catenin at Y142 disrupts the dissociation of the MET/β-catenin complex and prevents the increase in clusters in response to HGF. The data demonstrate a new mechanism for the modulation of synapse formation, whereby MET activation induces an alignment of presynaptic and postsynaptic elements that are necessary for assembly and formation of functional synapses by subsets of neocortical neurons that express MET/β-catenin complex. PMID:27595133

  20. Hepatitis B virus HBx protein activates Ras-GTP complex formation and establishes a Ras, Raf, MAP kinase signaling cascade.

    PubMed Central

    Benn, J; Schneider, R J

    1994-01-01

    Hepatitis B virus produces a small (154-amino acid) transcriptional transactivating protein, HBx, which is required for viral infection and has been implicated in virus-mediated liver oncogenesis. However, the molecular mechanism for HBx activity and its possible influence on cell proliferation have remained obscure. A number of studies suggest that HBx may stimulate transcription by indirectly activating transcription factors, possibly by influencing cell signaling pathways. We now present biochemical evidence that HBx activates Ras and rapidly induces a cytoplasmic signaling cascade linking Ras, Raf, and mitogen-activated protein kinase (MAP kinase), leading to transcriptional transactivation. HBx strongly elevates levels of GTP-bound Ras, activated and phosphorylated Raf, and tyrosine-phosphorylated and activated MAP kinase. Transactivation of transcription factor AP-1 by HBx is blocked by inhibition of Ras or Raf activities but not by inhibition of Ca(2+)- and diacylglycerol-dependent protein kinase C. HBx was also found to stimulate DNA synthesis in serum-starved cells. The hepatitis B virus HBx protein therefore stimulates Ras-GTP complex formation and promotes downstream signaling through Raf and MAP kinases, and may influence cell proliferation. Images PMID:7937954

  1. Wnt-5a/Frizzled9 Receptor Signaling through the Gαo-Gβγ Complex Regulates Dendritic Spine Formation.

    PubMed

    Ramírez, Valerie T; Ramos-Fernández, Eva; Henríquez, Juan Pablo; Lorenzo, Alfredo; Inestrosa, Nibaldo C

    2016-09-02

    Wnt ligands play crucial roles in the development and regulation of synapse structure and function. Specifically, Wnt-5a acts as a secreted growth factor that regulates dendritic spine formation in rodent hippocampal neurons, resulting in postsynaptic development that promotes the clustering of the PSD-95 (postsynaptic density protein 95). Here, we focused on the early events occurring after the interaction between Wnt-5a and its Frizzled receptor at the neuronal cell surface. Additionally, we studied the role of heterotrimeric G proteins in Wnt-5a-dependent synaptic development. We report that FZD9 (Frizzled9), a Wnt receptor related to Williams syndrome, is localized in the postsynaptic region, where it interacts with Wnt-5a. Functionally, FZD9 is required for the Wnt-5a-mediated increase in dendritic spine density. FZD9 forms a precoupled complex with Gαo under basal conditions that dissociates after Wnt-5a stimulation. Accordingly, we found that G protein inhibition abrogates the Wnt-5a-dependent pathway in hippocampal neurons. In particular, the activation of Gαo appears to be a key factor controlling the Wnt-5a-induced dendritic spine density. In addition, we found that Gβγ is required for the Wnt-5a-mediated increase in cytosolic calcium levels and spinogenesis. Our findings reveal that FZD9 and heterotrimeric G proteins regulate Wnt-5a signaling and dendritic spines in cultured hippocampal neurons.

  2. Enhanced conformational sampling to visualize a free-energy landscape of protein complex formation

    PubMed Central

    Iida, Shinji; Nakamura, Haruki; Higo, Junichi

    2016-01-01

    We introduce various, recently developed, generalized ensemble methods, which are useful to sample various molecular configurations emerging in the process of protein–protein or protein–ligand binding. The methods introduced here are those that have been or will be applied to biomolecular binding, where the biomolecules are treated as flexible molecules expressed by an all-atom model in an explicit solvent. Sampling produces an ensemble of conformations (snapshots) that are thermodynamically probable at room temperature. Then, projection of those conformations to an abstract low-dimensional space generates a free-energy landscape. As an example, we show a landscape of homo-dimer formation of an endothelin-1-like molecule computed using a generalized ensemble method. The lowest free-energy cluster at room temperature coincided precisely with the experimentally determined complex structure. Two minor clusters were also found in the landscape, which were largely different from the native complex form. Although those clusters were isolated at room temperature, with rising temperature a pathway emerged linking the lowest and second-lowest free-energy clusters, and a further temperature increment connected all the clusters. This exemplifies that the generalized ensemble method is a powerful tool for computing the free-energy landscape, by which one can discuss the thermodynamic stability of clusters and the temperature dependence of the cluster networks. PMID:27288028

  3. Efficient Super Energy Transfer Collisions Through Reactive-Complex Formation: H + SO2

    NASA Astrophysics Data System (ADS)

    Smith, Jonathan M.; Wilhelm, Michael J.; Ma, Jianqiang; Dai, HAI-LUNG

    2015-06-01

    Translational-to-vibrational energy transfer (ET) from a hyperthermal H atom to ambient SO2 was characterized using time-resolved Fourier transform infrared emission spectroscopy. Vibrational excitation of SO2, following collisions with H atoms containing 59 kcal/mol of kinetic energy, generated from the 193 nm photolysis of HBr, is detected in two distinct energy distributions: one with excitation predominantly at the fundamental vibrational levels is attributable to classical impulsive collisions, while the other, accounting for 80% of the excited SO2 with vibrational energy as high as 14,000 wn, is proposed to arise from the formation of a transient reactive-complex during the collision. The cross-section for this super ET collision is determined to be 0.53±0.05 Å2, or roughly 2% of all hard sphere collisions. This observation reveals that in collisions between a hyperthermal atom and an ambient molecule, for which a reactive-complex exists on the potential energy surface, a large quantity of translational energy can be transferred to the molecule with high efficiency.

  4. Requirements of fission yeast septins for complex formation, localization, and function.

    PubMed

    An, Hanbing; Morrell, Jennifer L; Jennings, Jennifer L; Link, Andrew J; Gould, Kathleen L

    2004-12-01

    Septins are GTP binding proteins important for cytokinesis in many eukaryotes. The Schizosaccaromyces pombe genome sequence predicts orthologues of four of five Saccharomyces cerevisiae septins involved in cytokinesis and these are named Spns1-4p. That spns1-4 are not essential genes permitted the application of a combined genetic and proteomics approach to determine their functional relationships. Our findings indicate that Spns1-4p are present throughout interphase as a diffusely localized approximately 8.5S complex containing two copies of each septin linked together as a chain in the order Spn3p-Spn4p-Spn1p-Spn2p. Septin recruitment to the medial region of the cell is genetically separable from ring formation, and whereas it is normally restricted to mitosis, it can be promoted without activation of the mitotic cell cycle machinery. Coalescence into ring structures requires Spn1p and Spn4p associate with at least one other septin subunit and the expression of Mid2p that is normally restricted to mitosis. This study establishes the functional requirements for septin complex organization in vivo.

  5. Requirements of Fission Yeast Septins for Complex Formation, Localization, and FunctionD⃞

    PubMed Central

    An, Hanbing; Morrell, Jennifer L.; Jennings, Jennifer L.; Link, Andrew J.; Gould, Kathleen L.

    2004-01-01

    Septins are GTP binding proteins important for cytokinesis in many eukaryotes. The Schizosaccaromyces pombe genome sequence predicts orthologues of four of five Saccharomyces cerevisiae septins involved in cytokinesis and these are named Spns1-4p. That spns1-4 are not essential genes permitted the application of a combined genetic and proteomics approach to determine their functional relationships. Our findings indicate that Spns1-4p are present throughout interphase as a diffusely localized ∼8.5S complex containing two copies of each septin linked together as a chain in the order Spn3p-Spn4p-Spn1p-Spn2p. Septin recruitment to the medial region of the cell is genetically separable from ring formation, and whereas it is normally restricted to mitosis, it can be promoted without activation of the mitotic cell cycle machinery. Coalescence into ring structures requires Spn1p and Spn4p associate with at least one other septin subunit and the expression of Mid2p that is normally restricted to mitosis. This study establishes the functional requirements for septin complex organization in vivo. PMID:15385632

  6. A SPITZER VIEW OF STAR FORMATION IN THE CYGNUS X NORTH COMPLEX

    SciTech Connect

    Beerer, I. M.; Koenig, X. P.; Hora, J. L.; Keto, E.; Smith, H. A.; Fazio, G. G.; Gutermuth, R. A.; Bontemps, S.; Schneider, N.; Megeath, S. T.; Motte, F.; Simon, R.; Allen, L. E.; Kraemer, K. E.; Price, S.; Mizuno, D.; Adams, J. D.; Hernandez, J.; Lucas, P. W.

    2010-09-01

    We present new images and photometry of the massive star-forming complex Cygnus X obtained with the Infrared Array Camera (IRAC) and the Multiband Imaging Photometer for Spitzer (MIPS) on board the Spitzer Space Telescope. A combination of IRAC, MIPS, UKIRT Deep Infrared Sky Survey, and Two Micron All Sky Survey data are used to identify and classify young stellar objects (YSOs). Of the 8231 sources detected exhibiting infrared excess in Cygnus X North, 670 are classified as class I and 7249 are classified as class II. Using spectra from the FAST Spectrograph at the Fred L. Whipple Observatory and Hectospec on the MMT, we spectrally typed 536 sources in the Cygnus X complex to identify the massive stars. We find that YSOs tend to be grouped in the neighborhoods of massive B stars (spectral types B0 to B9). We present a minimal spanning tree analysis of clusters in two regions in Cygnus X North. The fraction of infrared excess sources that belong to clusters with {>=}10 members is found to be 50%-70%. Most class II objects lie in dense clusters within blown out H II regions, while class I sources tend to reside in more filamentary structures along the bright-rimmed clouds, indicating possible triggered star formation.

  7. Electrocatalytic Oxidation of Formate with Nickel Diphosphane Dipeptide Complexes. Effect of Ligands Modified with Amino Acids

    SciTech Connect

    Galan, Brandon R.; Reback, Matthew L.; Jain, Avijita; Appel, Aaron M.; Shaw, Wendy J.

    2013-09-03

    A series of nickel bis-diphosphine complexes with dipeptides appended to the ligands were investigated for the catalytic oxidation of formate. Typical rates of ~7 s-1 were found, similar to the parent complex (~8 s-1), with amino acid size and positioning contributing very little to rate or operating potential. Hydroxyl functionalities did result in lower rates, which were recovered by protecting the hydroxyl group. The results suggest that the overall dielectric introduced by the dipeptides does not play an important role in catalysis, but free hydroxyl groups do influence activity suggesting contributions from intra- or intermolecular interactions. These observations are important in developing a fundamental understanding of the affect that an enzyme-like outer coordination sphere can have upon molecular catalysts. This work was funded by the US DOE Basic Energy Sciences, Chemical Sciences, Geoscience and Biosciences Division (BRG, AJ, AMA, WJS), the US DOE Basic Energy Sciences, Physical Bioscience program (MLR). Pacific Northwest National Laboratory is operated by Battelle for the U.S. Department of Energy.

  8. Associative and dissociative mechanisms in the formation of phthalazine bridged organodiplatinum(II) complexes.

    PubMed

    Rashidi, Mehdi; Nabavizadeh, S Masoud; Zare, Ahad; Jamali, Sirous; Puddephatt, Richard J

    2010-09-20

    The reaction of phthalazine with the binuclear organoplatinum complexes [Me(2)Pt(μ-SMe(2))(μ-dppm)PtR(2)], R = Me, Ph, 4-tolyl or R(2) = (CH(2))(4), dppm = bis(diphenylphosphino)methane, gives the corresponding complexes [Me(2)Pt(μ-phthalazine)(μ-dppm)PtR(2)] by displacement of the bridging dimethylsulfide ligand. The structures of [Me(2)Pt(μ-SMe(2))(μ-dppm)PtMe(2)] and [Me(2)Pt(μ-phthalazine)(μ-dppm)PtMe(2)] have been determined. Kinetic studies show that the reactions occur mostly by a second order reaction when R = Me or R(2) = (CH(2))(4) but entirely by a first order reaction when R = Ph or 4-tolyl. Evidence is presented that the reactions when R = Me or R(2) = (CH(2))(4) can occur by either associative or dissociative mechanisms but that the reactions when R = Ph or 4-tolyl occur only by an unusual dissociative mechanism involving formation of an intermediate with a donor-acceptor Pt-Pt bond.

  9. Enhanced conformational sampling to visualize a free-energy landscape of protein complex formation.

    PubMed

    Iida, Shinji; Nakamura, Haruki; Higo, Junichi

    2016-06-15

    We introduce various, recently developed, generalized ensemble methods, which are useful to sample various molecular configurations emerging in the process of protein-protein or protein-ligand binding. The methods introduced here are those that have been or will be applied to biomolecular binding, where the biomolecules are treated as flexible molecules expressed by an all-atom model in an explicit solvent. Sampling produces an ensemble of conformations (snapshots) that are thermodynamically probable at room temperature. Then, projection of those conformations to an abstract low-dimensional space generates a free-energy landscape. As an example, we show a landscape of homo-dimer formation of an endothelin-1-like molecule computed using a generalized ensemble method. The lowest free-energy cluster at room temperature coincided precisely with the experimentally determined complex structure. Two minor clusters were also found in the landscape, which were largely different from the native complex form. Although those clusters were isolated at room temperature, with rising temperature a pathway emerged linking the lowest and second-lowest free-energy clusters, and a further temperature increment connected all the clusters. This exemplifies that the generalized ensemble method is a powerful tool for computing the free-energy landscape, by which one can discuss the thermodynamic stability of clusters and the temperature dependence of the cluster networks.

  10. Monolayer kinetic model of formation of β-cyclodextrin-β-carotene inclusion complex.

    PubMed

    Ivanova, Tz; Mircheva, K; Balashev, K; Panaiotov, I; Boury, F

    2015-11-01

    The carotenoids are sensitive molecules and their chemical integrity must be preserved from pro-oxidant elements which could affect and decrease their physiological benefits. The encapsulation based on the inclusion of the carotenoids into cage molecules is a promising approach for preserving over time of the intrinsic properties of the carotenoids. It is well known that cyclic oligosaccharide β-cyclodextrin (CD) as a cage molecule possesses strong inclusion ability to β-carotene (C) and as a result of the hydrophobic interactions forms an inclusion complex. In the present paper a monolayer kinetic model was established with the notion to extract more information about the influence of the molecular structure and organization to the interfacial interactions between the interacting species as well as about the role of the specific areas, which are often underestimated in previously studied dispersed systems. We developed the monolayer kinetic model for the formation of the inclusion CD-C complex by applying an experimental approach for following the kinetics by means of measuring the decrease of the surface area (ΔA) versus time (t) at constant surface pressure (π) and the decrease of surface pressure (π) versus time (t) at constant surface area (A). We also visualized by AFM the state of the monolayers at the initial and end points of the kinetic process. The values for the degree (d) and constant (Ka) of the association were estimated and compared with those from the studies of dispersed systems.

  11. The development of folds and cleavages in slate belts by underplating in accretionary complexes: A comparison of the Kodiak Formation, Alaska and the Calaveras Complex, California

    NASA Astrophysics Data System (ADS)

    Paterson, Scott R.; Sample, James C.

    1988-08-01

    The development of folds and cleavages in slate and graywacke belts is commonly attributed to arc-continent or continent-continent collisions. However, the Kodiak Formation of southern Alaska and the Calaveras Complex of the western Sierra Nevada, California, are two slate and graywacke belts in which folds and slaty cleavages developed during simple underthrusting and underplating within accretionary wedges. The Maastrichtian Kodiak Formation is composed dominantly of coherent turbidites but includes lesser pebbly mudstone, minor conglomerate, and rare chert. The Kodiak Formation is part of a large accretionary complex that youngs in age seaward, but bedding tops generally show landward younging. A progression of structures has been determined by crosscutting relationships and includes (1) syndeformational depositional features; (2) broken formation; (3) slaty cleavage, folds, and thrust faults; (4) crenulations and crenulation cleavage; (5) late brittle thrust faults; and (6) right-lateral strike-slip faults. Broken formation, slaty cleavage, thrust faults, and folds developed during underthrusting and underplating within an accretionary wedge. Crenulations and brittle thrust faults are related to subsequent intrawedge shortening. Based on peak metamorphism in the uppermost zeolite to prehnite-pumpellyite facies, underplating occurred at a minimum depth of 10 km. The Calaveras Complex is composed of argillite, chert, graywacke, pebbly mudstone, limestone, and volcanic rocks. Its age of deposition has a maximum range from Permian to Early Jurassic. Overall, the unit appears to young westward, but local facing indicators show eastward younging of individual blocks. The sequence of structures developed in the Calaveras Complex is (1) syn-depositional olistostromes; (2) broken formation; (3) slaty cleavage, folds, and thrust faults; and (4) younger Jura-Triassic folds and crenulation cleavages. Broken formation and slaty cleavage developed during underthrusting and

  12. Ganglioside-magnetosome complex formation enhances uptake of gangliosides by cells

    PubMed Central

    Guan, Feng; Li, Xiang; Guo, Jia; Yang, Ganglong; Li, Xiang

    2015-01-01

    Bacterial magnetosomes, because of their nano-scale size, have a large surface-to-volume ratio and are able to carry large quantities of bioactive substances such as enzymes, antibodies, and genes. Gangliosides, a family of sialic acid-containing glycosphingolipids, function as distinctive cell surface markers and as specific determinants in cellular recognition and cell-to-cell communication. Exogenously added gangliosides are often used to study biological functions, transport mechanisms, and metabolism of their endogenous counterparts. Absorption of gangliosides into cells is typically limited by their tendency to aggregate into micelles in aqueous media. We describe here a simple strategy to remove proteins from the magnetosome membrane by sodium dodecyl sulfate treatment, and efficiently immobilize a ganglioside (GM1 or GM3) on the magnetosome by mild ultrasonic treatment. The maximum of 11.7±1.2 µg GM1 and 11.6±1.5 μg GM3 was loaded onto 1 mg magnetosome, respectively. Complexes of ganglioside-magnetosomes stored at 4°C for certain days presented the consistent stability. The use of GM1-magnetosome complex resulted in the greatest enhancement of ganglioside incorporation by cells. GM3-magnetosome complex significantly inhibited EGF-induced phosphorylation of the epidermal growth factor receptor. Both of these effects were further enhanced by the presence of a magnetic field. PMID:26609230

  13. Kinetics of self-assembly via facilitated diffusion: Formation of the transcription complex

    NASA Astrophysics Data System (ADS)

    Kalay, Ziya

    2015-10-01

    We present an analytically solvable model for self-assembly of a molecular complex on a filament. The process is driven by a seed molecule that undergoes facilitated diffusion, which is a search strategy that combines diffusion in three dimensions and one dimension. Our study is motivated by single-molecule-level observations revealing the dynamics of transcription factors that bind to the deoxyribonucleic acid at early stages of transcription. We calculate the probability that a complex made up of a given number of molecules is completely formed, as well as the distribution of completion times, upon the binding of a seed molecule at a target site on the filament (without explicitly modeling the three-dimensional diffusion that precedes binding). We compare two different mechanisms of assembly where molecules bind in sequential and random order. Our results indicate that while the probability of completion is greater for random binding, the completion time scales exponentially with the size of the complex; in contrast, it scales as a power law or slower for sequential binding, asymptotically. Furthermore, we provide model predictions for the dissociation and residence times of the seed molecule, which are observables accessible in single-molecule tracking experiments.

  14. Complex Patterns of Association between Pleiotropy and Transcription Factor Evolution

    PubMed Central

    Chesmore, Kevin N.; Bartlett, Jacquelaine; Cheng, Chao; Williams, Scott M.

    2016-01-01

    Pleiotropy has been claimed to constrain gene evolution but specific mechanisms and extent of these constraints have been difficult to demonstrate. The expansion of molecular data makes it possible to investigate these pleiotropic effects. Few classes of genes have been characterized as intensely as human transcription factors (TFs). We therefore analyzed the evolutionary rates of full TF proteins, along with their DNA binding domains and protein-protein interacting domains (PID) in light of the degree of pleiotropy, measured by the number of TF–TF interactions, or the number of DNA-binding targets. Data were extracted from the ENCODE Chip-Seq dataset, the String v 9.2 database, and the NHGRI GWAS catalog. Evolutionary rates of proteins and domains were calculated using the PAML CodeML package. Our analysis shows that the numbers of TF-TF interactions and DNA binding targets associated with constrained gene evolution; however, the constraint caused by the number of DNA binding targets was restricted to the DNA binding domains, whereas the number of TF-TF interactions constrained the full protein and did so more strongly. Additionally, we found a positive correlation between the number of protein–PIDs and the evolutionary rates of the protein–PIDs. These findings show that not only does pleiotropy associate with constrained protein evolution but the constraint differs by domain function. Finally, we show that GWAS associated TF genes are more highly pleiotropic. The GWAS data illustrates that mutations in highly pleiotropic genes are more likely to be associated with disease phenotypes. PMID:27635052

  15. Analyzing Chromatin Remodeling Complexes Using Shotgun Proteomics and Normalized Spectral Abundance Factors

    PubMed Central

    Florens, Laurence; Carozza, Michael J.; Swanson, Selene K; Fournier, Marjorie; Coleman, Michael K.; Workman, Jerry L.; Washburn, Michael P.

    2006-01-01

    Mass spectrometry based approaches are commonly used to identify proteins from multiprotein complexes, typically with the goal of identifying new complex members or identifying post translational modifications. However, with the recent demonstration that spectral counting is a powerful quantitative proteomic approach, the analysis of multiprotein complexes by mass spectrometry can be reconsidered in certain cases. Using the chromatography based approach named multidimensional protein identification technology, multiprotein complexes may be analyzed quantitatively using the normalized spectral abundance factor that allows comparison of multiple independent analyses of samples. This study describes an approach to visualize multiprotein complex datasets that provides structure function information that is superior to tabular lists of data. In this method review, we describe a reanalysis of the Rpd3/Sin3 small and large histone deacetylase complexes previously described in a tabular form to demonstrate the normalized spectral abundance factor approach. PMID:17101441

  16. Soft versus hard junction formation for α-terthiophene molecular wires and their charge transfer complexes

    NASA Astrophysics Data System (ADS)

    Vezzoli, Andrea; Grace, Iain M.; Brooke, Carly; Nichols, Richard J.; Lambert, Colin J.; Higgins, Simon J.

    2017-03-01

    We used a range of scanning tunnelling microscopy (STM)-based methods to conduct a detailed study of single molecule junction conductance enhancement upon charge transfer complex formation, using bis(thiaalkyl)arene molecular wires as electron donors and tetracyanoethylene (TCNE) as an electron acceptor. Using the "hard" STM break junction (STM-BJ) method, in which a Au STM tip is pushed into a Au substrate and then withdrawn in the presence of molecules, we see a single, very broad, peak in the resulting conductance histogram when all data are used; the conductance enhancement is 25-fold for a terthiophene donor and 15-fold for a phenyl group. After rational data selection, in which only current-distance curves that contain a current plateau >0.2 nm long are used in the conductance histogram, three sharper peaks are resolved in the histograms for the charge transfer complexes; two substantially lower-conductance peaks are resolved for the uncomplexed molecules. Using the "soft" STM I(s) technique, in which initial contact between tip and substrate is avoided and the current limit is about an order of magnitude lower, we were able to resolve two peaks for the uncomplexed molecules depending upon the initial set point current (i.e., tip height), one at the same value as the lower of the two data-selected STM-BJ histogram peaks and an additional peak beyond the low-current limit for the STM-BJ experiment. For the terthiophene, the low, medium, and high conductance peaks for the TCNE complex are, respectively, ca. 70, 70, and 46 times higher in conductance than the corresponding peaks for the free molecule.

  17. Oceanic crust formation in the Egeria Fracture Zone Complex (Central Indian Ocean)

    NASA Astrophysics Data System (ADS)

    Le Minor, Marine; Gaina, Carmen; Sigloch, Karin; Minakov, Alexander

    2016-04-01

    This study aims to analyse in detail the oceanic crust fabric and volcanic features (seamounts) formed for the last 10 million years at the Central Indian Ridge between 19 and 21 latitude south. Multibeam bathymetry and magnetic data has been collected in 2013 as part of the French-German expedition RHUM-RUM (Reunion hotspot and upper mantle - Reunion's unterer mantel). Three long profiles perpendicular on the Central Indian Ridge (CIR), south of the Egeria fracture zone, document the formation of oceanic crust since 10 million years, along with changes in plate kinematics and variations in the magmatic input. We have inspected the abyssal hill geometry and orientation along conjugate oceanic flanks and within one fracture zone segment where we could identify J-shaped features that are indicators of changes in plate kinematics. The magnetic anomaly data shows a slight asymmetry in seafloor spreading rates on conjugate flanks: while a steady increase in spreading rate from 10 Ma to the present is shown by the western flank, the eastern part displays a slowing down from 5 Ma onwards. The deflection of the anti J-shaped abyssal hill lineations suggest that the left-stepping Egeria fracture zone complex (including the Egeria, Flinders and an un-named fracture zone to the southeast) was under transpression from 9 to 6 Ma and under transtension since 3 Ma. The transpressional event was triggered by a clockwise mid-ocean ridge reorientation and a decrease of its offset, whereas the transtensional regime was probably due to a counter-clockwise change in the spreading direction and an increase of the ridge offset. The new multibeam data along the three profiles reveal that crust on the eastern side is smoother (as shown by the abyssal hill number and structure) and hosts several seamounts (with age estimations of 7.67, 6.10 and 0.79 Ma), in contrast to the rougher conjugate western flank. Considering that the western flank was closer to the Reunion plume, and therefore

  18. Growth Factor Signaling and Memory Formation: Temporal and Spatial Integration of a Molecular Network

    ERIC Educational Resources Information Center

    Kopec, Ashley M.; Carew, Thomas J.

    2013-01-01

    Growth factor (GF) signaling is critically important for developmental plasticity. It also plays a crucial role in adult plasticity, such as that required for memory formation. Although different GFs interact with receptors containing distinct types of kinase domains, they typically signal through converging intracellular cascades (e.g.,…

  19. Bi-Factor MIRT Observed-Score Equating for Mixed-Format Tests

    ERIC Educational Resources Information Center

    Lee, Guemin; Lee, Won-Chan

    2016-01-01

    The main purposes of this study were to develop bi-factor multidimensional item response theory (BF-MIRT) observed-score equating procedures for mixed-format tests and to investigate relative appropriateness of the proposed procedures. Using data from a large-scale testing program, three types of pseudo data sets were formulated: matched samples,…

  20. A new model for the computation of the formation factor of core rocks

    NASA Astrophysics Data System (ADS)

    Beltrán, A.; Chávez, O.; Zaldivar, J.; Godínez, F. A.; García, A.; Zenit, R.

    2017-04-01

    Among all the rock parameters measured by modern well logging tools, the formation factor is essential because it can be used to calculate the volume of oil- and/or gas in wellsite. A new mathematical model to calculate the formation factor is analytically derived from first principles. Given the electrical properties of both rock and brine (resistivities) and tortuosity (a key parameter of the model), it is possible to calculate the dependence of the formation factor with porosity with good accuracy. When the cementation exponent ceases to remain constant with porosity; the new model is capable of capturing both: the non-linear behavior (for small porosity values) and the typical linear one in log-log plots for the formation factor vs. porosity. Comparisons with experimental data from four different conventional core rock lithologies: sands, sandstone, limestone and volcanic are shown, for all of them a good agreement is observed. This new model is robust, simple and of easy implementation for practical applications. In some cases, it could substitute Archie's law replacing its empirical nature.

  1. Formation of ethylene glycol and other complex organic molecules in star-forming regions

    NASA Astrophysics Data System (ADS)

    Rivilla, V. M.; Beltrán, M. T.; Cesaroni, R.; Fontani, F.; Codella, C.; Zhang, Q.

    2017-02-01

    Context. The detection of complex organic molecules related with prebiotic chemistry in star-forming regions allows us to investigate how the basic building blocks of life are formed. Aims: Ethylene glycol (CH2OH)2 is the simplest sugar alcohol and the reduced alcohol of the simplest sugar glycoladehyde (CH2OHCHO). We study the molecular abundance and spatial distribution of (CH2OH)2, CH2OHCHO and other chemically related complex organic species (CH3OCHO, CH3OCH3, and C2H5OH) towards the chemically rich massive star-forming region G31.41+0.31. Methods: We analyzed multiple single-dish (Green Bank Telescope and IRAM 30 m) and interferometric (Submillimeter Array) spectra towards G31.41+0.31, covering a range of frequencies from 45 to 258 GHz. We fitted the observed spectra with a local thermodynamic equilibrium (LTE) synthetic spectra, and obtained excitation temperatures and column densities. We compared our findings in G31.41+0.31 with the results found in other environments, including low- and high-mass star-forming regions, quiescent clouds and comets. Results: We report for the first time the presence of the aGg' conformer of (CH2OH)2 towards G31.41+0.31, detecting more than 30 unblended lines. We also detected multiple transitions of other complex organic molecules such as CH2OHCHO, CH3OCHO, CH3OCH3, and C2H5OH. The high angular resolution images show that the (CH2OH)2 emission is very compact, peaking towards the maximum of the 1.3 mm continuum. These observations suggest that low abundance complex organic molecules, like (CH2OH)2 or CH2OHCHO, are good probes of the gas located closer to the forming stars. Our analysis confirms that (CH2OH)2 is more abundant than CH2OHCHO in G31.41+0.31, as previously observed in other interstellar regions. Comparing different star-forming regions we find evidence of an increase of the (CH2OH)2/CH2OHCHO abundance ratio with the luminosity of the source. The CH3OCH3/CH3OCHO and (CH2OH)2/C2H5OH ratios are nearly constant with

  2. The earliest phases of high-mass star formation: the NGC 6334-NGC 6357 complex

    NASA Astrophysics Data System (ADS)

    Russeil, D.; Zavagno, A.; Motte, F.; Schneider, N.; Bontemps, S.; Walsh, A. J.

    2010-06-01

    Context. Our knowledge of high-mass star formation has been mainly based on follow-up studies of bright sources found by IRAS, and has thus been incomplete for its earliest phases, which are inconspicuous at infrared wavelengths. With a new generation of powerful bolometer arrays, unbiased large-scale surveys of nearby high-mass star-forming complexes now search for the high-mass analog of low-mass cores and class 0 protostars. Aims: Following the pioneering study of Cygnus X, we investigate the star-forming region NGC 6334-NGC 6357 (~1.7 kpc). Methods: We study the complex NGC 6334-NGC 6357 in an homogeneous way following the previous work of Motte and collaborators. We used the same method to extract the densest cores which are the most likely sites for high-mass star formation. We analyzed the SIMBA/SEST 1.2 mm data presented in Munoz and coworkers, which covers all high-column density areas (A v ≥ 15 mag) of the NGC 6334-NGC 6357 complex and extracted dense cores following the method used for Cygnus X. We constrain the properties of the most massive dense cores (M > 100 M_⊙) using new molecular line observations (as SiO, N2H+,H13CO+, HCO+ (1-0) and CH3CN) with Mopra and a complete cross-correlation with infrared databases (MSX, GLIMPSE, MIPSGAL) and literature. Results: We extracted 163 massive dense cores of which 16 are more massive than 200 M_⊙. These high-mass dense cores have a typical FWHM size of 0.37 pc, an average mass of M ~ 600 M_⊙, and a volume-averaged density of ~ 1.5 × 105 cm-3. Among these massive dense cores, 6 are good candidates for hosting high-mass infrared-quiet protostars, 9 cores are classified as high-luminosity infrared protostars, and we find only one high-mass starless clump (~0.3 pc, ~ 4 × 104 cm-3) that is gravitationally bound. Conclusions: Since our sample is derived from a single molecular complex and covers every embedded phase of high-mass star formation, it provides a statistical estimate of the lifetime of massive

  3. SOXC Transcription Factors Induce Cartilage Growth Plate Formation in Mouse Embryos by Promoting Noncanonical WNT Signaling.

    PubMed

    Kato, Kenji; Bhattaram, Pallavi; Penzo-Méndez, Alfredo; Gadi, Abhilash; Lefebvre, Véronique

    2015-09-01

    Growth plates are specialized cartilage structures that ensure the elongation of most skeletal primordia during vertebrate development. They are made by chondrocytes that proliferate in longitudinal columns and then progress in a staggered manner towards prehypertrophic, hypertrophic and terminal maturation. Complex molecular networks control the formation and activity of growth plates, but remain incompletely understood. We investigated here the importance of the SoxC genes, which encode the SOX4, SOX11 and SOX12 transcription factors, in growth plates. We show that the three genes are expressed robustly in perichondrocytes and weakly in growth plate chondrocytes. SoxC(Prx1Cre) mice, which deleted SoxC genes in limb bud skeletogenic mesenchyme, were born with tiny appendicular cartilage primordia because of failure to form growth plates. In contrast, SoxC(Col2Cre) and SoxC(ATC) mice, which deleted SoxC genes primarily in chondrocytes, were born with mild dwarfism and fair growth plates. Chondrocytes in the latter mutants matured normally, but formed irregular columns, proliferated slowly and died ectopically. Asymmetric distribution of VANGL2 was defective in both SoxC(Prx1Cre) and SoxC(ATC) chondrocytes, indicating impairment of planar cell polarity, a noncanonical WNT signaling pathway that controls growth plate chondrocyte alignment, proliferation and survival. Accordingly, SoxC genes were necessary in perichondrocytes for expression of Wnt5a, which encodes a noncanonical WNT ligand required for growth plate formation, and in chondrocytes and perichondrocytes for expression of Fzd3 and Csnk1e, which encode a WNT receptor and casein kinase-1 subunit mediating planar cell polarity, respectively. Reflecting the differential strengths of the SOXC protein transactivation domains, SOX11 was more powerful than SOX4, and SOX12 interfered with the activity of SOX4 and SOX11. Altogether, these findings provide novel insights into the molecular regulation of skeletal

  4. Acrylamide in gingerbread: critical factors for formation and possible ways for reduction.

    PubMed

    Amrein, Thomas M; Schönbächler, Barbara; Escher, Felix; Amado, Renato

    2004-06-30

    The influence of ingredients, additives, and process conditions on acrylamide formation in gingerbread was investigated. The sources for reducing sugars and free asparagine were identified, and the effect of different baking agents on acrylamide formation was evaluated. Ammonium hydrogencarbonate strongly enhanced acrylamide formation, but its N atom was not incorporated into acrylamide, nor did acrylic acid form acrylamide in gingerbread. Acrylamide concentration and browning intensity both increased with baking time and correlated with each other. The use of sodium hydrogencarbonate as baking agent reduced the acrylamide concentration by >60%. Free asparagine was a limiting factor for acrylamide formation, but the acrylamide content could also be lowered by replacing reducing sugars with sucrose or by adding organic acids. It is concluded that a significant reduction of acrylamide in gingerbread can be achieved by using sodium hydrogencarbonate as baking agent, minimizing free asparagine, and avoiding prolonged baking.

  5. Modification of the protein corona-nanoparticle complex by physiological factors.

    PubMed

    Braun, Nicholas J; DeBrosse, Madeleine C; Hussain, Saber M; Comfort, Kristen K

    2016-07-01

    Nanoparticle (NP) effects in a biological system are driven through the formation and structure of the protein corona-NP complex, which is dynamic by nature and dependent upon factors from both the local environment and NP physicochemical parameters. To date, considerable data has been gathered regarding the structure and behavior of the protein corona in blood, plasma, and traditional cell culture medium. However, there exists a knowledge gap pertaining to the protein corona in additional biological fluids and following incubation in a dynamic environment. Using 13nm gold NPs (AuNPs), functionalized with either polyethylene glycol or tannic acid, we demonstrated that both particle characteristics and the associated protein corona were altered when exposed to artificial physiological fluids and under dynamic flow. Furthermore, the magnitude of observed behavioral shifts were dependent upon AuNP surface chemistry. Lastly, we revealed that exposure to interstitial fluid produced protein corona modifications, reshaping of the nano-cellular interface, modified AuNP dosimetry, and induction of previously unseen cytotoxicity. This study highlights the need to elucidate both NP and protein corona behavior in biologically representative environments in an effort to increase accurate interpretation of data and transfer of this knowledge to efficacy, behavior, and safety of nano-based applications.

  6. Synthesis, characterization and thermodynamics of complex formation of some new Schiff base ligands with some transition metal ions and the adduct formation of zinc Schiff base complexes with some organotin chlorides

    NASA Astrophysics Data System (ADS)

    Asadi, Mozaffar; Asadi, Zahra; Torabi, Susan; Lotfi, Najmeh

    Four new complexes, [M(Salpyr)] where Salpyr = N,N'-bis(Salicylidene)-2,3- and 3,4-diiminopyridine and M = Co, Cu, Mn, Ni and Zn were synthesized and characterized by 1H NMR, IR spectroscopy, elemental analysis and UV-vis spectrophotometry. UV-vis spectrophotometric study of the adduct formation of the zinc(II) complexes, [Zn(2,3-Salpyr)] and [Zn(3,4-Salpyr)], as donor with R2SnCl2 (R = methyl, phenyl, n-butyl), PhSnCl3 and Bu3SnCl as acceptors has been investigated in methanol, as solvent. The formation constants and the thermodynamic free energies were measured using UV-vis spectrophotometry. Titration of the organotin chlorides with Zn(II) complexes at various temperatures (T = 283-313 K) leads to 1:1 adduct formation. The results show that the formation constants were decreased by increasing the temperature. The trend of the reaction of RnSnCl4-n as acceptors toward given zinc complexes was as follows: PhSnCl3 > Me2SnCl2 > Ph2SnCl2 > Bu2SnCl2 > Bu3SnCl By considering the formation constants and the ΔG° of the complex formation for the Schiff base as donor and the M(II) as acceptor, the following conclusion was drawn: the formation constant for a given Schiff base changes according to the following trend: Ni > Cu > Co > Zn > Mn

  7. Formative assessment and design of a complex clinical decision support tool for pulmonary embolism.

    PubMed

    Khan, Sundas; McCullagh, Lauren; Press, Anne; Kharche, Manish; Schachter, Andy; Pardo, Salvatore; McGinn, Thomas

    2016-02-01

    Electronic health record (EHR)-based clinical decision support (CDS) tools are rolled out with the urgency to meet federal requirements without time for usability testing and refinement of the user interface. As part of a larger project to design, develop and integrate a pulmonary embolism CDS tool for emergency physicians, we conducted a formative assessment to determine providers' level of interest and input on designs and content. This was a study to conduct a formative assessment of emergency medicine (EM) physicians that included focus groups and key informant interviews. The focus of this study was twofold, to determine the general attitude towards CDS tool integration and the ideal integration point into the clinical workflow. To accomplish this, we first approached EM physicians in a focus group, then, during key informant interviews, we presented workflow designs and gave a scenario to help the providers visualise how the CDS tool works. Participants were asked questions regarding the trigger location, trigger words, integration into their workflow, perceived utility and heuristic of the tool. Results from the participants' survey responses to trigger location, perceived utility and efficiency, indicated that the providers felt the tool would be more of a hindrance than an aid. However, some providers commented that they had not had exposure to CDS tools but had used online calculators, and thought the tools would be helpful at the point-of-care if integrated into the EHR. Furthermore, there was a preference for an order entry wireframe. This study highlights several factors to consider when designing CDS tools: (1) formative assessment of EHR functionality and clinical environment workflow, (2) focus groups and key informative interviews to incorporate providers' perceptions of CDS and workflow integration and/or (3) the demonstration of proposed workflows through wireframes to help providers visualise design concepts.

  8. Formation of bacteriochlorophyll form B820 in light harvesting 2 complexes from purple sulfur bacteria treated with dioxane.

    PubMed

    Makhneva, Z K; Toropygina, O A; Moskalenko, A A

    2005-10-01

    Treatment of some sulfur bacteria (Allochromatium minutissimum, Thiorhodospira sibirica, and Ectothiorhodospira halovacuolata WN22) with dioxane results in formation of the bacteriochlorophyll form B820 in the light harvesting complex LH2. This form characterized by absorption maximum at 820 nm has the same absorption spectrum as B820 subcomplex from LH1 complex. Appearance of the B820 form was accompanied by a sharp decrease in absorption in the carotenoid region. This phenomenon observed in all LH2 complexes investigated may be attributed to formation of colorless carotenoid aggregates. This is very similar to the previously reported dissociation of the LH1 complex with carotenoids into B820 subcomplexes. Although the B820 form corresponded the bacteriochlorophyll dimer, its circular dichroism spectrum showed that pigment molecules in this dimer exhibit different interaction than those in the B820 subcomplex. The dioxane treatment of LH2 complexes isolated from Rhodopseudomonas palustris bacteria grown under normal or low intensity illumination did not result in formation of such dimers. It is suggested that bacteriochlorophyll B820 formation is related to unique structure of LH2 complexes from the sulfur bacteria.

  9. Mesoscopic Modeling of Thrombus Formation and Growth: Platelet Deposition in Complex Geometries

    NASA Astrophysics Data System (ADS)

    Yazdani, Alireza; Karniadakis, George

    2014-11-01

    Haemodynamics and blood rheology are important contributing factors to thrombus formation at a vulnerable vessel wall, and adhesion of platelets to a vascular surface, particularly in regions of flow stagnation, recirculation and reattachment is significantly important in formation of thrombi. For example, haemodynamic micro-environment can have effects on thrombosis inside the atherosclerotic plaques and aneurysms. To study these effects, we have developed and validated a model for platelet aggregation in blood flow using Dissipative Particle Dynamics (DPD) method. In this model platelets are considered as single DPD particles interacting with each other via Morse potential once activated. We assign an activation delay time to each platelet such that they remain passive during that time. We investigate the effect of different geometries on platelet aggregation by considering arterial stenosis at different levels of occlusion, and aneurysms of different shapes and sizes. The results show a marked increase in platelet aggregation within the boundaries of deceleration zone by increasing the degree of stenosis. Further, we observe enhanced platelet margination and wall deposition in the presence of red blood cells.

  10. Human Choline Kinase-α Promotes Hepatitis C Virus RNA Replication through Modulation of Membranous Viral Replication Complex Formation

    PubMed Central

    Wong, Mun-Teng

    2016-01-01

    ABSTRACT Hepatitis C virus (HCV) infection reorganizes cellular membranes to create an active viral replication site named the membranous web (MW). The role that human choline kinase-α (hCKα) plays in HCV replication remains elusive. Here, we first showed that hCKα activity, not the CDP-choline pathway, promoted viral RNA replication. Confocal microscopy and subcellular fractionation of HCV-infected cells revealed that a small fraction of hCKα colocalized with the viral replication complex (RC) on the endoplasmic reticulum (ER) and that HCV infection increased hCKα localization to the ER. In the pTM-NS3-NS5B model, NS3-NS5B expression increased the localization of the wild-type, not the inactive D288A mutant, hCKα on the ER, and hCKα activity was required for effective trafficking of hCKα and NS5A to the ER. Coimmunoprecipitation showed that hCKα was recruited onto the viral RC presumably through its binding to NS5A domain 1 (D1). hCKα silencing or treatment with CK37, an hCKα activity inhibitor, abolished HCV-induced MW formation. In addition, hCKα depletion hindered NS5A localization on the ER, interfered with NS5A and NS5B colocalization, and mitigated NS5A-NS5B interactions but had no apparent effect on NS5A-NS4B and NS4B-NS5B interactions. Nevertheless, hCKα activity was not essential for the binding of NS5A to hCKα or NS5B. These findings demonstrate that hCKα forms a complex with NS5A and that hCKα activity enhances the targeting of the complex to the ER, where hCKα protein, not activity, mediates NS5A binding to NS5B, thereby promoting functional membranous viral RC assembly and viral RNA replication. IMPORTANCE HCV infection reorganizes the cellular membrane to create an active viral replication site named the membranous web (MW). Here, we report that human choline kinase-α (hCKα) acts as an essential host factor for HCV RNA replication. A fraction of hCKα colocalizes with the viral replication complex (RC) on the endoplasmic reticulum

  11. Mercury(II) Complex Formation With Glutathione in Alkaline Aqueous Solution

    SciTech Connect

    Mah, V.; Jalilehvand, F.

    2009-05-19

    The structure and speciation of the complexes formed between mercury(II) ions and glutathione (GSH = L-glutamyl-L-cysteinyl-glycine) have been studied for a series of alkaline aqueous solutions (C{sub Hg{sup 2+}} {approx} 18 mmol dm{sup -3} and C{sub GSH} = 40-200 mmol dm{sup -3} at pH {approx} 10.5) by means of extended X-ray absorption fine structure (EXAFS) and {sup 199}Hg NMR spectroscopy at ambient temperature. The dominant complexes are [Hg(GS){sub 2}]{sup 4-} and [Hg(GS){sub 3}]{sup 7-}, with mean Hg-S bond distances of 2.32(1) and 2.42(2) {angstrom} observed in digonal and trigonal Hg-S coordination, respectively. The proportions of the Hg{sup 2+}-glutathione complexes were evaluated by fitting linear combinations of model EXAFS oscillations representing each species to the experimental EXAFS spectra. The [Hg(GS){sub 4}]{sup 10-} complex, with four sulfur atoms coordinated at a mean Hg-S bond distance of 2.52(2) {angstrom}, is present in minor amounts (<30%) in solutions containing a large excess of glutathione (C{sub GSH} {ge} 160 mmol dm{sup -3}). Comparable alkaline mercury(II) cysteine (H{sub 2}Cys) solutions were also investigated and a reduced tendency to form higher complexes was observed, because the deprotonated amino group of Cys{sup 2-} allows the stable [Hg(S,N-Cys){sub 2}]{sup 2-} chelate to form. The effect of temperature on the distribution of the Hg{sup 2+}-glutathione complexes was studied by comparing the EXAFS spectra at ambient temperature and at 25 K of a series of glycerol/water (33/67, v/v) frozen glasses with and C{sub Hg{sup 2+}} {approx} 7 mmol dm{sup -3} and C{sub GSH} = 16-81 mmol dm{sup -3}. Complexes with high Hg-S coordination numbers, [Hg(GS){sub 3}]{sup 7-} and [Hg(GS){sub 4}]{sup 10-}, became strongly favored when just a moderate excess of glutathione (C{sub GSH} {ge} 28 mmol dm{sup -3}) was used in the glassy samples, as expected for a stepwise exothermic bond formation. Addition of glycerol had no effect on the Hg

  12. Experimental study of the relationship between formation factor, porosity, and cementation

    SciTech Connect

    Harig, M.D.; Chaney, R.C.

    1999-07-01

    Cemented granular soils are classified based on the size and distribution of the individual grains and qualitatively on the basis of cementation. To uniquely classify these types of soils, information about the fabric (pore geometry and/or level of cementation) of the specimen needs to be quantified. Electrical resistivity, or its reciprocal, conductivity, methods have been extensively used both in situ and in the laboratory to provide a means for determining a variety of soil index, structural, erosional, and cyclic properties. The objective of this study was to determine the relationship between formation factor (F), porosity (n), and cementation factor (m) of remolded sand-cement specimens. This relationship is shown to provide a mechanism for estimating the level of cementation in undisturbed specimens. The formation factor is the ratio of the electrical resistivity of the sand-water-cement mixture to that of the interstitial water.

  13. Iron(II) Complexes with Scorpiand-Like Macrocyclic Polyamines: Kinetico-Mechanistic Aspects of Complex Formation and Oxidative Dehydrogenation of Coordinated Amines.

    PubMed

    Clares, M Paz; Acosta-Rueda, Laura; Castillo, Carmen E; Blasco, Salvador; Jiménez, Hermas R; García-España, Enrique; Basallote, Manuel G

    2017-03-24

    The Fe(II) coordination chemistry of a pyridinophane tren-derived scorpiand type ligand containing a pyridine ring in the pendant arm is explored by potentiometry, X-ray, NMR, and kinetics methods. Equilibrium studies in water show the formation of a stable [FeL](2+) complex that converts to monoprotonated and monohydroxylated species when the pH is changed. A [Fe(H-2L)](2+) complex containing an hexacoordinated dehydrogenated ligand has been isolated, and its crystal structure shows the formation of an imine bond involving the aliphatic nitrogen of the pendant arm. This complex is low spin Fe(II) both in the solid state and in solution, as revealed by the Fe-N bond lengths and by the NMR spectra, respectively. The formation rate of [Fe(H-2L)](2+) in aqueous solutions containing Fe(2+) and L (1:1 molar ratio) is strongly dependent on the pH, the process being completed in times that range from months in acid solutions to hours in basic conditions. However, detailed kinetic studies show that those differences are caused, at least in part, by the effect of pH on the rate of formation of the unoxidized [FeL](2+) complex. In this sense, the protonation of the donor atoms in the pendant arm of the scorpiand ligand leads to the formation of protonated species resistant to oxidative dehydrogenation. Complementary studies in acetonitrile solution indicate that the initial stage in the oxidative dehydrogenation process is the oxidation of the starting complex to form a [FeL](3+) complex, which then undergoes disproportionation into [Fe(H-2L)](2+) and [FeL](2+). Experiments starting with Fe(III) have allowed us to determine that disproportionation occurs with first order kinetics both in water and acetonitrile solutions. However, whereas a significant acceleration is observed in water when the pH is increased, no effect of the addition of acid or base on the rate of disproportionation is observed in acetonitrile. Oxidative dehydrogenation of the Fe(II) complex formed in

  14. Genome-wide analysis of transcription factors involved in maize embryonic callus formation.

    PubMed

    Ge, Fei; Luo, Xu; Huang, Xing; Zhang, Yanling; He, Xiujing; Liu, Min; Lin, Haijian; Peng, Huanwei; Li, Lujiang; Zhang, Zhiming; Pan, Guangtang; Shen, Yaou

    2016-12-01

    In this study, a maize inbred line with a strong capacity to induce embryonic callus, 18-599R, was used to analyze the transcription factors expressed during embryonic callus formation. A total of 1180 transcription factors were found to be expressed during three key stages of callus induction. Of these, compared with control, 361, 346 and 328 transcription factors were significantly downregulated during stages I, II and III, respectively. In contrast, 355, 372 and 401 transcription factors (TFs) were upregulated during the respective stages. We constructed a transcription factor-mediated regulatory network and found that plant hormone signal transduction was the pathway most significantly enriched among TFs. This pathway includes 48 TFs regulating cell enlargement, cell differentiation, cell division and cell dedifferentiation via the response to plant hormones. Through real-time polymerase chain reaction (PCR) and degradome sequencing, we identified 23 transcription factors that are regulated by miRNA. Through further analysis, ZmMYB138, a member of the MYB transcription factor family localized in the nucleus, was verified to promote embryonic callus formation in the maize embryo through GA signal transduction.

  15. An In Vitro Cord Formation Assay Identifies Unique Vascular Phenotypes Associated with Angiogenic Growth Factors

    PubMed Central

    Swearingen, Michelle; Gough, Wendy H.; Lee, Linda; Foreman, Robert; Uhlik, Mark; Hanson, Jeff C.; Lee, Jonathan A.; McClure, Don B.

    2014-01-01

    Vascular endothelial growth factor (VEGF) plays a dominant role in angiogenesis. While inhibitors of the VEGF pathway are approved for the treatment of a number of tumor types, the effectiveness is limited and evasive resistance is common. One mechanism of evasive resistance to inhibition of the VEGF pathway is upregulation of other pro-angiogenic factors such as fibroblast growth factor (FGF) and epidermal growth factor (EGF). Numerous in vitro assays examine angiogenesis, but many of these assays are performed in media or matrix with multiple growth factors or are driven by VEGF. In order to study angiogenesis driven by other growth factors, we developed a basal medium to use on a co-culture cord formation system of adipose derived stem cells (ADSCs) and endothelial colony forming cells (ECFCs). We found that cord formation driven by different angiogenic factors led to unique phenotypes that could be differentiated and combination studies indicate dominant phenotypes elicited by some growth factors. VEGF-driven cords were highly covered by smooth muscle actin, and bFGF-driven cords had thicker nodes, while EGF-driven cords were highly branched. Multiparametric analysis indicated that when combined EGF has a dominant phenotype. In addition, because this assay system is run in minimal medium, potential proangiogenic molecules can be screened. Using this assay we identified an inhibitor that promoted cord formation, which was translated into in vivo tumor models. Together this study illustrates the unique roles of multiple anti-angiogenic agents, which may lead to improvements in therapeutic angiogenesis efforts and better rational for anti-angiogenic therapy. PMID:25210890

  16. An in vitro cord formation assay identifies unique vascular phenotypes associated with angiogenic growth factors.

    PubMed

    Falcon, Beverly L; Swearingen, Michelle; Gough, Wendy H; Lee, Linda; Foreman, Robert; Uhlik, Mark; Hanson, Jeff C; Lee, Jonathan A; McClure, Don B; Chintharlapalli, Sudhakar

    2014-01-01

    Vascular endothelial growth factor (VEGF) plays a dominant role in angiogenesis. While inhibitors of the VEGF pathway are approved for the treatment of a number of tumor types, the effectiveness is limited and evasive resistance is common. One mechanism of evasive resistance to inhibition of the VEGF pathway is upregulation of other pro-angiogenic factors such as fibroblast growth factor (FGF) and epidermal growth factor (EGF). Numerous in vitro assays examine angiogenesis, but many of these assays are performed in media or matrix with multiple growth factors or are driven by VEGF. In order to study angiogenesis driven by other growth factors, we developed a basal medium to use on a co-culture cord formation system of adipose derived stem cells (ADSCs) and endothelial colony forming cells (ECFCs). We found that cord formation driven by different angiogenic factors led to unique phenotypes that could be differentiated and combination studies indicate dominant phenotypes elicited by some growth factors. VEGF-driven cords were highly covered by smooth muscle actin, and bFGF-driven cords had thicker nodes, while EGF-driven cords were highly branched. Multiparametric analysis indicated that when combined EGF has a dominant phenotype. In addition, because this assay system is run in minimal medium, potential proangiogenic molecules can be screened. Using this assay we identified an inhibitor that promoted cord formation, which was translated into in vivo tumor models. Together this study illustrates the unique roles of multiple anti-angiogenic agents, which may lead to improvements in therapeutic angiogenesis efforts and better rational for anti-angiogenic therapy.

  17. Fibroblast growth factor 10 markedly improves in vitro maturation of porcine cumulus-oocyte complexes.

    PubMed

    Son, Yeo-Jin; Lee, Seung-Eun; Hyun, Hyuk; Shin, Min-Young; Park, Yun-Gwi; Jeong, Sang-Gi; Kim, Eun-Young; Park, Se-Pill

    2017-01-01

    Growth factors synthesized by ovarian somatic cells affect cumulus cell expansion and oocyte maturation in vitro. Fibroblast growth factor 10 (FGF10), for example, is a known regulator of mammalian cumulus-oocyte complex maturation. In this study, we investigated the effects of 0, 5, 10, 50, and 100 ng/mL FGF10 (5F, 10F, 50F, and 100F, respectively) on in vitro cumulus cell expansion, oocyte maturation, and embryo development. The percentage of fully expanded cumulus cells at the oocyte's metaphase-II (MII) stage was significantly higher in the 10F-treated group than in the control. Transcript abundance of the cumulus cell expansion-related gene encoding hyaluronian synthase 2 (HAS2) in cumulus cells at oocyte germinal vesicle breakdown (GVBD) was significantly higher in the 10F- and 50F-treated groups compared to untreated controls, whereas the mRNA abundance of the protease cathepsin B (CTSB) at the oocyte MII stage was remarkably decreased in the 10F-treated group. The percentage of oocytes with normal spindles was greater in the 10F- and 50F-treated group at GVBD than in the other groups; the 5F-, 10F-, and 100F-treated groups were higher than the control; and the 50F-treated group was highest at MII. The abundance of GDF9 and BMP15 transcript at GVBD and BMP15 and CCNB1 transcripts at MII increased in the 10F-treated group. Cleavage rate, blastocyst formation rate, and total cell number were significantly higher in the 5F- to 50F-treated groups. These results demonstrate that FGF10 markedly improves cumulus cell expansion, oocyte maturation, and subsequent embryo development. Mol. Reprod. Dev. 84: 67-75, 2017. © 2016 Wiley Periodicals, Inc.

  18. Granodiorite Pluton Formation at the Mid-Cenozoic Never Summer Igneous Complex, North-Central Colorado

    NASA Astrophysics Data System (ADS)

    Jacob, K. H.; Farmer, G.

    2012-12-01

    Field observations, major- and trace-element geochemistry, and Sr and Nd isotopic data were used to assess the petrogenesis of epizonal intrusive rocks and related volcanic rocks from the ~28 Ma Never Summer igneous complex in north-central Colorado. Intrusive igneous rocks at this igneous center consist of an older granodiorite pluton (the Mt Richthofen stock, MRS) that is intruded by the granitic Mt. Cumulus stock. The latter has a uniform bulk composition equivalent to that of high silica rhyolite (~77 wt % SiO2, ɛNd(T) ~ -6). Whole rock studies of the MRS reveal that it is compositionally zoned (55-67 wt % SiO2,ɛNd(T) -0.5 to -5.7, 87Sr/86Sr(T) 0.7049 to 0.7119), with the lowest wt % SiO2 and highest ɛNd(T) occurring along the western margin of the pluton. Field observations, combined with the observed compositional variations, suggest that the pluton was originally a shallowly intruded (< 2 km), ~1 km thick sill that was vertically zoned from a mafic base to more felsic roof. The entire pluton has been tilted ~25 degrees to the west after emplacement. Given the lack of obvious wall-rock assimilation at the level of pluton emplacement, the isotopic variations in the pluton most likely reflect differences in the isotopic compositions of melts from which the pluton was assembled. Obvious field evidence exists for underplating of the developing pluton by mafic, high ɛNd (T) (>-2) melts and illustrates that mafic magmas were present in the uppermost crust and likely participated in pluton formation. The higher wt % SiO2 and lower ɛNd(T) portions of the MRS, however, could not have been derived directly from the mafic magmas in any closed system process. One option is that the MRS ultimately represents the product of mixing of >70 wt % SiO2 melts (+ crystals), analogous to the melts from which the Mt. Cumulus stock crystallized, and underplating mafic magma. This model implies that two primary magmas types, high silica rhyolite and basalt/basaltic andesite

  19. Classification Accuracy of Mixed Format Tests: A Bi-Factor Item Response Theory Approach

    PubMed Central

    Wang, Wei; Drasgow, Fritz; Liu, Liwen

    2016-01-01

    Mixed format tests (e.g., a test consisting of multiple-choice [MC] items and constructed response [CR] items) have become increasingly popular. However, the latent structure of item pools consisting of the two formats is still equivocal. Moreover, the implications of this latent structure are unclear: For example, do constructed response items tap reasoning skills that cannot be assessed with multiple choice items? This study explored the dimensionality of mixed format tests by applying bi-factor models to 10 tests of various subjects from the College Board's Advanced Placement (AP) Program and compared the accuracy of scores based on the bi-factor analysis with scores derived from a unidimensional analysis. More importantly, this study focused on a practical and important question—classification accuracy of the overall grade on a mixed format test. Our findings revealed that the degree of multidimensionality resulting from the mixed item format varied from subject to subject, depending on the disattenuated correlation between scores from MC and CR subtests. Moreover, remarkably small decrements in classification accuracy were found for the unidimensional analysis when the disattenuated correlations exceeded 0.90. PMID:26973568

  20. Pectoralis major myocutaneous flap for head and neck reconstruction: risk factors for fistula formation.

    PubMed

    Leite, A K N; de Matos, L L; Belli, M; Kulcsar, M A V; Cernea, C R; Garcia Brandão, L; Pinto, F R

    2014-12-01

    The pectoralis major myocutaneous flap (PMMF) is a safe and versatile flap used widely for head and neck cancer reconstructions, but one of the major and most feared complications is oro- or pharyngocutaneous fistula. Herein, we attempt to establish risk factors for fistula formation in reconstructions of mucosal defects in the head and neck using PMMF through retrospective analysis of PMMF performed during 3 years at a single institution, with a total of 84 procedures. There were 69 men and 15 women, with a mean age of 59.5 years. There were 15 cases of partial flap loss, two total flap losses and 31 fistulas. The independent risk factors for fistula formation were preoperative serum hemoglobin < 13 g/dl, preoperative serum albumin < 3.4 g/dl and hypopharynx reconstruction. The PMMF is still a very useful flap and this is the first multivariate analysis analysing risk factors for fistula formation. These findings are helpful in selecting patients with elevated risk of fistula formation, and therefore preventive measures can be undertaken to avoid potentially serious complications.

  1. Polyprotein-Driven Formation of Two Interdependent Sets of Complexes Supporting Hepatitis C Virus Genome Replication

    PubMed Central

    Gomes, Rafael G. B.; Isken, Olaf; Tautz, Norbert; McLauchlan, John

    2015-01-01

    ABSTRACT Hepatitis C virus (HCV) requires proteins from the NS3-NS5B polyprotein to create a replicase unit for replication of its genome. The replicase proteins form membranous compartments in cells to facilitate replication, but little is known about their functional organization within these structures. We recently reported on intragenomic replicons, bicistronic viral transcripts expressing an authentic replicase from open reading frame 2 (ORF2) and a second duplicate nonstructural (NS) polyprotein from ORF1. Using these constructs and other methods, we have assessed the polyprotein requirements for rescue of different lethal point mutations across NS3-5B. Mutations readily tractable to rescue broadly fell into two groupings: those requiring expression of a minimum NS3-5A and those requiring expression of a minimum NS3-5B polyprotein. A cis-acting mutation that blocked NS3 helicase activity, T1299A, was tolerated when introduced into either ORF within the intragenomic replicon, but unlike many other mutations required the other ORF to express a functional NS3-5B. Three mutations were identified as more refractile to rescue: one that blocked cleavage of the NS4B5A boundary (S1977P), another in the NS3 helicase (K1240N), and a third in NS4A (V1665G). Introduced into ORF1, these exhibited a dominant negative phenotype, but with K1240N inhibiting replication as a minimum NS3-5A polyprotein whereas V1665G and S1977P only impaired replication as a NS3-5B polyprotein. Furthermore, an S1977P-mutated NS3-5A polyprotein complemented other defects shown to be dependent on NS3-5A for rescue. Overall, our findings suggest the existence of two interdependent sets of protein complexes supporting RNA replication, distinguishable by the minimum polyprotein requirement needed for their formation. IMPORTANCE Positive-strand RNA viruses reshape the intracellular membranes of cells to form a compartment within which to replicate their genome, but little is known about the functional

  2. Pore-controlled formation of 0D metal complexes in anionic 3D metal-organic frameworks

    SciTech Connect

    Zhang, MW; Bosch, M; Zhou, HC

    2015-01-01

    The host-guest chemistry between a series of anionic MOFs and their trapped counterions was investigated by single crystal XRD. The PCN-514 series contains crystallographically identifiable metal complexes trapped in the pores, where their formation is controlled by the size and shape of the MOF pores. A change in the structure and pore size of PCN-518 indicates that the existence of guest molecules may reciprocally affect the formation of host MOFs.

  3. Protostellar Interferometric Line Survey (PILS): Constraining the formation of complex organic molecules with ALMA

    NASA Astrophysics Data System (ADS)

    Jorgensen, Jes K.; Coutens, Audrey; Bourke, Tyler L.; Favre, Cecile; Garrod, Robin; Lykke, Julie; Mueller, Holger; Oberg, Karin I.; Schmalzl, Markus; van der Wiel, Matthijs; van Dishoeck, Ewine; Wampfler, Susanne F.

    2015-08-01

    Understanding how, when and where complex organic and potentially prebiotic molecules are formed is a fundamental goal of astrochemistry and an integral part of origins of life studies. Already now ALMA is showing its capabilities for studies of the chemistry of solar-type stars with its high sensitivity for faint lines, high spectral resolution which limits line confusion, and high angular resolution making it possible to study the structure of young protostars on solar-system scales. We here present the first results from a large unbiased survey “Protostellar Interferometric Line Survey (PILS)” targeting one of the astrochemical template sources, the low-mass protostellar binary IRAS 16293-2422. The survey is more than an order of magnitude more sensitive than previous surveys of the source and provide imaging down to 25 AU scales (radius) around each of the two components of the binary. An example of one of the early highlights from the survey is unambiguous detections of the (related) prebiotic species glycolaldehyde, ethylene glycol (two lowest energy conformers), methyl formate and acetic acid. The glycolaldehyde-ethylene glycol abundance ratio is high in comparison to comets and other protostars - but agrees with previous measurements, e.g., in the Galactic Centre clouds possibly reflecting different environments and/or evolutionary histories. Complete mapping of this and other chemical networks in comparison with detailed chemical models and laboratory experiments will reveal the origin of complex organic molecules in a young protostellar system and investigate the link between these protostellar stages and the early Solar System.

  4. STAR FORMATION AND YOUNG POPULATION OF THE H II COMPLEX Sh2-294

    SciTech Connect

    Samal, M. R.; Pandey, A. K.; Chauhan, N.; Jose, J.; Ojha, D. K.; Pandey, B.

    2012-08-10

    The Sh2-294 H II region ionized by a single B0V star features several infrared excess sources, a photodissociation region, and also a group of reddened stars at its border. The star formation scenario in this region seems to be quite complex. In this paper, we present follow-up results of Sh2-294 H II region at 3.6, 4.5, 5.8, and 8.0 {mu}m observed with the Spitzer Space Telescope Infrared Array Camera (IRAC), coupled with H{sub 2} (2.12 {mu}m) observation, to characterize the young population of the region and to understand its star formation history. We identified 36 young stellar object (YSO, Class I, Class II, and Class I/II) candidates using IRAC color-color diagrams. It is found that Class I sources are preferentially located at the outskirts of the H II region and associated with enhanced H{sub 2} emission; none of them are located near the central cluster. Combining the optical to mid-infrared (MIR) photometry of the YSO candidates and using the spectral energy distribution fitting models, we constrained stellar parameters and the evolutionary status of 33 YSO candidates. Most of them are interpreted by the model as low-mass (<4 M{sub Sun }) YSOs; however, we also detected a massive YSO ({approx}9 M{sub Sun }) of Class I nature, embedded in a cloud of visual extinction of {approx}24 mag. Present analysis suggests that the Class I sources are indeed a younger population of the region relative to Class II sources (age {approx} 4.5 Multiplication-Sign 10{sup 6} yr). We suggest that the majority of the Class I sources, including the massive YSOs, are second-generation stars of the region whose formation is possibly induced by the expansion of the H II region powered by a {approx}4 Multiplication-Sign 10{sup 6} yr B0 main-sequence star.

  5. Formation of Complex Organic molecules from Formaldehyde Chemistry in Cometary Ice Analogues

    NASA Astrophysics Data System (ADS)

    Duvernay, fabrice; Vinogradoff, Vassilissa; Danger, Grégoire; Theulé, Patrice; Chiavassa, Thierry

    2015-04-01

    There is convincing evidence that the formation of complex organic molecules occurred in a variety of astrophysical environments. Among them, precursors of biomolecules are of particular significance due to their exobiological implications. Hexamethylenetetramine (HMT, C6H12N4) and the polyoxymethylene (POM, -(CH2-O)n-) are of prime interest since they are supposed to be present in cometary environments. They are also ones of the main components of the organic residue formed from the warming of photolysed interstellar/cometary ice analogs. In this work, we study the warming of water-dominated cometary ice analogs containing formaldehyde (H2CO). Based on infrared and mass spectrometry measurements, and complemented by quantum chemical calculations, we report that NH2CH2OH, HOCH2OH, and POM are the only reaction products when the ice also contains NH3. The branching ratio between the three products strongly depends on the initial H2CO/NH3 concentration ratio. Moreover, the influence of the initial ice composition on the formation of POM oligomers (HO-(CH2O)n-H, n<5) as well as their thermal instability between 200 and 320 K are investigated. Finally, the implications of these results with respect to cometary nucleus chemistry and their impact on POM detection by the Rosetta mission are discussed. In addition, the mechanism for HMT formation in interstellar or cometary ice analogs containing H2CO, NH3, and HCOOH has been determined by combining laboratory experiments and DFT calculations. We show that HMT is thermally formed from H2CO and NH3 activated by HCOOH. Two intermediates has been unambiguously detected: NH2CH2OH and the trimer of CH2NH (1,3,5-triazinane, TMT). Unlike to what it was previously thought, HMT is not an indicator of ice photochemistry, but an indicator of thermal processing of ice. These results strengthen the hypothesis that HMT and its intermediates should be present in comets, where they may be detected with the COSAC or COSIMA instrument of

  6. Factors influencing benzene formation from the decarboxylation of benzoate in liquid model systems.

    PubMed

    Medeiros Vinci, Raquel; De Meulenaer, Bruno; Andjelkovic, Mirjana; Canfyn, Michael; Van Overmeire, Ilse; Van Loco, Joris

    2011-12-28

    Benzene may occur in foods due to the oxidative decarboxylation of benzoate in the presence of hydroxyl radicals. This study investigated factors influencing benzene formation in liquid model systems. The type of buffer, other sources of hydroxyl radical formation in food (photo oxidation of riboflavin and lipid oxidation), transition metal ion concentrations, and the inhibitory effect of antioxidants were tested in benzoate containing model systems. Regarding the hydroxyl radical sources tested, the highest benzene formation was observed in light exposed model systems containing ascorbic acid, Cu(2+), and riboflavin in Na-citrate buffer (1250 ± 131 μg kg(-1)). In practice, it seems that the combination ascorbic acid/transition metal ion remains the biggest contributor to benzene formation in food. However, the concentration of Cu(2+) influences significantly benzene formation in such a system with highest benzene yields observed for Cu(2+) 50 μM (1400 μg kg(-1)). The presence of antioxidants with metal chelation or reduction properties could prevent completely benzene formation.

  7. Neonatal NET-inhibitory factor and related peptides inhibit neutrophil extracellular trap formation

    PubMed Central

    Yost, Christian C.; Schwertz, Hansjörg; Cody, Mark J.; Wallace, Jared A.; Campbell, Robert A.; Vieira-de-Abreu, Adriana; Araujo, Claudia V.; Schubert, Sebastian; Harris, Estelle S.; Rowley, Jesse W.; Rondina, Matthew T.; Koening, Curry L.; Weyrich, Andrew S.; Zimmerman, Guy A.

    2016-01-01

    Neutrophil granulocytes, also called polymorphonuclear leukocytes (PMNs), extrude molecular lattices of decondensed chromatin studded with histones, granule enzymes, and antimicrobial peptides that are referred to as neutrophil extracellular traps (NETs). NETs capture and contain bacteria, viruses, and other pathogens. Nevertheless, experimental evidence indicates that NETs also cause inflammatory vascular and tissue damage, suggesting that identifying pathways that inhibit NET formation may have therapeutic implications. Here, we determined that neonatal NET-inhibitory factor (nNIF) is an inhibitor of NET formation in umbilical cord blood. In human neonatal and adult neutrophils, nNIF inhibits key terminal events in NET formation, including peptidyl arginine deiminase 4 (PAD4) activity, neutrophil nuclear histone citrullination, and nuclear decondensation. We also identified additional nNIF-related peptides (NRPs) that inhibit NET formation. nNIFs and NRPs blocked NET formation induced by pathogens, microbial toxins, and pharmacologic agonists in vitro and in mouse models of infection and systemic inflammation, and they improved mortality in murine models of systemic inflammation, which are associated with NET-induced collateral tissue injury. The identification of NRPs as neutrophil modulators that selectively interrupt NET generation at critical steps suggests their potential as therapeutic agents. Furthermore, our results indicate that nNIF may be an important regulator of NET formation in fetal and neonatal inflammation. PMID:27599294

  8. Neonatal NET-inhibitory factor and related peptides inhibit neutrophil extracellular trap formation.

    PubMed

    Yost, Christian C; Schwertz, Hansjörg; Cody, Mark J; Wallace, Jared A; Campbell, Robert A; Vieira-de-Abreu, Adriana; Araujo, Claudia V; Schubert, Sebastian; Harris, Estelle S; Rowley, Jesse W; Rondina, Matthew T; Fulcher, James M; Koening, Curry L; Weyrich, Andrew S; Zimmerman, Guy A

    2016-10-03

    Neutrophil granulocytes, also called polymorphonuclear leukocytes (PMNs), extrude molecular lattices of decondensed chromatin studded with histones, granule enzymes, and antimicrobial peptides that are referred to as neutrophil extracellular traps (NETs). NETs capture and contain bacteria, viruses, and other pathogens. Nevertheless, experimental evidence indicates that NETs also cause inflammatory vascular and tissue damage, suggesting that identifying pathways that inhibit NET formation may have therapeutic implications. Here, we determined that neonatal NET-inhibitory factor (nNIF) is an inhibitor of NET formation in umbilical cord blood. In human neonatal and adult neutrophils, nNIF inhibits key terminal events in NET formation, including peptidyl arginine deiminase 4 (PAD4) activity, neutrophil nuclear histone citrullination, and nuclear decondensation. We also identified additional nNIF-related peptides (NRPs) that inhibit NET formation. nNIFs and NRPs blocked NET formation induced by pathogens, microbial toxins, and pharmacologic agonists in vitro and in mouse models of infection and systemic inflammation, and they improved mortality in murine models of systemic inflammation, which are associated with NET-induced collateral tissue injury. The identification of NRPs as neutrophil modulators that selectively interrupt NET generation at critical steps suggests their potential as therapeutic agents. Furthermore, our results indicate that nNIF may be an important regulator of NET formation in fetal and neonatal inflammation.

  9. Ab-initio calculation study on the formation mechanism of boron-oxygen complexes in c-Si

    SciTech Connect

    Yu, Xuegong; Chen, Peng; Chen, Xianzi; Liu, Yong; Yang, Deren

    2015-07-15

    Boron-oxygen (B-O) complex in crystalline silicon (c-Si) solar cells is responsible for the light-induced efficiency degradation of solar cell. However, the formation mechanism of B-O complex is not clear yet. By Ab-initio calculation, it is found that the stagger-type oxygen dimer (O{sub 2i}{sup st}) should be the component of B-O complex, whose movement occurs through its structure reconfiguration at low temperature, instead of its long-distance diffusion. The O{sub 2i}{sup st} can form two stable “latent centers” with the B{sub s}, which are recombination-inactive. The latent centers can be evolved into the metastable recombination centers via their structure transformation in the presence of excess carriers. These results can well explain the formation behaviors of B-O complexes in c-Si.

  10. Age range of formation of sedimentary-volcanogenic complex of the Vetreny Belt (the southeast of the Baltic Shield)

    NASA Astrophysics Data System (ADS)

    Mezhelovskaya, S. V.; Korsakov, A. K.; Mezhelovskii, A. D.; Bibikova, E. V.

    2016-03-01

    As a result of studying the Vetreny Belt greenstone structure (the southeast of the Baltic Shield), zircons from terrigenous deposits of the Toksha Formation, underlying the section of the sedimentary-volcanogenic complex, and zircons of the Vetreny Belt Formation, deposits of which crown the section, were dated. The results of analysis of age data of detrital zircons from quartzites of the Toksha Formation indicate that Mesoarchean greenstone complexes and paleo-Archean granitogneisses of the Vodlozero Block (Karelia) were the provenance area from which these zircons were derived. The occurrence of the youngest zircons with age of 2654.3 ± 38.5 Ma is evidence that the formation of the Vetreny Belt, including the Toksha Formation, began no earlier than this time. Zircons from volcanic rocks of the Vetreny Belt yielded the age of 2405 ± 5 Ma. Thus, the age interval of the formation of the sedimentary-volcanogenic complex of the Vetreny Belt ranges from 2654.3 ± 38.5 to 2405 ± 5 Ma.

  11. Forkhead transcription factor FoxF1 interacts with Fanconi anemia protein complexes to promote DNA damage response.

    PubMed

    Pradhan, Arun; Ustiyan, Vladimir; Zhang, Yufang; Kalin, Tanya V; Kalinichenko, Vladimir V

    2016-01-12

    Forkhead box F1 (Foxf1) transcription factor is an important regulator of embryonic development but its role in tumor cells remains incompletely understood. While 16 proteins were characterized in Fanconi anemia (FA) core complex, its interactions with cellular transcriptional machinery remain poorly characterized. Here, we identified FoxF1 protein as a novel interacting partner of the FA complex proteins. Using multiple human and mouse tumor cell lines and Foxf1+/- mice we demonstrated that FoxF1 physically binds to and increases stability of FA proteins. FoxF1 co-localizes with FANCD2 in DNA repair foci in cultured cells and tumor tissues obtained from cisplatin-treated mice. In response to DNA damage, FoxF1-deficient tumor cells showed significantly reduced FANCD2 monoubiquitination and FANCM phosphorylation, resulting in impaired formation of DNA repair foci. FoxF1 knockdown caused chromosomal instability, nuclear abnormalities, and increased tumor cell death in response to DNA-damaging agents. Overexpression of FoxF1 in DNA-damaged cells improved stability of FA proteins, decreased chromosomal and nuclear aberrations, restored formation of DNA repair foci and prevented cell death after DNA damage. These findings demonstrate that FoxF1 is a key component of FA complexes and a critical mediator of DNA damage response in tumor cells.

  12. Forkhead transcription factor FoxF1 interacts with Fanconi anemia protein complexes to promote DNA damage response

    PubMed Central

    Pradhan, Arun; Ustiyan, Vladimir; Zhang, Yufang; Kalin, Tanya V.; Kalinichenko, Vladimir V.

    2016-01-01

    Forkhead box F1 (Foxf1) transcription factor is an important regulator of embryonic development but its role in tumor cells remains incompletely understood. While 16 proteins were characterized in Fanconi anemia (FA) core complex, its interactions with cellular transcriptional machinery remain poorly characterized. Here, we identified FoxF1 protein as a novel interacting partner of the FA complex proteins. Using multiple human and mouse tumor cell lines and Foxf1+/− mice we demonstrated that FoxF1 physically binds to and increases stability of FA proteins. FoxF1 co-localizes with FANCD2 in DNA repair foci in cultured cells and tumor tissues obtained from cisplatin-treated mice. In response to DNA damage, FoxF1-deficient tumor cells showed significantly reduced FANCD2 monoubiquitination and FANCM phosphorylation, resulting in impaired formation of DNA repair foci. FoxF1 knockdown caused chromosomal instability, nuclear abnormalities, and increased tumor cell death in response to DNA-damaging agents. Overexpression of FoxF1 in DNA-damaged cells improved stability of FA proteins, decreased chromosomal and nuclear aberrations, restored formation of DNA repair foci and prevented cell death after DNA damage. These findings demonstrate that FoxF1 is a key component of FA complexes and a critical mediator of DNA damage response in tumor cells. PMID:26625197

  13. Formation, dynamic behavior, and chemical transformation of Pt complexes with a rotaxane-like structure.

    PubMed

    Suzaki, Yuji; Osakada, Kohtaro

    2006-09-18

    The reaction of [Pt(CH2COMe)(Ph)(cod)] (cod = 1,5-cyclooctadiene) with (ArCH2NH2CH2-C6H4COOH)+ (PF6)- (Ar = 4-tBuC6H4 or 9-anthryl) in the presence of cyclic oligoethers such as dibenzo[24]crown-8 (DB24C8) and dicyclohexano[24]crown-8 (DC24C8) produces {(ce)[ArCH2NH2CH2C6H4COOPt(Ph)(cod)]}+ (PF6)- (ce = DB24C8 or DC24C8, Ar = 4-tBuC6H4 or 9-anthryl) with interlocked structures. FABMS and NMR spectra of a solution of these compounds indicate that the Pt complexes with a secondary ammonium group and DB24C8 (or DC24C8) make up the axis and cyclic components, respectively. Temperature-dependent 1H NMR spectra of a solution of {(DB24C8)[4-tBuC6H4CH2NH2CH2-C6H4COOPt(Ph)(cod)]}+ (PF6)- ({(DB24C8)[4-H]}+ (PF6)-) show equilibration with free DB24C8 and the axis component. The addition of DB24C8 to a solution of {(DC24C8)[4-H]}+ (PF6)- causes partial exchange of the macrocyclic component of the interlocked molecules, giving a mixture of {(DC24C8)[4-H]}+ (PF6)-, {(DB24C8)[4-H]}+ (PF6)-, and free macrocyclic compounds. The reaction of 3,5-Me2C6H3COCl with {(DB24C8)[4-H]}+ (PF6)- affords the organic rotaxane {(DB24C8)(4-tBuC6H4CH2NH2CH2-C6H4COOCOC6H3Me2-3,5)}+ (PF6)- through C-O bond formation between the aroyl group and the carboxylate ligand of the axis component. The addition of 2,2'-bipyridine (bpy) to a solution of {(DB24C8)[4-H]}+ (PF6)- induces the degradation of the interlocked structure to form a complex with trigonal bipyramidal coordination, [Pt(Ph)(bpy)(cod)]+ (PF6)-, whereas the reaction of bpy with [Pt(OCOC6H4Me-4)(Ph)(cod)] produces the square-planar complex [Pt(OCOC6H4Me-4)(Ph)(bpy)].

  14. Apatite formation behaviour during metasomatism in the Bathtub Intrusion (Babbitt deposit, Duluth Complex, USA)

    NASA Astrophysics Data System (ADS)

    Raič, Sara; Mogessie, Aberra; Krenn, Kurt; Hauzenberger, Christoph A.; Tropper, Peter

    2016-04-01

    The mineralized troctolitic Bathtub intrusion (Duluth Complex, NE-Minnesota) is known for its famous Cu-Ni-Sulfide±PGM Babbitt deposit, where platinum group minerals (PGMs) are either hosted by primary magmatic sulfides (base metal sulfides) or associated with hydrothermally altered portions. This secondary generation of PGMs is present in alteration patches and suggests the involvement of hydrothermal fluids in the mobilization of platinum-group elements (PGEs). Accessory fluorapatite in these samples reveals besides H2O- and CO2-rich primary fluid inclusions, textural and compositional variations that also record magmatic and metasomatic events. Based on detailed back-scattered electron imaging (BSE) and laser ablation-inductively coupled plasma-mass spectrometry (LA-ICPMS), a primary magmatic origin is reflected by homogeneous or zoned grains, where zoning patterns are either concentric or oscillatory, with respect to LREE. Late magmatic to hydrothermal processes are indicated by grains with bright LREE-enriched rims or conversion textures with REE-enriched patches in the interior of the apatite. A metasomatic formation of monazite from apatite is documented by the presence of monazite inclusions in apatite and newly grown monazite at altered apatite rims. They formed by the release of REEs from the apatite during a fluid-induced alteration, based on the coupled substitution Ca2+ + P5+ = REE3+ + Si4+ (Rønsbo 1989; Rønsbo 2008). Samples with monazite inclusions in apatite further display occurrences of PGMs associated with hydrothermal alteration patches (chlorite + amphibole). The presence of H2O- and CO2-rich fluid inclusions in apatite, the metasomatically induced monazite growth, as well as the occurrence of PGMs in hydrothermally alteration zones, also suggest the involvement of aqueous chloride complexes in a H2O dominated fluid in the transportation of LREE and redistribution of the second generation of PGEs. Rønsbo, J.G. (1989): Coupled substitutions

  15. An unusual cytokine:Ig-domain interaction revealed in the crystal structure of leukemia inhibitory factor (LIF) in complex with the LIF receptor

    PubMed Central

    Huyton, Trevor; Zhang, Jian-Guo; Luo, Cindy S.; Lou, Mei-Zhen; Hilton, Douglas J.; Nicola, Nicos A.; Garrett, Thomas P. J.

    2007-01-01

    Leukemia inhibitory factor (LIF) receptor is a cell surface receptor that mediates the actions of LIF and other IL-6 type cytokines through the formation of high-affinity signaling complexes with gp130. Here we present the crystal structure of a complex of mouse LIF receptor with human LIF at 4.0 Å resolution. The structure is, to date, the largest cytokine receptor fragment determined by x-ray crystallography. The binding of LIF to its receptor via the central Ig-like domain is unlike other cytokine receptor complexes that bind ligand predominantly through their cytokine-binding modules. This structure, in combination with previous crystallographic studies, also provides a structural template to understand the formation and orientation of the high-affinity signaling complex between LIF, LIF receptor, and gp130. PMID:17652170

  16. Cluster formation by allelomimesis in real-world complex adaptive systems

    NASA Astrophysics Data System (ADS)

    Juanico, Dranreb Earl; Monterola, Christopher; Saloma, Caesar

    2005-04-01

    Animal and human clusters are complex adaptive systems and many organize in cluster sizes s that obey the frequency distribution D(s)∝s-τ . The exponent τ describes the relative abundance of the cluster sizes in a given system. Data analyses reveal that real-world clusters exhibit a broad spectrum of τ values, 0.7 (tuna fish schools) ⩽τ⩽4.61 (T4 bacteriophage gene family sizes). Allelomimesis is proposed as an underlying mechanism for adaptation that explains the observed broad τ spectrum. Allelomimesis is the tendency of an individual to imitate the actions of others and two cluster systems have different τ values when their component agents display unequal degrees of allelomimetic tendencies. Cluster formation by allelomimesis is shown to be of three general types: namely, blind copying, information-use copying, and noncopying. Allelomimetic adaptation also reveals that the most stable cluster size is formed by three strongly allelomimetic individuals. Our finding is consistent with available field data taken from killer whales and marmots.

  17. Mouse Sycp1 functions in synaptonemal complex assembly, meiotic recombination, and XY body formation

    PubMed Central

    de Vries, Femke A.T.; de Boer, Esther; van den Bosch, Mike; Baarends, Willy M.; Ooms, Marja; Yuan, Li; Liu, Jian-Guo; van Zeeland, Albert A.; Heyting, Christa; Pastink, Albert

    2005-01-01

    In meiotic prophase, synaptonemal complexes (SCs) closely appose homologous chromosomes (homologs) along their length. SCs are assembled from two axial elements (AEs), one along each homolog, which are connected by numerous transverse filaments (TFs). We disrupted the mouse gene encoding TF protein Sycp1 to analyze the role of TFs in meiotic chromosome behavior and recombination. Sycp1-/- mice are infertile, but otherwise healthy. Sycp1-/- spermatocytes form normal AEs, which align homologously, but do not synapse. Most Sycp1-/- spermatocytes arrest in pachynema, whereas a small proportion reaches diplonema, or, exceptionally, metaphase I. In leptotene Sycp1-/- spermatocytes, γH2AX (indicative of DNA damage, including double-strand breaks) appears normal. In pachynema, Sycp1-/- spermatocytes display a number of discrete γH2AX domains along each chromosome, whereas γH2AX disappears from autosomes in wild-type spermatocytes. RAD51/DMC1, RPA, and MSH4 foci (which mark early and intermediate steps in pairing/recombination) appear in similar numbers as in wild type, but do not all disappear, and MLH1 and MLH3 foci (which mark late steps in crossing over) are not formed. Crossovers were rare in metaphase I of Sycp1-/- mice. We propose that SYCP1 has a coordinating role, and ensures formation of crossovers. Unexpectedly, Sycp1-/- spermatocytes did not form XY bodies. PMID:15937223

  18. Calculation of equilibrium binding constants and cooperativity of Cu(II) mixed solvated complexes formation.

    PubMed

    Kudrev, A G

    2012-11-15

    A new extension of matrix approach is proposed to calculate the equilibrium constants of coordinated solvent substitution in a metal ion first salvation shell in the mixed solvent system. The proposed method allows reducing the number of independent variables, necessary to calculate the fractions of species in solution. The equilibrium model of MeCN substitution with DMF and DMSO in the presence of Cu(II) ion for the assessment of structure of intermediate species is presented and verified. The distribution diagrams of Cu(II) species in mixed organic solvents have been analyzed using the modified matrix method. The intrinsic equilibrium constants K of the first solvent molecule replacement in the Cu(II) coordination shell and the correction for the mutual influence between the solvent molecules as ligands in the successive complex formation (cooperativity parameter w) in acetonitrile solution have been calculated from the fitting procedure. It is shown that anticooperative substitution of MeCN by donor ligands in the first coordination shell of the Cu(II) ion is always governed by the change of coordination number during the stepwise process.

  19. Formation and Identification of Unresolved Complex Mixtures in Lacustrine Biodegraded Oil from Nanxiang Basin, China

    PubMed Central

    Guo, Pengfei; He, Sheng; Zhu, Shukui; Chai, Derong; Yin, Shiyan; Dai, Wei; Zhang, Wanfeng

    2014-01-01

    A comprehensive two-dimensional gas chromatography/time-of-flight mass spectrometry (GC × GC/TOFMS) method has been developed for the formation and identification of unresolved complex mixtures (UCMs) in lacustrine biodegraded oils that with the same source rock, similar maturity, and increasing degradation rank from Nanxiang Basin, China. Normal alkanes, light hydrocarbons, isoprenoids, steranes, and terpanes are degraded gradually from oil B330 to oil G574. The compounds in biodegraded oil (oil G574) have fewer types, the polarity difference of compounds in different types is minor, and the relative content of individual compounds is similar. All the features make the compounds in biodegraded oil coelute in GC analysis and form the raised “baseline hump” named UCMs. By injecting standard materials and analyzing mass spectrums of target compounds, it is shown that cyclic alkanes with one to five rings are the major components of UCMs. Furthermore, UCMs were divided into six classes. Classes I and II, composed of alkyl-cyclohexanes, alkyl-naphthanes, and their isomers, are originated from the enrichment of hydrocarbons resistant to degradation in normal oils. Classes III ~ VI, composed of sesquiterpenoids, tricyclic terpanes, low molecular steranes, diasteranes, norhopanes, and their isomers, are probably from some newly formed compounds during the microbial transformation of oil. PMID:25177711

  20. Decamethylytterbocene complexes of bipyridines and diazabutadines: multiconfigurational ground states and open-shell singlet formation

    SciTech Connect

    Bauer, Eric D; Booth, C H; Walter, M D; Kazhdan, D; Hu, Y - J; Lukens, Wayne; Maron, Laurent; Eisentein, Odile; Anderson, Richard

    2009-01-01

    Partial ytterbium f-orbital occupancy (i.e. intermediate valence) and open-shell singlet Draft 12/formation are established for a variety of bipyridine and diazabutadiene adducts to decamethylytterbocene, (C{sub 5}Me{sub 5}){sub 2}Yb or Cp*{sub 2}Yb. Data used to support this claim includes ytterbium valence measurements using Yb Lm-edge x-ray absorption near-edge structure (XANES) spectroscopy, magnetic susceptibility and Complete Active Space Self-Consistent Field (CASSCF) multi configurational calculations, as well as structural measurements compared to density-functional theory (DFT) calculations. The CASSCF calculations indicate that the intermediate valence is the result of a multiconfigurational ground state wave function that has both an open-shell singlet f{sup 13} and a closed-shell singlet f{sup 14} component. A number of other competing theories for the unusual magnetism in these materials are ruled out by the presence of intermediate valence and its lack of any significant temperature dependence. These results have implications for understanding chemical bonding not only in organolanthanide complexes, but also for organometallic chemistry in general, as well as understanding magnetic interactions in nanopartic1es and devices.

  1. Accelerated fluctuation analysis by graphic cards and complex pattern formation in financial markets

    NASA Astrophysics Data System (ADS)

    Preis, Tobias; Virnau, Peter; Paul, Wolfgang; Schneider, Johannes J.

    2009-09-01

    The compute unified device architecture is an almost conventional programming approach for managing computations on a graphics processing unit (GPU) as a data-parallel computing device. With a maximum number of 240 cores in combination with a high memory bandwidth, a recent GPU offers resources for computational physics. We apply this technology to methods of fluctuation analysis, which includes determination of the scaling behavior of a stochastic process and the equilibrium autocorrelation function. Additionally, the recently introduced pattern formation conformity (Preis T et al 2008 Europhys. Lett. 82 68005), which quantifies pattern-based complex short-time correlations of a time series, is calculated on a GPU and analyzed in detail. Results are obtained up to 84 times faster than on a current central processing unit core. When we apply this method to high-frequency time series of the German BUND future, we find significant pattern-based correlations on short time scales. Furthermore, an anti-persistent behavior can be found on short time scales. Additionally, we compare the recent GPU generation, which provides a theoretical peak performance of up to roughly 1012 floating point operations per second with the previous one. .

  2. Efficient formation of bipolar microtubule bundles requires microtubule-bound γ-tubulin complexes

    PubMed Central

    Janson, Marcel E.; Setty, Thanuja Gangi; Paoletti, Anne; Tran, P.T.

    2005-01-01

    The mechanism for forming linear microtubule (MT) arrays in cells such as neurons, polarized epithelial cells, and myotubes is not well understood. A simpler bipolar linear array is the fission yeast interphase MT bundle, which in its basic form contains two MTs that are bundled at their minus ends. Here, we characterize mto2p as a novel fission yeast protein required for MT nucleation from noncentrosomal γ-tubulin complexes (γ-TuCs). In interphase mto2Δ cells, MT nucleation was strongly inhibited, and MT bundling occurred infrequently and only when two MTs met by chance in the cytoplasm. In wild-type 2, we observed MT nucleation from γ-TuCs bound along the length of existing MTs. We propose a model on how these nucleation events can more efficiently drive the formation of bipolar MT bundles in interphase. Key to the model is our observation of selective antiparallel binding of MTs, which can both explain the generation and spatial separation of multiple bipolar bundles. PMID:15837798

  3. Decamethylytterbocene Complexes of Bipyridines and Diazabutadienes: Multiconfigurational Ground States and Open-Shell Singlet Formation

    SciTech Connect

    Booth, Corwin H.; Walter, Marc D.; Kazhdan, Daniel; Hu, Yung-Jin; Lukens, Wayne W.; Bauer, Eric D.; Maron, Laurent; Eisenstein, Odile; Andersen, Richard A.

    2009-04-22

    Partial ytterbium f-orbital occupancy (i.e., intermediate valence) and open-shell singlet formation are established for a variety of bipyridine and diazabutadiene adducts with decamethylytterbocene, (C5Me5)2Yb, abbreviated as Cp*2Yb. Data used to support this claim include ytterbium valence measurements using Yb LIII-edge X-ray absorption near-edge structure spectroscopy, magnetic susceptibility, and complete active space self-consistent field (CASSCF) multiconfigurational calculations, as well as structural measurements compared to density functional theory calculations. The CASSCF calculations indicate that the intermediate valence is the result of a multiconfigurational ground-state wave function that has both an open-shell singlet f13(?*)1, where pi* is the lowest unoccupied molecular orbital of the bipyridine or dpiazabutadiene ligands, and a closed-shell singlet f14 component. A number of other competing theories for the unusual magnetism in these materials are ruled out by the lack of temperature dependence of the measured intermediate valence. These results have implications for understanding chemical bonding not only in organolanthanide complexes but also for f-element chemistry in general, as well as understanding magnetic interactions in nanoparticles and devices.

  4. Formation and identification of unresolved complex mixtures in lacustrine biodegraded oil from Nanxiang Basin, China.

    PubMed

    Guo, Pengfei; He, Sheng; Zhu, Shukui; Chai, Derong; Yin, Shiyan; Dai, Wei; Zhang, Wanfeng

    2014-01-01

    A comprehensive two-dimensional gas chromatography/time-of-flight mass spectrometry (GC × GC/TOFMS) method has been developed for the formation and identification of unresolved complex mixtures (UCMs) in lacustrine biodegraded oils that with the same source rock, similar maturity, and increasing degradation rank from Nanxiang Basin, China. Normal alkanes, light hydrocarbons, isoprenoids, steranes, and terpanes are degraded gradually from oil B330 to oil G574. The compounds in biodegraded oil (oil G574) have fewer types, the polarity difference of compounds in different types is minor, and the relative content of individual compounds is similar. All the features make the compounds in biodegraded oil coelute in GC analysis and form the raised "baseline hump" named UCMs. By injecting standard materials and analyzing mass spectrums of target compounds, it is shown that cyclic alkanes with one to five rings are the major components of UCMs. Furthermore, UCMs were divided into six classes. Classes I and II, composed of alkyl-cyclohexanes, alkyl-naphthanes, and their isomers, are originated from the enrichment of hydrocarbons resistant to degradation in normal oils. Classes III ~ VI, composed of sesquiterpenoids, tricyclic terpanes, low molecular steranes, diasteranes, norhopanes, and their isomers, are probably from some newly formed compounds during the microbial transformation of oil.

  5. Measurement of the formation of complexes in tyrosine kinase-mediated signal transduction

    SciTech Connect

    Ladbury, John E.

    2007-01-01

    The use of isothermal titration calorimetry (ITC) provides a full thermodynamic characterization of an interaction in one experiment. The determination of the affinity is an important value; however, the additional layer of information provided by the change in enthalpy and entropy can help in understanding the biology. This is demonstrated with respect to tyrosine kinase-mediated signal transduction. Isothermal titration calorimetry (ITC) provides highly complementary data to high-resolution structural detail. An overview of the methodology of the technique is provided. Ultimately, the correlation of the thermodynamic parameters determined by ITC with structural perturbation observed on going from the free to the bound state should be possible at an atomic level. Currently, thermodynamic data provide some insight as to potential changes occurring on complex formation. Here, this is demonstrated in the context of in vitro quantification of intracellular tyrosine kinase-mediated signal transduction and the issue of specificity of the important interactions. The apparent lack of specificity in the interactions of domains of proteins involved in early signalling from membrane-bound receptors is demonstrated using data from ITC.

  6. Reaction of a copper(II)-nitrosyl complex with hydrogen peroxide: putative formation of a copper(I)-peroxynitrite intermediate.

    PubMed

    Kalita, Apurba; Kumar, Pankaj; Mondal, Biplab

    2012-05-14

    The reaction of a Cu(II)-nitrosyl complex (1) with hydrogen peroxide at -20 °C in acetonitrile results in the formation of the corresponding Cu(I)-peroxynitrite intermediate. The reduction of the Cu(II) center was monitored by UV-visible spectroscopic studies. Formation of the peroxynitrite intermediate has been confirmed by its characteristic phenol ring nitration reaction as well as isolation of corresponding Cu(I)-nitrate (2). On air oxidation, 2 resulted in the corresponding Cu(II)-nitrate (3). Thus, these results demonstrate a possible decomposition pathway for H(2)O(2) and NO through the formation of a peroxynitrite intermediate in biological systems.

  7. Cord Formation in BACTEC Medium Is a Reliable, Rapid Method for Presumptive Identification of Mycobacterium tuberculosis Complex

    PubMed Central

    McCarter, Yvette S.; Ratkiewicz, Irene N.; Robinson, Ann

    1998-01-01

    Serpentine cord formation in BACTEC 12B medium was evaluated as a rapid method for the presumptive identification of M. tuberculosis complex. Kinyoun acid-fast stained smears were prepared from 666 positive BACTEC 12B bottles and examined for the presence or absence of serpentine cording. Cord formation had a sensitivity, specificity, positive predictive value, and negative predictive value of 89.2, 99.2, 98.5, and 94.2%, respectively. The evaluation of the presence of cord formation in BACTEC 12B medium is reliable and permits the rapid presumptive reporting of M. tuberculosis. PMID:9705435

  8. Cord formation in BACTEC medium is a reliable, rapid method for presumptive identification of Mycobacterium tuberculosis complex.

    PubMed

    McCarter, Y S; Ratkiewicz, I N; Robinson, A

    1998-09-01

    Serpentine cord formation in BACTEC 12B medium was evaluated as a rapid method for the presumptive identification of M. tuberculosis complex. Kinyoun acid-fast stained smears were prepared from 666 positive BACTEC 12B bottles and examined for the presence or absence of serpentine cording. Cord formation had a sensitivity, specificity, positive predictive value, and negative predictive value of 89.2, 99.2, 98.5, and 94.2%, respectively. The evaluation of the presence of cord formation in BACTEC 12B medium is reliable and permits the rapid presumptive reporting of M. tuberculosis.

  9. Human transforming growth factor. beta. -. cap alpha. /sub 2/-macroglobulin complex is a latent form of transforming growth factor. beta

    SciTech Connect

    Huang, S.S.; O'Grady, P.; Huang, J.S.

    1987-05-01

    Human platelet-derived transforming growth factor ..beta.. (TGF..beta..) has been shown to be present as a high molecular weight latent form in human serum. Appearance of transforming growth factor activity, along with the change from high molecular weight form to low molecular weight form, was observed following treatment of the latent form of TGF..beta.. with acid or urea, suggesting that the latent form of TGF..beta.. is a complex of TGF..beta.. and a high molecular weight binding protein. Human ..cap alpha../sub 2/-M has been found to be a plasma binding protein for platelet-derived growth factor (PDGF) in serum or plasma. TGF..beta.. and PDGF share similar properties. They, therefore, investigated the interaction between /sup 125/I-TGF..beta.. and ..cap alpha../sub 2/M. /sup 125/I-TGF..beta.. and purified human ..cap alpha../sub 2/M formed a complex as demonstrated by polyacrylamide gel electrophoresis. Most of the /sup 125/I-TGF..beta..-..cap alpha../sub 2/M complex could be dissociated by acid or urea treatment. These results suggest that ..cap alpha../sub 2/M is a binding protein for TGF..beta.. and that TGF..beta..-..cap alpha../sub 2/M complex may be the latent form of TGF..beta.. in serum.

  10. Determination of the equilibrium formation constants of two U(VI)-peroxide complexes at alkaline pH.

    PubMed

    Meca, S; Martínez-Torrents, A; Martí, V; Giménez, J; Casas, I; de Pablo, J

    2011-08-21

    The formation of uranyl-peroxide complexes was studied at alkaline media by using UV-Visible spectrophotometry and the STAR code. Two different complexes were found at a H(2)O(2)/U(VI) ratio lower than 2. A graphical method was used in order to obtain the formation constants of such complexes and the STAR program was used to refine the formation constants values because of its capacity to treat multiwavelength absorbance data and refining equilibrium constants. The values obtained for the two complexes identified were: UO(2)(2+) + H(2)O(2) + 4OH(-) <−> UO(2)(O(2))(OH)(2)(2-) + 2H(2)O: log β°(1,1,4) = 28.1 ± 0.1 (1). UO(2)(2+) + 2H(2)O(2) + 6OH(-) <−> UO(2)(O(2))(2)(OH)(2)(4-) + 4H(2)O: log β°(1,2,6) = 36.8 ± 0.2 (2). At hydrogen peroxide concentrations higher than 10(-5) mol dm(-3), and in the absence of carbonate, the UO(2)(O(2))(2)(OH)(2)(4-) complex is predominant in solution, indicating the significant peroxide affinity of peroxide ions for uranium and the strong complexes of uranium(VI) with peroxide.

  11. Chrysanthemum transcription factor CmLBD1 direct lateral root formation in Arabidopsis thaliana

    PubMed Central

    Zhu, Lu; Zheng, Chen; Liu, Ruixia; Song, Aiping; Zhang, Zhaohe; Xin, Jingjing; Jiang, Jiafu; Chen, Sumei; Zhang, Fei; Fang, Weimin; Chen, Fadi

    2016-01-01

    The plant-specific LATERAL ORGAN BOUNDARIES DOMAIN (LBD) genes are important regulators of growth and development. Here, a chrysanthemum class I LBD transcription factor gene, designated CmLBD1, was isolated and its function verified. CmLBD1 was transcribed in both the root and stem, but not in the leaf. The gene responded to auxin and was shown to participate in the process of adventitious root primordium formation. Its heterologous expression in Arabidopsis thaliana increased the number of lateral roots formed. When provided with exogenous auxin, lateral root emergence was promoted. CmLBD1 expression also favored callus formation from A. thaliana root explants in the absence of exogenously supplied phytohormones. In planta, CmLBD1 probably acts as a positive regulator of the response to auxin fluctuations and connects auxin signaling with lateral root formation. PMID:26819087

  12. Two Adjacent Trimeric Fas Ligands Are Required for Fas Signaling and Formation of a Death-Inducing Signaling Complex

    PubMed Central

    Holler, Nils; Tardivel, Aubry; Kovacsovics-Bankowski, Magdalena; Hertig, Sylvie; Gaide, Olivier; Martinon, Fabio; Tinel, Antoine; Deperthes, David; Calderara, Silvio; Schulthess, Therese; Engel, Jürgen; Schneider, Pascal; Tschopp, Jürg

    2003-01-01

    The membrane-bound form of Fas ligand (FasL) signals apoptosis in target cells through engagement of the death receptor Fas, whereas the proteolytically processed, soluble form of FasL does not induce cell death. However, soluble FasL can be rendered active upon cross-linking. Since the minimal extent of oligomerization of FasL that exerts cytotoxicity is unknown, we engineered hexameric proteins containing two trimers of FasL within the same molecule. This was achieved by fusing FasL to the Fc portion of immunoglobulin G1 or to the collagen domain of ACRP30/adiponectin. Trimeric FasL and hexameric FasL both bound to Fas, but only the hexameric forms were highly cytotoxic and competent to signal apoptosis via formation of a death-inducing signaling complex. Three sequential early events in Fas-mediated apoptosis could be dissected, namely, receptor binding, receptor activation, and recruitment of intracellular signaling molecules, each of which occurred independently of the subsequent one. These results demonstrate that the limited oligomerization of FasL, and most likely of some other tumor necrosis factor family ligands such as CD40L, is required for triggering of the signaling pathways. PMID:12556501

  13. A peroxynitrite complex of copper: formation from a copper-nitrosyl complex, transformation to nitrite and exogenous phenol oxidative coupling or nitration.

    PubMed

    Park, Ga Young; Deepalatha, Subramanian; Puiu, Simona C; Lee, Dong-Heon; Mondal, Biplab; Narducci Sarjeant, Amy A; del Rio, Diego; Pau, Monita Y M; Solomon, Edward I; Karlin, Kenneth D

    2009-11-01

    Reaction of nitrogen monoxide with a copper(I) complex possessing a tridentate alkylamine ligand gives a Cu(I)-(*NO) adduct, which when exposed to dioxygen generates a peroxynitrite (O=NOO(-))-Cu(II) species. This undergoes thermal transformation to produce a copper(II) nitrito (NO(2) (-)) complex and 0.5 mol equiv O(2). In the presence of a substituted phenol, the peroxynitrite complex effects oxidative coupling, whereas addition of chloride ion to dissociate the peroxynitrite moiety instead leads to phenol ortho nitration. Discussions include the structures (including electronic description) of the copper-nitrosyl and copper-peroxynitrite complexes and the formation of the latter, based on density functional theory calculations and accompanying spectroscopic data.

  14. The factor VIIIa C2 domain (residues 2228-2240) interacts with the factor IXa Gla domain in the factor Xase complex.

    PubMed

    Soeda, Tetsuhiro; Nogami, Keiji; Nishiya, Katsumi; Takeyama, Masahiro; Ogiwara, Kenichi; Sakata, Yoichi; Yoshioka, Akira; Shima, Midori

    2009-02-06

    Factor VIIIa functions as a cofactor for factor IXa in the phospholipid surface-dependent activation of factor X. Both the C2 domain of factor VIIIa and the Gla domain of factor IXa are involved in phospholipid binding and are required for the activation of factor X. In this study, we have examined the close relationship between these domains in the factor Xase complex. Enzyme-linked immunosorbent assay-based and surface plasmon resonance-based assays in the absence of phospholipid showed that Glu-Gly-Arg active site-modified factor IXa bound to immobilized recombinant C2 domain (rC2) dose-dependently (Kd = 108 nm). This binding ability was optimal under physiological conditions. A monoclonal antibody against the Gla domain of factor IXa inhibited binding by approximately 95%, and Gla domainless factor IXa failed to bind to rC2. The addition of monoclonal antibody or rC2 with factor VIIIa inhibited factor IXa-catalyzed factor X activation in the absence of phospholipid. Inhibition was not evident, however, in similar experiments in the absence of factor VIIIa, indicating that the C2 domain interacted with the Gla domain of factor IXa. A fragment designated C2-(2182-2259), derived from V8 protease-cleaved rC2, bound to Glu-Gly-Arg active site-modified factor IXa. Competitive assays, using overlapping synthetic peptides encompassing residues 2182-2259, demonstrated that peptide 2228-2240 significantly inhibited both this binding and factor Xa generation, independently of phospholipid. Our results indicated that residues 2228-2240 in the factor VIIIa C2 domain constitutes an interactive site for the Gla domain of factor IXa. The findings provide the first evidence for an essential role for this interaction in factor Xase assembly.

  15. [Factors affecting formation of THMs during dissolved organic nitrogen acetamide chlorination in drinking water].

    PubMed

    Chu, Wen-Hai; Gao, Nai-Yun; Zhao, Shi-Jia; Li, Qing-Song

    2009-05-15

    Chlorination disinfection greatly reduced bacteria and virus in drinking water. However, there is an unintended consequence of disinfection, the generation of chemical disinfection by-products (DBPs). Dissolved organic nitrogen (DON) as the important precursor of DBPs is of current concern. As acetamide (AcAm) occur in important bimolecular, we studied formation pathways for THMs during chlorination of model AcAm. The experiments are designed by Plackett-Burman and Box-Behnken methods. Factors affecting formation of THMs such as AcAm initial concentration, chlorine dosage, pH, temperature, Br(-) concentration and contact time were investigated. The results indicate that AcAm initial concentration, pH and temperature have little effects on formation of THMs. On the contrary, three other factors have important effects on formation of THMs, especially Br(-) concentration. The capacity of THMs generation varies very little when Br(-) has a constant concentration. Generation amount of THMs attach maximum under the condition that dosage of active chlorine, Br(-) concentration and contact time is 8.77 mg/L, 0.77 mg/L and 6.20 h respectively. Bromine ion plays a catalysis role on THMs formation. Controlling the concentration of bromine ion can reduce total generation amount of THMs via AcAm. Bromine partition coefficient tends to increasing along with contact time lapse. Controlling chlorination reaction time can lower the cancer risk. At last, the pathway is proposed for THMs formation via AcAm, and the catalysis mechanism of Br(-) was addressed.

  16. Repression of PDGF-R-α after cellular injury involves TNF-α, formation of a c-Fos-YY1 complex, and negative regulation by HDAC.

    PubMed

    Zhang, Ning; Chan, Cecilia W S; Sanchez-Guerrero, Estella; Khachigian, Levon M

    2012-06-01

    Wound healing is a complex dynamic process involving a variety of cell types, including fibroblasts that express and respond to cytokines and growth factors in the local microenvironment. The mechanisms controlling gene expression after injury at a transcriptional level are poorly understood. Here we show that decreased expression of a key receptor, PDGF-receptor (R)-α, after fibroblast injury is due to the release and paracrine activity of TNF-α. TNF-α inhibits PDGF-R-α expression and this involves formation of a c-Fos-Yin Yang 1 (YY1) complex and histone deacetylase (HDAC) activity. c-Fos, induced by TNF-α, negatively regulates PDGF-R-α transcription. Small interfering RNA (siRNA) targeting c-Fos or the zinc finger transcription factor YY1 inhibits TNF-α suppression of PDGF-R-α expression. Coimmunoprecipitation studies show that TNF-α stimulates the formation of a complex between c-Fos with YY1. Furthermore, chromatin immunoprecipitation (ChIP) analysis reveals the enrichment of c-Fos, YY1, and HDAC-1 at the PDGF-R-α promoter in cells exposed to TNF-α. With suberoylanilide hydroxamic acid (SAHA) and HDAC-1 siRNA, we demonstrate that HDAC mediates TNF-α repression of PDGF-R-α. These findings demonstrate that transcriptional repression of PDGF-R-α after fibroblast injury involves paracrine activity of endogenous TNF-α, the formation of a c-Fos-YY1 complex, and negative regulatory activity by HDAC.

  17. [The role of environmental factors in the formation of kidney calculi].

    PubMed

    Jung, A; Kamińska, A; Samol, B; Zuber, J

    2000-04-01

    Various endo- and exogenous factors play a role in the urinary stones formation tract. The aim of the study was to define the type and frequency of hyperexcretion of lithogenic substances in school children population and to determine an influence of risk factors on hyperexcretion of crystallizing substances. The study included 220 school children. Preurolithiasis state (PS) was found in 30% children. The most frequently hyperoxaluria, hyperuricosuria and hypercalciuria were diagnosed and it may be connected with abnormal nutritional habits, excessive application of multivitamins, vitamin D and calcium, disturbances in drinking water chemical composition (higher amount of calcium, smaller amount of magnesium, abnormal pH). Urinary tract infections, particularly in children with obstructive uropathy are an important risk factor in the examined population. Positive familial history of urolithiasis in 43.3% children may indicate for the important role of the genetic factor in the pathogenesis of the disease.

  18. The alternative splicing factor Nova2 regulates vascular development and lumen formation

    PubMed Central

    Giampietro, Costanza; Deflorian, Gianluca; Gallo, Stefania; Di Matteo, Anna; Pradella, Davide; Bonomi, Serena; Belloni, Elisa; Nyqvist, Daniel; Quaranta, Valeria; Confalonieri, Stefano; Bertalot, Giovanni; Orsenigo, Fabrizio; Pisati, Federica; Ferrero, Elisabetta; Biamonti, Giuseppe; Fredrickx, Evelien; Taveggia, Carla; Wyatt, Chris D. R.; Irimia, Manuel; Di Fiore, Pier Paolo; Blencowe, Benjamin J.; Dejana, Elisabetta; Ghigna, Claudia

    2015-01-01

    Vascular lumen formation is a fundamental step during angiogenesis; yet, the molecular mechanisms underlying this process are poorly understood. Recent studies have shown that neural and vascular systems share common anatomical, functional and molecular similarities. Here we show that the organization of endothelial lumen is controlled at the post-transcriptional level by the alternative splicing (AS) regulator Nova2, which was previously considered to be neural cell-specific. Nova2 is expressed during angiogenesis and its depletion disrupts vascular lumen formation in vivo. Similarly, Nova2 depletion in cultured endothelial cells (ECs) impairs the apical distribution and the downstream signalling of the Par polarity complex, resulting in altered EC polarity, a process required for vascular lumen formation. These defects are linked to AS changes of Nova2 target exons affecting the Par complex and its regulators. Collectively, our results reveal that Nova2 functions as an AS regulator in angiogenesis and is a novel member of the ‘angioneurins' family. PMID:26446569

  19. Antiplatelet agents affecting the interaction of Tissue Factor-Factor VIIa complex with Factor X in a continuous-flow reactor.

    PubMed

    Gir, S; Reavis, R; Turitto, V T; Gollamudi, R

    1996-02-01

    The purpose of the present study was to examine the role of antithrombotic agents in the activation of Factor X in the presence of the Tissue Factor-Factor VIIa (TF-VIIa) complex in a continuous-flow reactor. Tissue Factor immobilized in a phospholipid bilayer on the inner surface of a capillary tube (internal diameter = 0.27 mm) was exposed to a perfusate containing Factors VIIa and X flowing at a flow rate of 12.7 microliters/min, corresponding to a wall shear rate of 100 s-1. Factor Xa (the activated form of Factor X) in the effluent was determined by a chromogenic assay. The effectiveness of two platelet aggregation inhibitors, alpha,alpha'-bis-[3-(N,N-diethylcarbamoyl)piperidino-p-xylene dihydrobromide (A-1) and alpha,alpha'-bis-[3-N-benzyl-N-methylcarbamoyl)piperidino]-p-xylen e dihydrobromide (A-4) in inhibiting Factor X activation is reported here. The results suggest that the Tissue Factor pathway, mediated through TF-VIIa complex, produces significantly lower levels of Factor Xa in the presence of compounds A-1 and A-4. On the basis of these findings, it appears that the anticoagulation action of these compounds reinforces their platelet aggregation-inhibitory properties. These carbamoylpiperidines (nipecotamides) therefore appear to be useful antithrombotic agents.

  20. HTLV-1 Tax Induces Formation of the Active Macromolecular IKK Complex by Generating Lys63- and Met1-Linked Hybrid Polyubiquitin Chains.

    PubMed

    Shibata, Yuri; Tokunaga, Fuminori; Goto, Eiji; Komatsu, Ginga; Gohda, Jin; Saeki, Yasushi; Tanaka, Keiji; Takahashi, Hirotaka; Sawasaki, Tatsuya; Inoue, Satoshi; Oshiumi, Hiroyuki; Seya, Tsukasa; Nakano, Hiroyasu; Tanaka, Yuetsu; Iwai, Kazuhiro; Inoue, Jun-Ichiro

    2017-01-01

    The Tax protein of human T-cell leukemia virus type 1 (HTLV-1) is crucial for the development of adult T-cell leukemia (ATL), a highly malignant CD4+ T cell neoplasm. Among the multiple aberrant Tax-induced effects on cellular processes, persistent activation of transcription factor NF-κB, which is activated only transiently upon physiological stimulation, is essential for leukemogenesis. We and others have shown that Tax induces activation of the IκB kinase (IKK) complex, which is a critical step in NF-κB activation, by generating Lys63-linked polyubiquitin chains. However, the molecular mechanism underlying Tax-induced IKK activation is controversial and not fully understood. Here, we demonstrate that Tax recruits linear (Met1-linked) ubiquitin chain assembly complex (LUBAC) to the IKK complex and that Tax fails to induce IKK activation in cells that lack LUBAC activity. Mass spectrometric analyses revealed that both Lys63-linked and Met1-linked polyubiquitin chains are associated with the IKK complex. Furthermore, treatment of the IKK-associated polyubiquitin chains with Met1-linked-chain-specific deubiquitinase (OTULIN) resulted in the reduction of high molecular weight polyubiquitin chains and the generation of short Lys63-linked ubiquitin chains, indicating that Tax can induce the generation of Lys63- and Met1-linked hybrid polyubiquitin chains. We also demonstrate that Tax induces formation of the active macromolecular IKK complex and that the blocking of Tax-induced polyubiquitin chain synthesis inhibited formation of the macromolecular complex. Taken together, these results lead us to propose a novel model in which the hybrid-chain-dependent oligomerization of the IKK complex triggered by Tax leads to trans-autophosphorylation-mediated IKK activation.

  1. HTLV-1 Tax Induces Formation of the Active Macromolecular IKK Complex by Generating Lys63- and Met1-Linked Hybrid Polyubiquitin Chains

    PubMed Central

    Tokunaga, Fuminori; Goto, Eiji; Komatsu, Ginga; Saeki, Yasushi; Tanaka, Keiji; Takahashi, Hirotaka; Sawasaki, Tatsuya; Inoue, Satoshi; Oshiumi, Hiroyuki; Seya, Tsukasa; Nakano, Hiroyasu; Tanaka, Yuetsu; Iwai, Kazuhiro

    2017-01-01

    The Tax protein of human T-cell leukemia virus type 1 (HTLV-1) is crucial for the development of adult T-cell leukemia (ATL), a highly malignant CD4+ T cell neoplasm. Among the multiple aberrant Tax-induced effects on cellular processes, persistent activation of transcription factor NF-κB, which is activated only transiently upon physiological stimulation, is essential for leukemogenesis. We and others have shown that Tax induces activation of the IκB kinase (IKK) complex, which is a critical step in NF-κB activation, by generating Lys63-linked polyubiquitin chains. However, the molecular mechanism underlying Tax-induced IKK activation is controversial and not fully understood. Here, we demonstrate that Tax recruits linear (Met1-linked) ubiquitin chain assembly complex (LUBAC) to the IKK complex and that Tax fails to induce IKK activation in cells that lack LUBAC activity. Mass spectrometric analyses revealed that both Lys63-linked and Met1-linked polyubiquitin chains are associated with the IKK complex. Furthermore, treatment of the IKK-associated polyubiquitin chains with Met1-linked-chain-specific deubiquitinase (OTULIN) resulted in the reduction of high molecular weight polyubiquitin chains and the generation of short Lys63-linked ubiquitin chains, indicating that Tax can induce the generation of Lys63- and Met1-linked hybrid polyubiquitin chains. We also demonstrate that Tax induces formation of the active macromolecular IKK complex and that the blocking of Tax-induced polyubiquitin chain synthesis inhibited formation of the macromolecular complex. Taken together, these results lead us to propose a novel model in which the hybrid-chain-dependent oligomerization of the IKK complex triggered by Tax leads to trans-autophosphorylation-mediated IKK activation. PMID:28103322

  2. Ab initio study on the formation of triiodide CT complex from the reaction of iodine with 2,3-diaminopyridine.

    PubMed

    Al-Hashimi, Nessreen A; Hussein, Yasser H A

    2010-01-01

    The charge transfer (CT) interaction between iodine and 2,3-diaminopyridine (DAPY) has been thoroughly investigated via theoretical calculations. A Hartree-Fock, 3-21G level of theory was used to optimize and calculate the Mullican charge distribution scheme as well as the vibrational frequencies of DAPY alone and both its CT complexes with one and two iodine molecules. A very good agreement was found between experiment and theory. New illustrations were concluded with a deep analysis and description for the vibrational frequencies of the formed CT complexes. The two-step CT complex formation mechanism published earlier was supported.

  3. Theoretical Study on the Factors Controlling the Stability of the Borate Complexes of Ribose, Arabinose, Lyxose and Xylose

    SciTech Connect

    Sumpter, Bobby G; Fuentes-Cabrera, Miguel A; Leszczynski, Jerzy; Sponer, Judit; Sponer, Jiri

    2008-01-01

    Recent views on the origin of the "RNA world" suggest that complexation with borate minerals had an indispensable role at stabilizing the cyclic form of aldopentoses that are the potential building blocks of RNA. Experimental investigations by Li Q, Ricardo A, Benner SA, Winefordner JD, Powell DH (2005) Anal Chem 77:4503-4508 and Chapelle S, Verchere J-F (1988) Tetrahedron 44:4469-4482 have shown that stability of the 2:1 complexes formed between ribose and borate is superior to those of the analogous compounds of the other three aldopentoses (xylose, arabinose and lyxose). The distinct stability of the ribose-borate 2:1 complexes is thought to be one of the basic reasons why evolution selected ribose (out of the four aldopentoses) to build up RNA molecules. Here we disclose the factors governing the stability of the aldopentose-borate 2:1 complexes using Density Functional Theory electronic structure calculations with inclusion of solvation effects using a continuum solvent approach. Our results show that the strong electrostatic field of the borate anion leads to the reorientation of the hydroxyl groups of the aldopentoses relative to the geometry adopted in the non-complexed form. The reasons why complex formation between borate and ribose is clearly preferred over the other three aldopentoses is (i) the ribose 3-OH is involved in a H-bond with one of the borate-oxygens and (ii) its 5-CH2OH group is well separated in space from the negatively charged region of the complex and ensures favorable contact with the aqueous medium.

  4. Impact of skeletal unloading on bone formation: Role of systemic and local factors

    NASA Astrophysics Data System (ADS)

    Bikle, Daniel D.; Halloran, Bernard P.; Morey-Holton, Emily

    We have developed a model of skeletal unloading using growing rats whose hindlimbs are unweighted by tail suspension. The bones in the hindlimbs undergo a transient cessation of bone growth; when reloaded bone formation is accelerated until bone mass is restored. These changes do not occur in the normally loaded bones of the forelimbs. Associated with the fall in bone formation is a fall in 1,25(OH) 2D 3 production and osteocalcin levels. In contrast, no changes in parathyroid hormone, calcium, or corticosterone levels are seen. To examine the role of locally produced growth factors, we have measured the mRNA and protein levels of insulin like growth factor-1 (IGF-1) in bone during tail suspension. Surprisingly, both the mRNA and protein levels of IGF-1 increase during tail suspension as bone formation is reduced. Furthermore, the bones in the hindlimbs of the suspended animals develop a resistance to the growth promoting effects of both growth hormone and IGF-1 when given parenterally. Thus, the cessation of bone growth with skeletal unloading is apparently associated with a resistance to rather than failure to produce local growth factors. The cause of this resistance remains under active investigation.

  5. N-Nitrosodimethylamine formation from ozonation of chlorpheniramine: Influencing factors and transformation mechanism.

    PubMed

    Lv, Juan; Wang, Lin; Song, Yun; Li, Yongmei

    2015-12-15

    As a disinfection byproduct, the detection of N-nitrosodimethylamine (NDMA) in aquatic environments across the globe has caused widespread concern due to its potential carcinogenicity. In this study, the possibility of NDMA formation from chlorpheniramine ozonation was investigated. The influencing factors including the initial chlorpheniramine concentration, ozone dose, pH, and water matrix were quantified. Furthermore, the mechanisms for chlorpheniramine transformation and NDMA formation were explored. Our results demonstrate that ozonation is effective in removing chlorpheniramine. Generation of dimethylamine (DMA) and NDMA was observed during chlorpheniramine ozonation. Higher initial chlorpheniramine concentration and ozone dose resulted in higher production of NDMA. Acidic conditions (pH≤5) did not facilitate the production of NDMA. Ozone molecules played a dominant role in chlorpheniramine degradation, and influenced DMA release and NDMA formation. DMA and NDMA generations as well as their degradations were mainly attributed to hydroxyl radicals (·OH) produced by ozone decomposition. Water matrix properties such as HCO3(-) and humic acid affected DMA and NDMA generation due to ·OH competition. The degradation intermediates of chlorpheniramine were identified, among which only the intermediates with a DMA group were attributable to NDMA formation. A possible pathway for NDMA formation from chlorpheniramine ozonation is proposed.

  6. Identification of ORC1/CDC6-Interacting Factors in Trypanosoma brucei Reveals Critical Features of Origin Recognition Complex Architecture

    PubMed Central

    Tiengwe, Calvin; Marcello, Lucio; Farr, Helen; Gadelha, Catarina; Burchmore, Richard; Barry, J. David; Bell, Stephen D.; McCulloch, Richard

    2012-01-01

    DNA Replication initiates by formation of a pre-replication complex on sequences termed origins. In eukaryotes, the pre-replication complex is composed of the Origin Recognition Complex (ORC), Cdc6 and the MCM replicative helicase in conjunction with Cdt1. Eukaryotic ORC is considered to be composed of six subunits, named Orc1–6, and monomeric Cdc6 is closely related in sequence to Orc1. However, ORC has been little explored in protists, and only a single ORC protein, related to both Orc1 and Cdc6, has been shown to act in DNA replication in Trypanosoma brucei. Here we identify three highly diverged putative T. brucei ORC components that interact with ORC1/CDC6 and contribute to cell division. Two of these factors are so diverged that we cannot determine if they are eukaryotic ORC subunit orthologues, or are parasite-specific replication factors. The other we show to be a highly diverged Orc4 orthologue, demonstrating that this is one of the most widely conserved ORC subunits in protists and revealing it to be a key element of eukaryotic ORC architecture. Additionally, we have examined interactions amongst the T. brucei MCM subunits and show that this has the conventional eukaryotic heterohexameric structure, suggesting that divergence in the T. brucei replication machinery is limited to the earliest steps in origin licensing. PMID:22412905

  7. Complex caddisfly-dominated bioherms from the Eocene Green River Formation

    NASA Astrophysics Data System (ADS)

    Leggitt, V. Leroy; Cushman, Robert A.

    2001-12-01

    Complex, caddisfly-dominated (Insecta: Trichoptera) carbonate mounds up to 9 m tall and 40 m in diameter formed in the nearshore environment of Eocene Lake Gosiute. The mounds outcrop for 70 km in reef-like geometries along the northern margin of Lake Gosiute in Wyoming. The relationships among the caddisfly larvae, the benthic microbial mat and physicochemical nearshore processes of Eocene Lake Gosiute resulted in unique external and internal carbonate mound morphology. Externally, the large carbonate mounds are formed by the lateral and vertical coalescence of several layers of smaller columns. The smaller columns are generally 1-2 m tall and are 0.5-1 m in diameter. Each layer or generation of smaller columns tends to have a unique external morphology. This suggests that variable paleoenvironmental conditions produced subtle differences in tufa and stromatolite morphology. Internally, each of the smaller columns is composed of a core of caddisfly larval cases surrounded by layers of tufa and stromatolites. The smaller column cores are characterized by centimeter thick microbial-caddisfly couplets in which layers or packets of calcified caddisfly larval cases are covered by microbial mat-mediated, microlaminated carbonate. The microbial-caddisfly couplets suggest that both metazoans and microbes were responsible for column height and shape. In this paper, we propose a mechanism for the growth of these caddisfly-dominated mounds. The base of the Laney Member of the Green River Formation records a freshwater lacustrine transgression over the surrounding floodplains and mudflats of the Cathedral Bluffs Tongue of the Wasatch Formation. In nearshore areas of the lake's northern margin, carbonate hardgrounds developed in some areas of the softer, carbonate-rich, bottom muds. These hardgrounds provided nucleation sites for the carbonate mounds and columns by providing a stable substrate for the benthic microbial mat and for caddisfly larval case attachment during

  8. Monitoring the formation of carbide crystal phases during the thermal decomposition of 3d transition metal dicarboxylate complexes

    SciTech Connect

    Huba, ZJ; Carpenter, EE

    2014-06-06

    Single molecule precursors can help to simplify the synthesis of complex alloys by minimizing the amount of necessary starting reagents. However, single molecule precursors are time consuming to prepare with very few being commercially available. In this study, a simple precipitation method is used to prepare Fe, Co, and Ni fumarate and succinate complexes. These complexes were then thermally decomposed in an inert atmosphere to test their efficiency as single molecule precursors for the formation of metal carbide phases. Elevated temperature X-ray diffraction was used to identify the crystal phases produced upon decomposition of the metal dicarboxylate complexes. Thermogravimetric analysis coupled with an infrared detector was used to identify the developed gaseous decomposition products. All complexes tested showed a reduction from the starting M2+ oxidation state to the M oxidation state, upon decomposition. Also, each complex tested showed CO2 and H2O as gaseous decomposition products. Nickel succinate, iron succinate, and iron fumarate complexes were found to form carbide phases upon decomposition. This proves that transition metal dicarboxylate salts can be employed as efficient single molecule precursors for the formation of metal carbide crystal phases.

  9. Formation of palladium nanofilms using electrochemical atomic layer deposition (E-ALD) with chloride complexation.

    PubMed

    Sheridan, Leah B; Gebregziabiher, Daniel K; Stickney, John L; Robinson, David B

    2013-02-05

    Pd thin films were formed by electrochemical atomic layer deposition (E-ALD) using surface-limited redox replacement (SLRR) of Cu underpotential deposits (UPD) on polycrystalline Au substrates. An automated electrochemical flow deposition system was used to deposit Pd atomic layers using a sequence of steps referred to as a cycle. The initial step was Cu UPD, followed by its exchange for Pd ions at open circuit, and finishing with a blank rinse to complete the cycle. Deposits were formed with up to 75 cycles and displayed proportional deposit thicknesses. Previous reports by this group indicated excess Pd deposition at the flow cell ingress, from electron probe microanalysis (EPMA). Those results suggested that the SLRR mechanism did not involve direct transfer between a Cu(UPD) atom and a Pd(2+) ion that would take its position. Instead, it was proposed that electrons are transferred through the metallic surface to reduce Pd(2+) ions near the surface where their activity is highest. It was proposed that if the cell was filled completely before a significant fraction of the Cu(UPD) atoms had been oxidized then the deposit would be homogeneous. Previous work with EDTA indicated that the hypothesis had merit, but it proved to be very sensitive to the EDTA concentration. In the present study, chloride was used to complex Pd(2+) ions, forming PdCl(4)(2-), to slow the exchange rate. Both complexing agents led to a decrease in the rate of replacement, producing more homogeneous films. Although the use of EDTA improved the homogeneity, it also decreased the deposit thickness by a factor of 3 compared to the thickness obtained via the use of chloride.

  10. Formation and dissociation of the BSS1 protein complex regulates plant development via brassinosteroid signaling.

    PubMed

    Shimada, Setsuko; Komatsu, Tomoyuki; Yamagami, Ayumi; Nakazawa, Miki; Matsui, Minami; Kawaide, Hiroshi; Natsume, Masahiro; Osada, Hiroyuki; Asami, Tadao; Nakano, Takeshi

    2015-02-01

    Brassinosteroids (BRs) play important roles in plant development and the response to environmental cues. BIL1/BZR1 is a master transcription factor in BR signaling, but the mechanisms that lead to the finely tuned targeting of BIL1/BZR1 by BRs are unknown. Here, we identified BRZ-SENSITIVE-SHORT HYPOCOTYL1 (BSS1) as a negative regulator of BR signaling in a chemical-biological analysis involving brassinazole (Brz), a specific BR biosynthesis inhibitor. The bss1-1D mutant, which overexpresses BSS1, exhibited a Brz-hypersensitive phenotype in hypocotyl elongation. BSS1 encodes a BTB-POZ domain protein with ankyrin repeats, known as BLADE ON PETIOLE1 (BOP1), which is an important regulator of leaf morphogenesis. The bss1-1D mutant exhibited an increased accumulation of phosphorylated BIL1/BZR1 and a negative regulation of BR-responsive genes. The number of fluorescent BSS1/BOP1-GFP puncta increased in response to Brz treatment, and the puncta were diffused by BR treatment in the root and hypocotyl. We show that BSS1/BOP1 directly interacts with BIL1/BZR1 or BES1. The large protein complex formed between BSS1/BOP1 and BIL1/BZR1 was only detected in the cytosol. The nuclear BIL1/BZR1 increased in the BSS1/BOP1-deficient background and decreased in the BSS1/BOP1-overexpressing background. Our study suggests that the BSS1/BOP1 protein complex inhibits the transport of BIL1/BZR1 to the nucleus from the cytosol and negatively regulates BR signaling.

  11. Core Formation in Planetesimals: Textural Analyses From 3D Synchrotron Imaging and Complex Systems Modeling

    NASA Astrophysics Data System (ADS)

    Rushmer, T. A.; Tordesillas, A.; Walker, D. M.; Parkinson, D. Y.; Clark, S. M.

    2012-12-01

    Recent scenarios of core formation in planetesimals using calculations from planetary dynamists and from extinct radionuclides (e.g. 26Al, 60Fe), call for segregation of a metal liquid (core) from both solid silicate and a partially molten silicate - a silicate mush - matrix. These segregation scenarios require segregation of metallic metal along fracture networks or by the growth of molten core material into blebs large enough to overcome the strength of the mush matrix. Such segregation scenarios usually involve high strain rates so that separation can occur, which is in agreement with the accretion model of planetary growth. Experimental work has suggested deformation and shear can help develop fracture networks and coalesce metallic blebs. Here, we have developed an innovative approach that currently combines 2D textures in experimental deformation experiments on a partially molten natural meteorite with complex network analyses. 3D textural data from experimental samples, deformed at high strain rates, with or without silicate melts present, have been obtained by synchrotron-based high resolution hard x-ray microtomography imaging. A series of two-dimensional images is collected as the sample is rotated, and tomographic reconstruction yields the full 3D representation of the sample. Virtual slices through the 3D object in any arbitrary direction can be visualized, or the full data set can be visualized by volume rendering. More importantly, automated image filtering and segmentation allows the extraction of boundaries between the various phases. The volumes, shapes, and distributions of each phase, and the connectivity between them, can then be quantitatively analysed, and these results can be compared to models. We are currently using these new visual data sets to augment our 2D data. These results will be included in our current complex system analytical approach. This integrated method can elucidate and quantify the growth of metallic blebs in regions where

  12. Complex formation in alkyldimethylamine oxide/sodium palmitate/water mixtures.

    PubMed

    Tanaka, Shimon; Kawasaki, Hideya; Maeda, Hiroshi

    2005-03-01

    The complex formation between nonionic alkyldimethylamine oxide (CnDMAO, n=14, 16, and 18) and sodium palmitate (NaPa) in the solid phase of CnDMAO/NaPa mixtures and the dependence of the interaction parameter beta of the regular solution theory (RST) on the mixed micelle composition of C16DMAO/NaPa mixtures were investigated. The dissolution temperature showed a maximum at a NaPa mole fraction X(Pa)(*) of 0.3-0.4 for C16DMAO/NaPa and 0.2 for C18DMAO/NaPa. The compositions of the complexes suggested by X(Pa)(*) are C16DMAO: NaPa=3:2 or 2:1 and C18DMAO:NaPa=4:1. The composition X(Pa)(*) depended on the chain length of the amine oxides. The maximum was not observed in the case of the C14DMAO/NaPa/water system. In the range 0.7< or =X(Pa)< or =1.0, dissolution temperature depression was observed with decreasing X(Pa). The dissolution temperature depression was analyzed by taking into account the nonideal behavior in the mixed micelles and the counterion binding on the mixed micelle surface. The negative beta values were obtained for all three mixed systems. It was shown that the counterion activity remained practically constant in the range of 0.7< or =X(Pa)< or =1.0. The cmc values of C16DMAO/NaPa mixtures were determined by pyrene fluorescence measurement. For C16DMAO/NaPa mixtures, the dependence of the RST interaction parameter beta on the mixed micelle composition X(Pa) was determined for a wide range (0.2< or =X(Pa) < or =0.9). In the range 0.2< or =X(Pa)< or =0.5, the beta values were obtained from an analysis of cmc based on the RST. In the range 0.7< or=X(Pa)< or=0.9, the beta values were obtained from an analysis of the dissolution temperature depression. From the analysis of the micelle composition dependence of the beta values, a short-range attractive interaction between the headgroup of C16DMAO and palmitate anion is suggested.

  13. [Epidermal growth factor receptor expression and epidermal growth factor blood plasma content in simple and complex endometrial hyperplasia].

    PubMed

    Dznelashvili, N; Kasradze, D; Tavartkiladze, A; Mariamidze, A

    2014-01-01

    The goal of our study was to concurrently determine the prognostic significance of Epidermal Growth Factor Receptor (EGFR) expression in endometrium and Epidermal Growth Factor (EGF) blood content in simple and complex hyperplasia. In order to detect EGFR expression, immunohistochemical examination of endometrial scarp from 35 patients was done along with HPLC (High performance liquid chromatography) method, for measuring EGF blood plasma content. The numerical data obtained were processed statistically using computer program SPSS-12. According to the results: 1. A significant/marked increase in EGF blood plasma level together with pronounced EGFR expression in simple endometrial hyperplasia (without atypia) suggests that simple hyperplasia is likely to transform into complex form, while unchanged level of EGF against the background of mild EGFR expression is probably indicative of not very bad prognosis. 2. Normal indices of EGF blood plasma level in simple endometrial hyperplasia (without atypia), accompanied by mild EGFR expression is suggestive of good prognosis. 3. A sharp or extremely sharp increase in EGF blood plasma level with pronounced EGFR expression in complex endometrial hyperplasia (without atypia) is likely to indicate poor prognosis that may lead to the transformation into atypical form. However, unchanged EGF blood plasma level against the background of mild EGFR expression in complex endometrial hyperplasia (without atypia) is likely to point to not very bad prognosis. 4. A marked increase in EGF blood plasma level with a pronounced EGFR expression in complex endometrial hyperplasia (without atypia) is likely to indicate poor prognosis that may lead to the transformation into atypical form. Because it is evident that drastic increase in EGF blood plasma level is not necessary, other factor should be suspected to play the major role, i.e the substance that will (or will not) withstand neoplasia.

  14. Equilibrium and kinetic studies on complex formation and decomposition and the movement of Cu(2+)metal ions within polytopic receptors.

    PubMed

    Castillo, Carmen Ester; González-García, Jorge; Llinares, José M; Máñez, M Angeles; Jimenez, Hermas R; García-España, Enrique; Basallote, Manuel G

    2013-05-07

    Potentiometric studies carried out on the interaction of two tritopic double-scorpiand receptors in which two equivalent 5-(2-aminoethyl)-2,5,8-triaza[9]-(2,6)-pyridinophane moieties are linked with 2,9-dimethylphenanthroline (L1) and 2,6-dimethylpyridine (L2) establish the formation of mono-, bi- and trinuclear Cu(2+) complexes. The values of the stability constants and paramagnetic (1)H NMR studies permit one to infer the most likely coordination modes of the various complexes formed. Kinetic studies on complex formation and decomposition have also been carried out. Complex formation occurs with polyphasic kinetics for both receptors, although a significant difference is found between both ligands with respect to the relative values of the rate constants for the metal coordination steps and the structural reorganizations following them. Complex decomposition occurs with two separate kinetic steps, the first one being so fast that it occurs within the stopped-flow mixing time, whereas the second one is slow enough to allow kinetic studies using a conventional spectrophotometer. As a whole, the kinetic experiments also provide information about the movement of the metal ion within the receptors. The differences observed between the different receptors can be interpreted in terms of changes in the network of hydrogen bonds formed in the different species.

  15. Mechanism and functions of membrane binding by the Atg5-Atg12/Atg16 complex during autophagosome formation.

    PubMed

    Romanov, Julia; Walczak, Marta; Ibiricu, Iosune; Schüchner, Stefan; Ogris, Egon; Kraft, Claudine; Martens, Sascha

    2012-11-14

    Autophagy is a conserved process for the bulk degradation of cytoplasmic material. Triggering of autophagy results in the formation of double membrane-bound vesicles termed autophagosomes. The conserved Atg5-Atg12/Atg16 complex is essential for autophagosome formation. Here, we show that the yeast Atg5-Atg12/Atg16 complex directly binds membranes. Membrane binding is mediated by Atg5, inhibited by Atg12 and activated by Atg16. In a fully reconstituted system using giant unilamellar vesicles and recombinant proteins, we reveal that all components of the complex are required for efficient promotion of Atg8 conjugation to phosphatidylethanolamine and are able to assign precise functions to all of its components during this process. In addition, we report that in vitro the Atg5-Atg12/Atg16 complex is able to tether membranes independently of Atg8. Furthermore, we show that membrane binding by Atg5 is downstream of its recruitment to the pre-autophagosomal structure but is essential for autophagy and cytoplasm-to-vacuole transport at a stage preceding Atg8 conjugation and vesicle closure. Our findings provide important insights into the mechanism of action of the Atg5-Atg12/Atg16 complex during autophagosome formation.

  16. Specificity and Membrane Partitioning of Grsp1 Signaling Complexes with Grp1 Family ARF Exchange Factors

    PubMed Central

    DiNitto, Jonathan P.; Lee, Meng-Tse; Malaby, Andrew W.; Lambright, David G.

    2010-01-01

    The Arf exchange factor Grp1 selectively binds phosphatidylinositol 3,4,5-triphosphate (PtdIns(3,4,5)P3), which is required for recruitment to the plasma membrane in stimulated cells. The mechanisms for phosphoinositide recognition by the PH domain, catalysis of nucleotide exchange by the Sec7 domain, and autoinhibition by elements proximal to the PH domain are well characterized. The N-terminal heptad repeats in Grp1 have also been shown to mediate homodimerization in vitro as well as heteromeric interactions with heptad repeats in the FERM domain-containing protein Grsp1 both in vitro and in cells (1). Here, we have characterized the oligomeric state of Grsp1 and Grp1 family proteins (Grp1, ARNO, and Cytohesin-1) as well as the oligomeric state, stoichiometry, and specificity of Grsp1 complexes with Grp1, ARNO and Cytohesin-1. At low micromolar concentrations, Grp1 and ARNO are homodimeric whereas Cytohesin-1 and Grsp1 are monomeric. When mixed with Grsp1, Grp1 homodimers and Cytohesin-1 monomers spontaneously re-equilibrate to form heterodimers whereas approximately 50% of ARNO remains homodimeric under the same conditions. Fluorescence resonance energy transfer experiments suggest that the Grsp1 heterodimers with Grp1 and Cytohesin-1 adopt a largely anti-parallel orientation. Finally, formation of Grsp1-Grp1 heterodimers does not substantially influence Grp1 binding to the head groups of PtdIns(3,4,5)P3 or PtdIns(4,5)P2 nor does it influence partitioning with liposomes containing PtdIns(3,4,5)P3, PtdIns(4,5)P2 and/or phosphatidyl serine. PMID:20527794

  17. Functional diversification of FD transcription factors in rice, components of florigen activation complexes.

    PubMed

    Tsuji, Hiroyuki; Nakamura, Hiroyuki; Taoka, Ken-ichiro; Shimamoto, Ko

    2013-03-01

    Florigen, a protein encoded by the FLOWERING LOCUS T (FT) in Arabidopsis and Heading date 3a (Hd3a) in rice, is the universal flowering hormone in plants. Florigen is transported from leaves to the shoot apical meristem and initiates floral evocation. In shoot apical cells, conserved cytoplasmic 14-3-3 proteins act as florigen receptors. A hexameric florigen activation complex (FAC) composed of Hd3a, 14-3-3 proteins, and OsFD1, a transcription factor, activates OsMADS15, a rice homolog of Arabidopsis APETALA1, leading to flowering. Because FD is a key component of the FAC, we characterized the FD gene family and their functions. Phylogenetic analysis of FD genes indicated that this family is divided into two groups: (i) canonical FD genes that are conserved among eudicots and non-Poaceae monocots; and (ii) Poaceae-specific FD genes that are organized into three subgroups: Poaceae FD1, FD2 and FD3. The Poaceae FD1 group shares a small sequence motif, T(A/V)LSLNS, with FDs of eudicots and non-Poaceae monocots. Overexpression of OsFD2, a member of the Poaceae FD2 group, produced smaller leaves with shorter plastochrons, suggesting that OsFD2 controls leaf development. In vivo subcellular localization of Hd3a, 14-3-3 and OsFD2 suggested that in contrast to OsFD1, OsFD2 is restricted to the cytoplasm through its interaction with the cytoplasmic 14-3-3 proteins, and interaction of Hd3a with 14-3-3 facilitates nuclear translocation of the FAC containing OsFD2. These results suggest that FD function has diverged between OsFD1 and OsFD2, but formation of a FAC is essential for their function.

  18. Functional Diversification of FD Transcription Factors in Rice, Components of Florigen Activation Complexes

    PubMed Central

    Tsuji, Hiroyuki; Nakamura, Hiroyuki; Taoka, Ken-ichiro; Shimamoto, Ko

    2013-01-01

    Florigen, a protein encoded by the FLOWERING LOCUS T (FT) in Arabidopsis and Heading date 3a (Hd3a) in rice, is the universal flowering hormone in plants. Florigen is transported from leaves to the shoot apical meristem and initiates floral evocation. In shoot apical cells, conserved cytoplasmic 14-3-3 proteins act as florigen receptors. A hexameric florigen activation complex (FAC) composed of Hd3a, 14-3-3 proteins, and OsFD1, a transcription factor, activates OsMADS15, a rice homolog of Arabidopsis APETALA1, leading to flowering. Because FD is a key component of the FAC, we characterized the FD gene family and their functions. Phylogenetic analysis of FD genes indicated that this family is divided into two groups: (i) canonical FD genes that are conserved among eudicots and non-Poaceae monocots; and (ii) Poaceae-specific FD genes that are organized into three subgroups: Poaceae FD1, FD2 and FD3. The Poaceae FD1 group shares a small sequence motif, T(A/V)LSLNS, with FDs of eudicots and non-Poaceae monocots. Overexpression of OsFD2, a member of the Poaceae FD2 group, produced smaller leaves with shorter plastochrons, suggesting that OsFD2 controls leaf development. In vivo subcellular localization of Hd3a, 14-3-3 and OsFD2 suggested that in contrast to OsFD1, OsFD2 is restricted to the cytoplasm through its interaction with the cytoplasmic 14-3-3 proteins, and interaction of Hd3a with 14-3-3 facilitates nuclear translocation of the FAC containing OsFD2. These results suggest that FD function has diverged between OsFD1 and OsFD2, but formation of a FAC is essential for their function. PMID:23324168

  19. Microcalorimetric determination of the thermodynamics of formation of the mono- and bi-sulfato complexes of lanthanum in aqueous solutions between 25 and 55 degrees C

    SciTech Connect

    Simpson, C.; Matijevic, E.

    1987-05-01

    Using a differential microcalorimeter, the formation constants and enthalpies of formation of the mono- and bi-sulfato complexes of lanthanum ion have been evaluated for aqueous acidic solutions over a temperature range of 25 to 55/sup 0/C.

  20. Promoter Escape with Bacterial Two-component σ Factor Suggests Retention of σ Region Two in the Elongation Complex.

    PubMed

    Sengupta, Shreya; Prajapati, Ranjit Kumar; Mukhopadhyay, Jayanta

    2015-11-20

    The transition from the formation of the RNA polymerase (RNAP)-promoter open complex step to the productive elongation complex step involves "promoter escape" of RNAP. From the structure of RNAP, a promoter escape model has been proposed that suggests that the interactions between σR4 and RNAP and σR4 and DNA are destabilized upon transition to elongation. This accounts for the reduced affinity of σ to RNAP and stochastic release of σ. However, as the loss of interaction of σR4 with RNAP results in the release of intact σ, assessing this interaction remains challenging to be experimentally verified. Here we study the promoter escape model using a two-component σ factor YvrI and YvrHa from Bacillus subtilis that independently contributes to the functions of σR4 and σR2 in a RNAP-promoter complex. Our results show that YvrI, which mimics σR4, is released gradually as transcription elongation proceeds, whereas YvrHa, which mimics σR2 is retained throughout the elongation complexes. Thus our result validates the proposed model for promoter escape and also suggests that promoter escape involves little or no change in the interaction of σR2 with RNAP.

  1. Promoter Escape with Bacterial Two-component σ Factor Suggests Retention of σ Region Two in the Elongation Complex*

    PubMed Central

    Sengupta, Shreya; Prajapati, Ranjit Kumar; Mukhopadhyay, Jayanta

    2015-01-01

    The transition from the formation of the RNA polymerase (RNAP)-promoter open complex step to the productive elongation complex step involves “promoter escape” of RNAP. From the structure of RNAP, a promoter escape model has been proposed that suggests that the interactions between σR4 and RNAP and σR4 and DNA are destabilized upon transition to elongation. This accounts for the reduced affinity of σ to RNAP and stochastic release of σ. However, as the loss of interaction of σR4 with RNAP results in the release of intact σ, assessing this interaction remains challenging to be experimentally verified. Here we study the promoter escape model using a two-component σ factor YvrI and YvrHa from Bacillus subtilis that independently contributes to the functions of σR4 and σR2 in a RNAP-promoter complex. Our results show that YvrI, which mimics σR4, is released gradually as transcription elongation proceeds, whereas YvrHa, which mimics σR2 is retained throughout the elongation complexes. Thus our result validates the proposed model for promoter escape and also suggests that promoter escape involves little or no change in the interaction of σR2 with RNAP. PMID:26400263

  2. Protein phosphatase 2A regulates interleukin-2 receptor complex formation and JAK3/STAT5 activation.

    PubMed

    Ross, Jeremy A; Cheng, Hanyin; Nagy, Zsuzsanna S; Frost, Jeffrey A; Kirken, Robert A

    2010-02-05

    Reversible protein phosphorylation plays a key role in interleukin-2 (IL-2) receptor-mediated activation of Janus tyrosine kinase 3 (JAK3) and signal transducer and activator of transcription 5 (STAT5) in lymphocytes. Although the mechanisms governing IL-2-induced tyrosine phosphorylation and activation of JAK3/STAT5 have been extensively studied, the role of serine/threonine phosphorylation in controlling these effectors remains to be elucidated. Using phosphoamino acid analysis, JAK3 and STAT5 were determined to be serine and tyrosine-phosphorylated in response to IL-2 stimulation of the human natural killer-like cell line, YT. IL-2 stimulation also induced serine/threonine phosphorylation of IL-2Rbeta, but not IL-2Rgamma. To investigate the regulation of serine/threonine phosphorylation in IL-2 signaling, the roles of protein phosphatase 1 (PP1) and 2A (PP2A) were examined. Inhibition of phosphatase activity by calyculin A treatment of YT cells resulted in a significant induction of serine phosphorylation of JAK3 and STAT5, and serine/threonine phosphorylation of IL-2Rbeta. Moreover, inhibition of PP2A, but not PP1, diminished IL-2-induced tyrosine phosphorylation of IL-2Rbeta, JAK3, and STAT5, and abolished STAT5 DNA binding activity. Serine/threonine phosphorylation of IL-2Rbeta by a staurosporine-sensitive kinase also blocked its association with JAK3 and IL-2Rgamma in YT cells. Taken together, these data indicate that serine/threonine phosphorylation negatively regulates IL-2 signaling at multiple levels, including receptor complex formation and JAK3/STAT5 activation, and that this regulation is counteracted by PP2A. These findings also suggest that PP2A may serve as a therapeutic target for modulating JAK3/STAT5 activation in human disease.

  3. Petrological and geochemical constraints on granitoid formation: The Waldoboro Pluton Complex, Maine

    SciTech Connect

    Barton, M. . Dept. of Geological Science); Sidle, W.S. )

    1992-01-01

    The Waldoboro Pluton Complex (WPC) comprises seven units ranging from qtz-diorite to aplite. The country rocks are biotite-rich metagraywackes with minor shales mostly belonging to the Proterozoic Z-Ordovician Bucksport Formation. Field evidence strongly suggests that the WPC formed in-situ: contacts with the country rock are cryptic, transitional and concordant; restitic minerals in the granitoids are identical to those in the country rocks; prolific metasedimentary enclaves in the WPC are locally derived. Major and trace element data for country rock and the most voluminous units of the WPC define consistent linear trends suggesting limited melt segregation and retention of a high proportion of restite. Mixing models and partial melting models require 54--76% melting for generation of the gneissic granites and two-mica granites. Garnet-biotite geothermometry and garnet-Al[sub 2]SiO[sub 5]-SiO[sub 2]-plagioclase geobarometry indicate that the WPC formed at T = 740--780 C and P = 0.4--0.7 GPa. Published experimental data show that < 50% melting is likely under these conditions if melting is controlled by dehydration reactions. Bucksport lithologies contain < 20% biotite, suggesting that the maximum amount of melt that could have formed by dehydration melting is < 20%, even if all biotite was consumed during melting. It seems probable that a free fluid phase was required to generate the WPC. Migmatization is apparent in all lithologies (including amphibolites) in the vicinity of the WPC, consistent with fluid-present melting. Fluid may have ingressed along the St. George thrust, but the source of the fluid is unknown.

  4. Characterizing Extragalactic Star Formation with GALEX Legacy Photometric Analysis of UV-Bright Stellar Comple