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Sample records for stabilizes multimer formation

  1. Arachidonic acid mediates the formation of abundant alpha-helical multimers of alpha-synuclein

    NASA Astrophysics Data System (ADS)

    Iljina, Marija; Tosatto, Laura; Choi, Minee L.; Sang, Jason C.; Ye, Yu; Hughes, Craig D.; Bryant, Clare E.; Gandhi, Sonia; Klenerman, David

    2016-09-01

    The protein alpha-synuclein (αS) self-assembles into toxic beta-sheet aggregates in Parkinson’s disease, while it is proposed that αS forms soluble alpha-helical multimers in healthy neurons. Here, we have made αS multimers in vitro using arachidonic acid (ARA), one of the most abundant fatty acids in the brain, and characterized them by a combination of bulk experiments and single-molecule Fӧrster resonance energy transfer (sm-FRET) measurements. The data suggest that ARA-induced oligomers are alpha-helical, resistant to fibril formation, more prone to disaggregation, enzymatic digestion and degradation by the 26S proteasome, and lead to lower neuronal damage and reduced activation of microglia compared to the oligomers formed in the absence of ARA. These multimers can be formed at physiologically-relevant concentrations, and pathological mutants of αS form less multimers than wild-type αS. Our work provides strong biophysical evidence for the formation of alpha-helical multimers of αS in the presence of a biologically relevant fatty acid, which may have a protective role with respect to the generation of beta-sheet toxic structures during αS fibrillation.

  2. Formation of highly ordered multimers in G-quadruplexes.

    PubMed

    Tóthová, Petra; Krafčíková, Petra; Víglaský, Viktor

    2014-11-18

    G-Rich DNA and RNA have a higher propensity to form G-quadruplex structures, but the presence of G-runs alone is not sufficient to prove that such sequences can form stable G-quadruplexes. While G-rich sequences are essential for G-quadruplex formation, not all G-rich sequences have the propensity to form G-quadruplex structures. In addition, monovalent metal ions, dehydrating agents, and loop sequences connecting the G-runs also play important roles in the topology of G-quadruplex folding. To date, no quantitative analysis of the CD spectra of G-quadruplexes in confrontation with the electrophoretic results has been performed. Therefore, in this study, we use information gained through the analysis of a series of well-known G-quadruplex-forming sequences to evaluate other less-studied sets of aptameric sequences. A simple and cost-effective methodology that can verify the formation of G-quadruplex motifs from oligomeric DNA sequences and a technique to determine the molecularity of these structures are also described. This methodology could be of great use in the prediction of G-quadruplex assembly, and the basic principles of our techniques can be extrapolated for any G-rich DNA sequences. This study also presents a model that can predict the multimerization of G-quadruplexes; the predictions offered by this model are shown to match the results obtained using circular dichroism.

  3. Multimer Formation Explains Allelic Suppression of PRDM9 Recombination Hotspots

    PubMed Central

    Baker, Christopher L.; Petkova, Pavlina; Walker, Michael; Flachs, Petr; Mihola, Ondrej; Trachtulec, Zdenek; Petkov, Petko M.; Paigen, Kenneth

    2015-01-01

    Genetic recombination during meiosis functions to increase genetic diversity, promotes elimination of deleterious alleles, and helps assure proper segregation of chromatids. Mammalian recombination events are concentrated at specialized sites, termed hotspots, whose locations are determined by PRDM9, a zinc finger DNA-binding histone methyltransferase. Prdm9 is highly polymorphic with most alleles activating their own set of hotspots. In populations exhibiting high frequencies of heterozygosity, questions remain about the influences different alleles have in heterozygous individuals where the two variant forms of PRDM9 typically do not activate equivalent populations of hotspots. We now find that, in addition to activating its own hotspots, the presence of one Prdm9 allele can modify the activity of hotspots activated by the other allele. PRDM9 function is also dosage sensitive; Prdm9 +/- heterozygous null mice have reduced numbers and less active hotspots and increased numbers of aberrant germ cells. In mice carrying two Prdm9 alleles, there is allelic competition; the stronger Prdm9 allele can partially or entirely suppress chromatin modification and recombination at hotspots of the weaker allele. In cell cultures, PRDM9 protein variants form functional heteromeric complexes which can bind hotspots sequences. When a heteromeric complex binds at a hotspot of one PRDM9 variant, the other PRDM9 variant, which would otherwise not bind, can still methylate hotspot nucleosomes. We propose that in heterozygous individuals the underlying molecular mechanism of allelic suppression results from formation of PRDM9 heteromers, where the DNA binding activity of one protein variant dominantly directs recombination initiation towards its own hotspots, effectively titrating down recombination by the other protein variant. In natural populations with many heterozygous individuals, allelic competition will influence the recombination landscape. PMID:26368021

  4. Multimer Formation Explains Allelic Suppression of PRDM9 Recombination Hotspots.

    PubMed

    Baker, Christopher L; Petkova, Pavlina; Walker, Michael; Flachs, Petr; Mihola, Ondrej; Trachtulec, Zdenek; Petkov, Petko M; Paigen, Kenneth

    2015-09-01

    Genetic recombination during meiosis functions to increase genetic diversity, promotes elimination of deleterious alleles, and helps assure proper segregation of chromatids. Mammalian recombination events are concentrated at specialized sites, termed hotspots, whose locations are determined by PRDM9, a zinc finger DNA-binding histone methyltransferase. Prdm9 is highly polymorphic with most alleles activating their own set of hotspots. In populations exhibiting high frequencies of heterozygosity, questions remain about the influences different alleles have in heterozygous individuals where the two variant forms of PRDM9 typically do not activate equivalent populations of hotspots. We now find that, in addition to activating its own hotspots, the presence of one Prdm9 allele can modify the activity of hotspots activated by the other allele. PRDM9 function is also dosage sensitive; Prdm9+/- heterozygous null mice have reduced numbers and less active hotspots and increased numbers of aberrant germ cells. In mice carrying two Prdm9 alleles, there is allelic competition; the stronger Prdm9 allele can partially or entirely suppress chromatin modification and recombination at hotspots of the weaker allele. In cell cultures, PRDM9 protein variants form functional heteromeric complexes which can bind hotspots sequences. When a heteromeric complex binds at a hotspot of one PRDM9 variant, the other PRDM9 variant, which would otherwise not bind, can still methylate hotspot nucleosomes. We propose that in heterozygous individuals the underlying molecular mechanism of allelic suppression results from formation of PRDM9 heteromers, where the DNA binding activity of one protein variant dominantly directs recombination initiation towards its own hotspots, effectively titrating down recombination by the other protein variant. In natural populations with many heterozygous individuals, allelic competition will influence the recombination landscape.

  5. Involvement of surface cysteines in activity and multimer formation of thimet oligopeptidase.

    PubMed

    Sigman, J A; Sharky, M L; Walsh, S T; Pabon, A; Glucksman, M J; Wolfson, A J

    2003-08-01

    Thimet oligopeptidase is a metalloenzyme involved in regulating neuropeptide processing. Three cysteine residues (246, 248, 253) are known to be involved in thiol activation of the enzyme. In contrast to the wild-type enzyme, the triple mutant (C246S/C248S/C253S) displays increased activity in the absence of dithiothreitol. Dimers, purportedly formed through cysteines 246, 248 and 253, have been thought to be inactive. However, analysis of the triple mutant by native gel electrophoresis reveals the existence of dimers and multimers, implying that oligomer formation is mediated by other cysteines, probably on the surface, and that some of these forms are enzymatically active. Isolation and characterization of iodoacetate-modified monomers and dimers of the triple mutant revealed that, indeed, certain dimeric forms of the enzyme are still fully active, whereas others show reduced activity. Cysteine residues potentially involved in dimerization were identified by modeling of thimet oliogopeptidase to its homolog, neurolysin. Five mutants were constructed; all contained the triple mutation C246S/C248S/C253S and additional substitutions. Substitutions at C46 or C682 and C687 prevented multimer formation and inhibited dimer formation. The C46S mutant had enzymatic activity comparable to the parent triple mutant, whereas that of C682S/C687S was reduced. Thus, the location of intermolecular disulfide bonds, rather than their existence per se, is relevant to activity. Dimerization close to the N-terminus is detrimental to activity, whereas dimerization near the C-terminus has little effect. Altering disulfide bond formation is a potential regulatory factor in the cell owing to the varying oxidation states in subcellular compartments and the different compartmental locations and functions of the enzyme.

  6. Seed-Specific Expression of Spider Silk Protein Multimers Causes Long-Term Stability

    PubMed Central

    Weichert, Nicola; Hauptmann, Valeska; Helmold, Christine; Conrad, Udo

    2016-01-01

    Seeds enable plants to germinate and to grow in situations of limited availability of nutrients. The stable storage of different seed proteins is a remarkable presumption for successful germination and growth. These strategies have been adapted and used in several molecular farming projects. In this study, we explore the benefits of seed-based expression to produce the high molecular weight spider silk protein FLAG using intein-based trans-splicing. Multimers larger than 460 kDa in size are routinely produced, which is above the native size of the FLAG protein. The storage of seeds for 8 weeks and 1 year at an ambient temperature of 15°C does not influence the accumulation level. Even the extended storage time does not influence the typical pattern of multimerized bands. These results show that seeds are the method of choice for stable accumulation of products of complex transgenes and have the capability for long-term storage at moderate conditions, an important feature for the development of suitable downstream processes. PMID:26858734

  7. A conserved motif mediates both multimer formation and allosteric activation of phosphoglycerate mutase 5.

    PubMed

    Wilkins, Jordan M; McConnell, Cyrus; Tipton, Peter A; Hannink, Mark

    2014-09-05

    Phosphoglycerate mutase 5 (PGAM5) is an atypical mitochondrial Ser/Thr phosphatase that modulates mitochondrial dynamics and participates in both apoptotic and necrotic cell death. The mechanisms that regulate the phosphatase activity of PGAM5 are poorly understood. The C-terminal phosphoglycerate mutase domain of PGAM5 shares homology with the catalytic domains found in other members of the phosphoglycerate mutase family, including a conserved histidine that is absolutely required for catalytic activity. However, this conserved domain is not sufficient for maximal phosphatase activity. We have identified a highly conserved amino acid motif, WDXNWD, located within the unique N-terminal region, which is required for assembly of PGAM5 into large multimeric complexes. Alanine substitutions within the WDXNWD motif abolish the formation of multimeric complexes and markedly reduce phosphatase activity of PGAM5. A peptide containing the WDXNWD motif dissociates the multimeric complex and reduces but does not fully abolish phosphatase activity. Addition of the WDXNWD-containing peptide in trans to a mutant PGAM5 protein lacking the WDXNWD motif markedly increases phosphatase activity of the mutant protein. Our results are consistent with an intermolecular allosteric regulation mechanism for the phosphatase activity of PGAM5, in which the assembly of PGAM5 into multimeric complexes, mediated by the WDXNWD motif, results in maximal activation of phosphatase activity. Our results suggest the possibility of identifying small molecules that function as allosteric regulators of the phosphatase activity of PGAM5.

  8. Increased Length of Long Terminal Repeats Inhibits Ty1 Transposition and Leads to the Formation of Tandem Multimers

    PubMed Central

    Lauermann, V.; Hermankova, M.; Boeke, J. D.

    1997-01-01

    The Ty1 retrotransposon of Saccharomyces cerevisiae is bounded by long-terminal repeats (LTRs). We have constructed a variety of Ty1 elements in which the LTR length has been increased from the normal length of 334 bp to >2 kb. Although small insertions in the LTR have minimal effects on transposition frequency, larger insertions dramatically reduce it. Nevertheless, elements with long LTRs are incorporated into the genome at a low frequency. Most of these rare insertion events represent Ty1 tandem (head to tail) multimers. PMID:9093846

  9. Enhanced expression of tandem multimers of the antimicrobial peptide buforin II in Escherichia coli by the DEAD-box protein and trxB mutant.

    PubMed

    Lee, J H; Kim, M S; Cho, J H; Kim, S C

    2002-05-01

    The tandem multimeric expression of various peptides has been explored by many researchers. However, expression levels have usually not been proportional to the degree of multimerization. To increase the expression level in Escherichia coli of tandem multimers of a cationic antimicrobial peptide, buforin II, fused to an anionic peptide, we studied the effect of the DEAD-box protein and the trxB mutant on the expression of tandem multimers. An expression vector with a tac promoter was more effective in directing multimeric expression than one with a T7 promoter. The expression level of large multimers was substantially increased with the tac promoter, possibly through stabilization of long transcripts by synchronization of transcription and translation. Coexpression of the DEAD-box protein, an RNA-binding protein, with the T7 expression system increased the expression level of multimers, especially large multimers, due to protection of the long RNA transcripts. In addition, the use of the trxB mutant also enhanced the expression level of tandem multimers, which contain two cysteine residues at both ends of the monomeric unit. It seems that disulfide bonds formed in the multimers in the trxB mutant might help efficient charge neutralization for inclusion body formation of the multimers, resulting in enhancement of expression. Our results show that the expression of multimers can be improved through the stabilization of the long transcripts by the DEAD-box protein or the expression, under an oxidizing environment, of the trxB mutant in which covalent cross-links through disulfide bonds facilitate inclusion body formation of the multimeric fusion peptide.

  10. α-Synuclein assembles into higher-order multimers upon membrane binding to promote SNARE complex formation

    PubMed Central

    Burré, Jacqueline; Sharma, Manu; Südhof, Thomas C.

    2014-01-01

    Physiologically, α-synuclein chaperones soluble NSF attachment protein receptor (SNARE) complex assembly and may also perform other functions; pathologically, in contrast, α-synuclein misfolds into neurotoxic aggregates that mediate neurodegeneration and propagate between neurons. In neurons, α-synuclein exists in an equilibrium between cytosolic and membrane-bound states. Cytosolic α-synuclein appears to be natively unfolded, whereas membrane-bound α-synuclein adopts an α-helical conformation. Although the majority of studies showed that cytosolic α-synuclein is monomeric, it is unknown whether membrane-bound α-synuclein is also monomeric, and whether chaperoning of SNARE complex assembly by α-synuclein involves its cytosolic or membrane-bound state. Here, we show using chemical cross-linking and fluorescence resonance energy transfer (FRET) that α-synuclein multimerizes into large homomeric complexes upon membrane binding. The FRET experiments indicated that the multimers of membrane-bound α-synuclein exhibit defined intermolecular contacts, suggesting an ordered array. Moreover, we demonstrate that α-synuclein promotes SNARE complex assembly at the presynaptic plasma membrane in its multimeric membrane-bound state, but not in its monomeric cytosolic state. Our data delineate a folding pathway for α-synuclein that ranges from a monomeric, natively unfolded form in cytosol to a physiologically functional, multimeric form upon membrane binding, and show that only the latter but not the former acts as a SNARE complex chaperone at the presynaptic terminal, and may protect against neurodegeneration. PMID:25246573

  11. Rapid Restoration of Thrombus Formation and High-Molecular-Weight von Willebrand Factor Multimers in Patients with Severe Aortic Stenosis After Valve Replacement

    PubMed Central

    Yamashita, Keigo; Yagi, Hideo; Hayakawa, Masaki; Abe, Takehisa; Hayata, Yoshihiro; Yamaguchi, Naoko; Sugimoto, Mitsuhiko; Fujimura, Yoshihiro; Taniguchi, Shigeki

    2016-01-01

    Aim: Patients with severe aortic stenosis (AS) may have bleeding episodes due to the loss of high-molecular-weight (HMW) von Willebrand factor multimers (VWFMs). The absence of HMW-VWFMs and bleeding tendency are usually corrected after aortic valve replacement (AVR). To investigate the process of VWFM recovery and symptoms in patients with severe AS, we analyzed changes in VWF antigen (VWF:Ag), ADAMTS13 activity (ADAMTS13:AC), and platelet thrombus formation under high shear stress conditions. Methods: Nine patients with severe AS undergoing AVR were analyzed. Results: Evident deficiency of HMW-VWFMs was observed in six patients before surgery, which was rapidly restored within 8 days after AVR. Median levels of VWF:Ag before surgery, on postoperative days (PODs) 1, 8, 15, and 22, and one year after AVR were 78.1%, 130%, 224%, 155%, 134%, and 142%, respectively. In contrast, ADAMTS13:AC was 50.5%, 35.5%, 25.5%, 25.1%, 30.3%, and 84.6%, respectively. Preoperative thrombus formation but not surface coverage was significantly lower than that on POD 22, which was considered as normal level in each patient. Compared with preoperative levels, thrombus volume was significantly lower on POD 1, but rapidly increased by POD 8. Conclusion: Bleeding tendency and loss of HMW-VWFMs observed in patients with severe AS before surgery was rapidly corrected after AVR. Instead, patients were in a VWF-predominant state between POD 8 and 22. PMID:27052664

  12. Stabilizing clayey formations

    SciTech Connect

    Lipowski, S. A.; Miskel Jr., J. J.; Schick, M. J.

    1985-03-19

    Process for treating a clayey geological formation to prevent, inhibit or reduce swelling or migrating of clay particles in a formation by treating the formation with an effective amount of a quaternized oligomer which is the reaction product of a polyamine having a primary amino group and a tertiary amino group with a difunctional reactant to form a precondensate monomer which is then chain extended and quaternized by reaction with a dihalogenated hydrocarbon ether. A preferred oligomer is a product of: (I) about 1.0 mole of a precondensate which is the reaction product of (A) from about 2.0 to about 3.0 mole of a polyamine having a primary amino group and a tertiary amino group, the polyamine having a non-cyclic backbone containing between 1 and 6 carbon atoms, with (B) about 1.0 mole of a difunctional reactant which is a diester of a mixture of dicarboxylic acids such as adipic, glutaric and succinic acid, with (II) from about 1.0 to about 1.2 mole of a chain extender such as dichloroethylether. Process is useful in oil producing operations.

  13. Binding of factor VIII to von willebrand factor is enabled by cleavage of the von Willebrand factor propeptide and enhanced by formation of disulfide-linked multimers.

    PubMed

    Bendetowicz, A V; Morris, J A; Wise, R J; Gilbert, G E; Kaufman, R J

    1998-07-15

    von Willebrand factor (vWF) is a multimeric adhesive glycoprotein with one factor VIII binding site/subunit. Prior reports suggest that posttranslational modifications of vWF, including formation of N-terminal intersubunit disulfide bonds and subsequent cleavage of the propeptide, influence availability and/or affinity of factor VIII binding sites. We found that deletion of the vWF propeptide produced a dimeric vWF molecule lacking N-terminal intersubunit disulfide bonds. This molecule bound fluorescein-labeled factor VIII with sixfold lower affinity than multimeric vWF in an equilibrium flow cytometry assay (approximate KDs, 5 nmol/L v 0.9 nmol/L). Coexpression of propeptide-deleted vWF with the vWF propeptide in trans yielded multimeric vWF that displayed increased affinity for factor VIII. Insertion of an alanine residue at the N-terminus of the mature vWF subunit destroyed binding to factor VIII, indicating that the native mature N-terminus is required for factor VIII binding. The requirement for vWF propeptide cleavage was shown by (1) a point mutation of the vWF propeptide cleavage site yielding pro-vWF that was defective in factor VIII binding and (2) correlation between efficiency of intracellular propeptide cleavage and factor VIII binding. Furthermore, in a cell-free system, addition of the propeptide-cleaving enzyme PACE/furin enabled factor VIII binding in parallel with propeptide cleavage. Our results indicate that high-affinity factor VIII binding sites are located on N-terminal disulfide-linked vWF subunits from which the propeptide has been cleaved.

  14. Clay stabilization in low-permeability formations

    SciTech Connect

    Himes, R.E.; Vinson, E.F.; Simon, D.E. )

    1991-08-01

    The most popular clay stabilizers used recently in well-treating solutions are classified as cationic organic polymers (COP's). This paper reports on studies that have shown these stabilizers to be ineffective in microdarcy to low-millidarcy sandstones. Recent research led to the development of a stabilizer applicable to formations with permeabilities of 0.010 md and higher that also provides enhanced load-water recovery and more efficient placement from gelled-water solutions.

  15. Identity Formation in Adolescence: Change or Stability?

    ERIC Educational Resources Information Center

    Klimstra, Theo A.; Hale, William W., III; Raaijmakers, Quinten A. W.; Branje, Susan J. T.; Meeus, Wim H. J.

    2010-01-01

    The aim of this five-wave longitudinal study of 923 early to middle adolescents (50.7% boys; 49.3% girls) and 390 middle to late adolescents (43.3% boys and 56.7% girls) is to provide a comprehensive view on change and stability in identity formation from ages 12 to 20. Several types of change and stability (i.e., mean-level change, rank-order…

  16. Cyclic Imide Dioxime: Formation and Hydrolytic Stability

    SciTech Connect

    Kang, S.O.; Vukovic, Sinisa; Custelcean, Radu; Hay, Benjamin

    2012-01-01

    Poly(acrylamidoximes) play an important role in the uranium extraction from seawater. The present work reports solution studies of simple analogs to address the formation and stability of two binding sites present in these polymers, open-chain amidoximes and cyclic imide dioximes, including: 1) conditions that maximize the formation of the cyclic form, 2) existence of a base-induced conversion from open-chain to cyclic form, and 3) degradation under acid and base conditions.

  17. Two Cys residues essential for von Willebrand factor multimer assembly in the Golgi.

    PubMed

    Purvis, Angie R; Gross, Julia; Dang, Luke T; Huang, Ren-Huai; Kapadia, Milan; Townsend, R Reid; Sadler, J Evan

    2007-10-02

    Von Willebrand factor (VWF) dimerizes through C-terminal CK domains, and VWF dimers assemble into multimers in the Golgi by forming intersubunit disulfide bonds between D3 domains. This unusual oxidoreductase reaction requires the VWF propeptide (domains D1D2), which acts as an endogenous pH-dependent chaperone. The cysteines involved in multimer assembly were characterized by using a VWF construct that encodes the N-terminal D1D2D'D3 domains. Modification with thiol-specific reagents demonstrated that secreted D'D3 monomer contained reduced Cys, whereas D'D3 dimer and propeptide did not. Reduced Cys in the D'D3 monomer were alkylated with N-ethylmaleimide and analyzed by mass spectrometry. All 52 Cys within the D'D3 region were observed, and only Cys(1099) and Cys(1142) were modified by N-ethylmaleimide. When introduced into the D1D2D'D3 construct, the mutation C1099A or C1142A markedly impaired the formation of D'D3 dimers, and the double mutation prevented dimerization. In full-length VWF, the mutations C1099A and C1099A/C1142A prevented multimer assembly; the mutation C1142A allowed the formation of almost exclusively dimers, with few tetramers and no multimers larger than hexamers. Therefore, Cys(1099) and Cys(1142) are essential for the oxidoreductase mechanism of VWF multimerization. Cys(1142) is reported to form a Cys(1142)-Cys(1142) intersubunit bond, suggesting that Cys(1099) also participates in a Cys(1099)-Cys(1099) disulfide bond between D3 domains. This arrangement of intersubunit disulfide bonds implies that the dimeric N-terminal D'D3 domains of VWF subunits align in a parallel orientation within VWF multimers.

  18. Model format for a vaccine stability report and software solutions.

    PubMed

    Shin, Jinho; Southern, James; Schofield, Timothy

    2009-11-01

    A session of the International Association for Biologicals Workshop on Stability Evaluation of Vaccine, a Life Cycle Approach was devoted to a model format for a vaccine stability report, and software solutions. Presentations highlighted the utility of a model format that will conform to regulatory requirements and the ICH common technical document. However, there need be flexibility to accommodate individual company practices. Adoption of a model format is premised upon agreement regarding content between industry and regulators, and ease of use. Software requirements will include ease of use and protections against inadvertent misspecification of stability design or misinterpretation of program output.

  19. Characterization of α-Synuclein Multimer Stoichiometry in Complex Biological Samples by Electrophoresis.

    PubMed

    Killinger, Bryan A; Moszczynska, Anna

    2016-04-05

    The aberrant aggregation of α-synuclein in the brain is a hallmark of Parkinson's disease (PD). In vivo soluble α-synuclein occurs as a monomer and several multimers, the latter of which may be important for the biological function of α-synuclein. Currently, there is a lack of reproducible methods to compare α-synuclein multimer abundance between complex biological samples. Here we developed a method, termed "multimer-PAGE," that combines in-gel chemical cross-linking with several common electrophoretic techniques to measure the stoichiometry of soluble α-synuclein multimers in brain tissue lysates. Results show that soluble α-synuclein from the rat brain exists as several high molecular weight species of approximately 56 kDa (αS56), 80 kDa (αS80), and 100 kDa (αS100) that comigrate with endogenous lipids, detergents, and/or micelles during blue native gel electrophoresis (BN-PAGE). Co-extraction of endogenous lipids with α-synuclein was essential for the detection of soluble α-synuclein multimers. Homogenization of brain tissue in small buffer volumes (>50 mg tissue per 1 mL buffer) increased relative lipid extraction and subsequently resulted in abundant soluble multimer detection via multimer-PAGE. α-Synuclein multimers captured by directly cross-linking soluble lysates resembled those observed following multimer-PAGE. The ratio of multimer (αS80) to monomer (αS17) increased linearly with protein input into multimer-PAGE, suggesting to some extent, multimers were also formed during electrophoresis. Overall, soluble α-synuclein maintains lipid interactions following tissue disruption and readily forms multimers when this lipid-protein complex is preserved. Once the multimer-PAGE technique was validated, relative stoichiometric comparisons could be conducted simultaneously between 14 biological samples. Multimer-PAGE provides a simple inexpensive biochemical technique to study the molecular factors influencing α-synuclein multimerization.

  20. Unique profile of chicken adiponectin, a predominantly heavy molecular weight multimer, and relationship to visceral adiposity.

    PubMed

    Hendricks, Gilbert L; Hadley, Jill A; Krzysik-Walker, Susan M; Prabhu, K Sandeep; Vasilatos-Younken, Regina; Ramachandran, Ramesh

    2009-07-01

    Adiponectin, a 30-kDa adipokine hormone, circulates as heavy, medium, and light molecular weight isoforms in mammals. Plasma heavy molecular weight (HMW) adiponectin isoform levels are inversely correlated with the incidence of type 2 diabetes in humans. The objectives of the present study were to characterize adiponectin protein and quantify plasma adiponectin levels in chickens, which are naturally hyperglycemic relative to mammals. Using gel filtration column chromatography and Western blot analysis under nonreducing and non-heat-denaturing native conditions, adiponectin in chicken plasma, and adipose tissue is predominantly a multimeric HMW isoform that is larger than 669 kDa mass. Under reducing conditions and heating to 70-100 C, however, a majority of the multimeric adiponectin in chicken plasma and adipose tissue was reduced to oligomeric and/or monomeric forms. Immunoprecipitation and elution under neutral pH preserved the HMW adiponectin multimer, whereas brief exposure to acidic pH led to dissociation of HMW multimer into multiple oligomers. Mass spectrometric analysis of chicken adiponectin revealed the presence of hydroxyproline and differential glycosylation of hydroxylysine residues in the collagenous domain. An enzyme immunoassay was developed and validated for quantifying plasma adiponectin in chickens. Plasma adiponectin levels were found to be significantly lower in 8- compared with 4-wk-old male chickens and inversely related to abdominal fat pad mass. Collectively, our results provide novel evidence that adiponectin in chicken plasma and tissues is predominantly a HMW multimer, suggesting the presence of unique multimerization and stabilization mechanisms in the chicken that favors preponderance of HMW adiponectin over other oligomers.

  1. Formation and stability of samarium iron carbides

    NASA Astrophysics Data System (ADS)

    Mao, Ou

    Phase formation and transformation in mechanically alloyed iron-rich Sm-Fe-C is the principal subject of this thesis. Ternary Sm-Fe-C is a complicated system. The strategy was therefore to start with a binary system. A series of mechanically alloyed R2Fe17 powders were investigated for a better understanding of both the Sm-Fe alloy system in general and the Sm2Fe17 compound in particular. The objective was to learn (1) what is the steady-state in the mechanically alloyed R2Fe17, and (2) how the 2-17 structure is formed from the mechanically alloyed precursors. Phase formation and transformation in the mechanically alloyed Sm2Fe17Cx with various carbon contents was then studied. The objective in this case was to learn (1) how the 2-17 structure with interstitial carbon is formed, (2) what is the maximum C content in the 2-17 structure, the critical content xc, and (3) what phase(s) is (are) formed with x>xc. Phase transformation from Sm2Fe17Cx to Sm2Fe14C was the second subject for study. As required by this study, the grain refinement process was investigated first. The objective was to prepare the nanocrystalline Sm2Fe17Cx with various grain sizes. Emphasis was on the ball milling of Sm2Fe17/graphite mixture in the hope of forming a nano-scale mixing of Sm2Fe17 and graphite by ball milling. Solid-solid reaction between the Sm2Fe17 and graphite leading to the formation of nanocrystalline Sm2Fe17Cx was then studied. The phase transformation from Sm2Fe17 was carried out with nanocrystalline Sm2Fe17Cx samples. Samples prepared by other methods were also studied. The objective was to learn (1) what the transformation product is and (2) what the kinetics of the phase transformation and its grain size dependence are. (Abstract shortened by UMI.)

  2. String Stability of a Linear Formation Flight Control System

    NASA Technical Reports Server (NTRS)

    Allen, Michael J.; Ryan, Jack; Hanson, Curtis E.; Parle, James F.

    2002-01-01

    String stability analysis of an autonomous formation flight system was performed using linear and nonlinear simulations. String stability is a measure of how position errors propagate from one vehicle to another in a cascaded system. In the formation flight system considered here, each i(sup th) aircraft uses information from itself and the preceding ((i-1)(sup th)) aircraft to track a commanded relative position. A possible solution for meeting performance requirements with such a system is to allow string instability. This paper explores two results of string instability and outlines analysis techniques for string unstable systems. The three analysis techniques presented here are: linear, nonlinear formation performance, and ride quality. The linear technique was developed from a worst-case scenario and could be applied to the design of a string unstable controller. The nonlinear formation performance and ride quality analysis techniques both use nonlinear formation simulation. Three of the four formation-controller gain-sets analyzed in this paper were limited more by ride quality than by performance. Formations of up to seven aircraft in a cascaded formation could be used in the presence of light gusts with this string unstable system.

  3. Theranostic Value of Multimers: Lessons Learned from Trimerization of Neurotensin Receptor Ligands and Other Targeting Vectors

    PubMed Central

    Maschauer, Simone; Einsiedel, Jürgen; Reich, Dominik; Hübner, Harald; Gmeiner, Peter; Wester, Hans-Jürgen; Prante, Olaf; Notni, Johannes

    2017-01-01

    Neurotensin receptor 1 (NTS1) is overexpressed on a variety of cancer entities; for example, prostate cancer, ductal pancreatic adenocarcinoma, and breast cancer. Therefore, it represents an interesting target for the diagnosis of these cancers types by positron emission tomography (PET). The metabolically-stabilized neurotensin (NT) derivative peptide Nlys8-Lys9-Pro10-Tyr11-Tle12-Leu13-OH was elongated at the N-terminus with 6-azido norleucine and coupled with the 1,4,7-triazacyclononane-1,4,7-tris[(2-carboxyethyl)methylenephosphinic acid] (TRAP) chelator TRAP(alkyne)3 in order to synthesize a NT trimer with subnanomolar affinity and high stability. The 68Ga-labeled peptide [68Ga]Ga-TRAP(NT4)3 was characterized in vitro using the NTS1-expressing human colorectal adenocarcinoma cell line HT29. It displayed fast and high internalization rates of >90%, but also fast efflux rates of 50% over 15 min. In vivo, [68Ga]Ga-TRAP(NT4)3 showed moderate HT29 tumor uptake values of 1.7 %ID/g at 60 min post-injection (p.i.), but also high uptake and retention in the kidneys and liver. A comparison of data for trimer/monomer pairs of NT ligands and other targeting vectors (peptides and peptoids targeting integrins αvβ3, α5β1, and αvβ6, the PSMA-ligand DUPA (2-[3-(1,3-dicarboxypropyl)-ureido]pentanedioic acid), and nitroimidazoles targeting hypoxia) revealed that multimers always exhibit higher target affinities and tumor uptake, but not necessarily improved tumor-to-tissue ratios. Thus, although in vitro data are not suitable for prediction of in vivo performance, multimers are potentially superior to monomers, particularly for applications where high tumor accumulation is crucial. PMID:28287433

  4. Association of adiponectin multimers with Barrett’s oesophagus

    PubMed Central

    Rubenstein, J H; Kao, J Y; Madanick, R D; Zhang, M; Wang, M; Spacek, M B; Donovan, J L; Bright, S D; Shaheen, N J

    2012-01-01

    Objective Barrett’s oesophagus is associated with abdominal obesity. Adiponectin is a peptide that is secreted from adipocytes and circulates in three multimeric forms: low molecular weight (LMW), middle molecular weight (MMW), and high molecular weight (HMW). The anti-inflammatory effects of adiponectin are specific to individual multimers, with LMW being most anti-inflammatory. We postulated that circulating levels of adiponectin and its multimers would be associated with the risk of Barrett’s oesophagus. Design Cross-sectional study. Setting Outpatient clinic in North Carolina, USA. Patients Cases of Barrett’s oesophagus and controls undergoing upper endoscopy for gastro-oesophageal reflux disease (GORD). Main outcome measures Adjusted odds ratios of plasma adiponectin levels and its multimers for Barrett’s oesophagus. Results There were 112 cases of Barrett’s oesophagus and 199 GORD controls. Total adiponectin was not associated with Barrett’s oesophagus (3rd tertile vs 1st tertile adjusted odds ratio (aOR) = 0.88; 95% confidence interval (CI) = 0.44 to 1.78). High levels of LMW adiponectin were associated with a decreased risk of Barrett’s oesophagus (3rd tertile vs 1st tertile aOR = 0.33; 95% CI, 0.16 to 0.69), and a high LMW/total ratio appeared particularly inversely associated with Barrett’s oesophagus (3rd tertile vs 1st tertile aOR = 0.27; 95% CI, 0.13 to 0.58). Conclusions High levels of LMW adiponectin are associated with a decreased risk of Barrett’s oesophagus among patients with GORD. Further human studies are required to confirm these findings, and in vitro studies are needed to understand if there is a mechanism whereby adiponectin may affect Barrett’s metaplasia. PMID:19570765

  5. Characterization of α-Synuclein Multimer Stoichiometry in Complex Biological Samples by Electrophoresis

    PubMed Central

    2016-01-01

    The aberrant aggregation of α-synuclein in the brain is a hallmark of Parkinson’s disease (PD). In vivo soluble α-synuclein occurs as a monomer and several multimers, the latter of which may be important for the biological function of α-synuclein. Currently, there is a lack of reproducible methods to compare α-synuclein multimer abundance between complex biological samples. Here we developed a method, termed “multimer-PAGE,” that combines in-gel chemical cross-linking with several common electrophoretic techniques to measure the stoichiometry of soluble α-synuclein multimers in brain tissue lysates. Results show that soluble α-synuclein from the rat brain exists as several high molecular weight species of approximately 56 kDa (αS56), 80 kDa (αS80), and 100 kDa (αS100) that comigrate with endogenous lipids, detergents, and/or micelles during blue native gel electrophoresis (BN-PAGE). Co-extraction of endogenous lipids with α-synuclein was essential for the detection of soluble α-synuclein multimers. Homogenization of brain tissue in small buffer volumes (>50 mg tissue per 1 mL buffer) increased relative lipid extraction and subsequently resulted in abundant soluble multimer detection via multimer-PAGE. α-Synuclein multimers captured by directly cross-linking soluble lysates resembled those observed following multimer-PAGE. The ratio of multimer (αS80) to monomer (αS17) increased linearly with protein input into multimer-PAGE, suggesting to some extent, multimers were also formed during electrophoresis. Overall, soluble α-synuclein maintains lipid interactions following tissue disruption and readily forms multimers when this lipid–protein complex is preserved. Once the multimer-PAGE technique was validated, relative stoichiometric comparisons could be conducted simultaneously between 14 biological samples. Multimer-PAGE provides a simple inexpensive biochemical technique to study the molecular factors influencing α-synuclein multimerization

  6. New Insight into Cataract Formation: Enhanced Stability through Mutual Attraction

    SciTech Connect

    Stradner, A.; Schurtenberger, P.; Foffi, G.; Dorsaz, N.; Thurston, G.

    2007-11-09

    Small-angle neutron scattering experiments and molecular dynamics simulations combined with an application of concepts from soft matter physics to complex protein mixtures provide new insight into the stability of eye lens protein mixtures. Exploring this colloid-protein analogy we demonstrate that weak attractions between unlike proteins help to maintain lens transparency in an extremely sensitive and nonmonotonic manner. These results not only represent an important step towards a better understanding of protein condensation diseases such as cataract formation, but provide general guidelines for tuning the stability of colloid mixtures, a topic relevant for soft matter physics and industrial applications.

  7. Formation and Stability of Partially-Neutralized Plasma Clumps.

    DTIC Science & Technology

    1987-01-01

    propagation in the vacuum region, to the extent studied in the experiments. The goal of that related work is the generation of nearly charge-neutral...A179 444 FORMATION AND STABILITY OF PARTIALLY-NEUTRALIZED PLOSMA Y CLUNPS(U) MARYLAND UNIV COLLEGE PARK LAS FOR PLASMA AND FUSION ENERGY STUDIES J...Energy Studies / Bldg 410 Energy Research 3ldg, College Park Md 20742 Bolling AFB, D.C. 20332-6448 Ga. NAME OF FUNOING;SPONSORINGB. OFFICE SYMBOL 9

  8. Formation and stabilization of C6- by radiative electron attachment

    NASA Astrophysics Data System (ADS)

    Chandrasekaran, Vijayanand; Prabhakaran, Aneesh; Kafle, Bhim; Rubinstein, Hilel; Heber, Oded; Rappaport, Michael; Toker, Yoni; Zajfman, Daniel

    2017-03-01

    Radiative electron attachment (REA) plays an important role in forming molecular anions in various astrophysical environments. In this work, we determined the rate coefficient for the formation of C6- by REA based on a detailed balance approach. C6- ions are stored in an electrostatic ion beam trap and are photoexcited above their adiabatic detachment energy (4.18 eV). Due to fast internal conversion and intramolecular vibrational redistribution, photoexcitation leads to the formation of temporary negative ions (TNIs), the same as those one formed by the electron attachment. Absolute vibrational autodetachment and recurrent (or Poincaré) fluorescence (RF) rate coefficients have already been reported [V. Chandrasekaran et al., J. Phys. Chem. Lett. 5, 4078 (2014)]. Knowing the branching ratios of the various competing rate coefficients is decisive to the understanding of the formation probability of anions via REA. The radiative stabilization rate of C6-, shown to be dominated by RF, was determined to be 5 × 104 s-1 at the electron detachment energy, i.e., at least a factor of 100 faster than the stabilization by infrared transitions. The RF is found to very effectively stabilize the TNI formed by electron attachment. Using detailed balance to link the measured delayed detachment rate to the rate of electron attachment, we estimate the REA rate leading to the formation of C6- to be 3 × 10-7 cm3 s-1 at 300 K in agreement with theory (1.7 × 10-7 cm3 s-1 [R. Terzieva and E. Herbst, Int. J. Mass Spectrom. 201, 135 (2000)]). Such a high rate for REA to C6 indicates that REA may play a prominent role in the formation of anions in the interstellar medium.

  9. Detergent Stabilized Nanopore Formation Kinetics of an Anthrax Protein

    NASA Astrophysics Data System (ADS)

    Peterson, Kelby

    2015-03-01

    This summer research project funded through the Society of Physics Students Internship Program and The National Institute of Standards and Technology focused on optimization of pore formation of Protective Antigen protein secreted by Bacillus Anthraces. This experiment analyzes the use of N-tetradecylphosphocholine (FOS-14 Detergent) to stabilize the water soluble protein, protective antigen protein (PA63) to regulate the kinetics of pore formation in a model bilayer lipid membrane. The FOS-14 Detergent was tested under various conditions to understand its impact on the protein pore formation. The optimization of this channel insertion is critical in preparing samples of oriented for neutron reflectometry that provide new data to increase the understanding of the protein's structure.

  10. Formation, early evolution, and gravitational stability of protoplanetary disks

    NASA Technical Reports Server (NTRS)

    Nakamoto, Taishi; Nakagawa, Yoshitsugo

    1994-01-01

    The formation, viscous evolution, and gravitational stability of protoplanetary disks are investigated. The formation process is parameterized by the angular velocity of the molecular cloud core omega, while the viscous evolution is parameterized by the viscosity parameter alpha in the disk; in this study we consider a range of (0.4-6) x 10(exp -14)/s for omega and from 10(exp -5) to 10(exp -1) for alpha. The axisymmetric gravitational stabilities of the disks are checked using Toomre's criterion. The resulting disk surface temperature distribution, (d log T(sub s)/d log R) approximately = -0.6 (R is the cylindrical radius), can be attributed to two heating sources: the viscous heating dominant in the inner disk region, and the accretion shock heating dominant in the outer disk region. This surface temperature distribution matches that observed in many disks around young stellar objects. During the infall stage, disks with alpha less than 10(exp -1.5) become gravitationally unstable independent of omega. The gravitational instabilities occur at radii ranging from 5 to 40 AU. The ratio of the disk mass to the central star mass ranges from 0.2 to 0.5 at the times of instability, about 4 x 10(exp -5) x (omega/10(exp -14)/s)(exp -0.67) yr. Most disks with low alpha and high omega become gravitationally unstable during their formation phase.

  11. The Formation and Stability of Alkylthiol Monolayers on Carbon Substrates

    PubMed Central

    Lockett, Matthew R.; Smith, Lloyd M.

    2010-01-01

    The formation and stability of alkylthiol monolayers on amorphous carbon thin films are investigated. Alkylthiol monolayers were prepared via a two-step, wet chemical process in which the carbon surface was first halogenated and then incubated with (4-(trifluoromethyl)phenyl)methanethiol (4tBM). The 4tBM covalently attaches to the surface in a substitution reaction in which the 4tBM thiol replaces the surface halogen. Studies of the substitution mechanism showed that monolayer formation is affected by the nature of the surface-bound halogen as well as the concentration and nucleophilicity of the 4tBM sulfur atom, consistent with a bimolecular (SN2) substitution reaction mechanism. The alkylthiol monolayers are stable over a wide range of solvent, pH, and temperature conditions. PMID:20706614

  12. Pickering emulsions stabilized by oppositely charged colloids: Stability and pattern formation

    NASA Astrophysics Data System (ADS)

    Christdoss Pushpam, Sam David; Basavaraj, Madivala G.; Mani, Ethayaraja

    2015-11-01

    A binary mixture of oppositely charged colloids can be used to stabilize water-in-oil or oil-in-water emulsions. A Monte Carlo simulation study to address the effect of charge ratio of colloids on the stability of Pickering emulsions is presented. The colloidal particles at the interface are modeled as aligned dipolar hard spheres, with attractive interaction between unlike-charged and repulsive interaction between like-charged particles. The optimum composition (fraction of positively charged particles) required for the stabilization corresponds to a minimum in the interaction energy per particle. In addition, for each charge ratio, there is a range of compositions where emulsions can be stabilized. The structural arrangement of particles or the pattern formation at the emulsion interface is strongly influenced by the charge ratio. We find well-mixed isotropic, square, and hexagonal arrangements of particles on the emulsion surface for different compositions at a given charge ratio. The distribution of coordination numbers is calculated to characterize structural features. The simulation study is useful for the rational design of Pickering emulsifications wherein oppositely charged colloids are used, and for the control of pattern formation that can be useful for the synthesis of colloidosomes and porous shells derived thereof.

  13. Polymer Stabilized Nanosuspensions Formed via Flash Nanoprecipitation: Nanoparticle Formation, Formulation, and Stability

    NASA Astrophysics Data System (ADS)

    Zhu, ZhengXi

    Nanoparticles loaded with hydrophobic components (e.g., active pharmaceutical ingredients, medical diagnostic agents, nutritional or personal care chemicals, catalysts, dyes/pigments, and substances with exceptional magnetic/optical/electronic/thermal properties) have tremendous industrial applications. The common desire is to efficiently generate nanoparticles with a desired size, size distribution, and size stability. Recently, Flash NanoPrecipition (FNP) technique with a fast, continuous, and easily scalable process has been developed to efficiently generate hydrophobe-loaded nanoparticles. This dissertation extended this technique, optimized process conditions and material formulations, and gave new insights into the mechanism and kinetics of nanoparticle formation. This dissertation demonstrated successful generation of spherical beta-carotene nanoparticles with an average diameter of 50--100 nm (90 wt% nanoparticles below 200 nm), good size stability (maintained an average diameter below 200 nm for at least one week in saline), and much higher loading (80--90 wt%) than traditional carriers, such as micelles and polymersomes (typically <20 wt%). Moreover, the nanoparticles are amorphous and expected to have a high dissolution rate and bioavailability. To give insights into the mechanism and kinetics of nanoparticle formation, much remarkable evidence supported the kinetically frozen structures of the nanoparticles rather than the thermodynamic equilibrium micelles. Time scales of the particle formation via FNP were proposed. To optimize the material formulations, either polyelectrolytes (i.e., epsilon-polylysine, branched and linear poly(ethylene imine), and chitosan) or amphiphilic diblock copolymers (i.e., polystyrene-b-poly(ethylene glycol) (PS-b-PEG), polycarprolactone-b-poly(ethylene glycol) (PCL-b-PEG), poly(lactic acid)-b-poly(ethylene glycol) (PLA-b-PEG), and poly(lactic-co-glycolic acid)-b-poly(ethylene glycol) (PLGA-b-PEG)) were selectively screened

  14. Formation and Stability of Radiation Products in Europa's Icy Shell

    NASA Technical Reports Server (NTRS)

    Moore, M. H.; Hudson, R. L.; Carlson, R. W.; Ferrante, R. F.

    2004-01-01

    Spectra of Europa reveal a surface dominated by water-ice along with hydrated materials and minor amounts of SO2, CO2, and H2O2. Jovian magnetospheric ions (protons, sulfur, and oxygen) and electrons produce significant chemical modifications of the surface on time scales of a few years at micrometer depths. Our laboratory studies examine the formation and stability of radiation products in H2O-rich ices relevant to Europa. Infrared (IR) spectra of ices before and after irradiation reveal the radiation destruction of molecules and the formation of products at 86 - 132 K. In addition, spectra of ices during warming track thermal evolution due to chemical changes and sublimation processes. IR-identified radiation products in 86 - 132 K irradiated H2O + SO2 ices are the bisulfate ion, HSO4(-), sulfate ion, SO4(2-) and the hydronium ion, H3O(+). Warming results in the formation of a residual spectrum similar to liquid sulfuric acid, H2SO4, for H2O:SO2 ratios of 30:1, whereas hydrated sulfuric acid, H2SO4 4 H2O, forms for ratios of 30:1. Radiation products identified for irradiated H2O + H2S ices at 86 K are H2S2 and SO2. When irradiated at 110 and 132 K, ices with H2O:H2S ratios if either 3:1 or 30:1 show the formation of H2SO4 4 H2O on warming to 175 K. We have also examined the radiation stability of H2SO4. Addition of CO2 to H2O + SO2 ices results in the formation of CO3 at 2046 cm (sup -1) (4.89 m). This is the strongest band from a carbon-containing product in the mid-IR spectral region, and it is also seen when either pure CO2 or H2O + CO2 ice is irradiated. Experiments with CH4 added to H2O + SO2 + CO2 ices addressed the question of methane's use as a marker of methanogens in an irradiated ice environment. New results on the near-IR spectrum of pure H2O2 will be included in this presentation. Interpretations of near-IR water bands, with H2O2 present, will be discussed. Irradiations of H2O2 and H2O + H2O2 mixtures, to examine the possibility of O2 and O3

  15. Thermal Stability Threshold for Amyloid Formation in Light Chain Amyloidosis

    PubMed Central

    Poshusta, Tanya L.; Katoh, Nagaaki; Gertz, Morie A.; Dispenzieri, Angela; Ramirez-Alvarado, Marina

    2013-01-01

    Light chain (AL) amyloidosis is a devastating disease characterized by amyloid deposits formed by immunoglobulin light chains. Current available treatments involve conventional chemotherapy and autologous stem cell transplant. We have recently concluded a phase III trial comparing these two treatments. AL amyloidosis patients who achieve hematological complete response (CR) do not necessarily achieve organ response regardless of the treatment they received. In order to investigate the possible correlation between amyloid formation kinetics and organ response, we selected AL amyloidosis patients from the trial with kidney involvement and CR after treatment. Six patients were selected and their monoclonal immunoglobulin light chains were characterized. The proteins showed differences in their stability and their kinetics of amyloid formation. A correlation was detected at pH 7.4, showing that less stable proteins are more likely to form amyloid fibrils. AL-T03 is too unstable to form amyloid fibrils at pH 7.4. This protein was found in the only patient in the study that had organ response, suggesting that partially folded species are required for amyloid formation to occur in AL amyloidosis. PMID:24248061

  16. Analysis of von Willebrand factor multimers using a commercially available enhanced chemiluminescence kit.

    PubMed Central

    Cumming, A M; Wensley, R T

    1993-01-01

    AIMS--To develop a rapid, sensitive, and safe method for the analysis of von Willebrand factor (vWf) multimers in plasma or platelet lysates. METHOD--Analysis of vWf multimers was carried out by sodium dodecyl sulphate-agarose discontinuous gel electrophoresis followed by protein transfer to nitrocellulose membranes by western blotting. Blots were probed using horseradish peroxidase (HRP) conjugated rabbit anti-vWf; visualisation of vWf multimers was achieved using a commercially available enhanced chemi-Luminescence (ECL) kit for detecting HRP labelled antibodies on western blots. RESULTS--Electrophoretic transfer of vWf multimers to nitrocellulose membranes, including the higher molecular weight forms, was achieved satisfactorily and there was good resolution of individual multimer bands and of the triplet sub-band structure. Type II vWD variants were readily identifiable. The use of ECL conferred a high degree of sensitivity to the method and the end result on autoradiography film provided a permanent record which did not fade and which was suitable for scanning densitometry. CONCLUSION--The method for vWf multimer analysis described here is sensitive, simple to carry out, uses minimal amounts of reagents, produces results within 48 hours, and does not require the use of potentially hazardous radioactive materials or carcinogenic enzyme substrates. Images PMID:8320330

  17. Twinned silicon and germanium nanocrystals: Formation, stability and quantum confinement

    SciTech Connect

    Yu, Ting; Pi, Xiaodong Ni, Zhenyi; Zhang, Hui; Yang, Deren

    2015-03-15

    Although twins are often observed in Si/Ge nanocrystals (NCs), little theoretical investigation has been carried out to understand this type of important planar defects in Si/Ge NCs. We now study the twinning of Si/Ge NCs in the frame work of density functional theory by representatively considering single-twinned and fivefold-twinned Si/Ge NCs. It is found that the formation of twinned Si/Ge NCs is thermodynamically possible. The effect of twinning on the formation of Si NCs is different from that of Ge NCs. For both Si and Ge NCs twinning enhances their stability. The quantum confinement effect is weakened by twinning for Si NCs. Twinning actually enhances the quantum confinement of Ge NCs when they are small (<136 atoms), while weakening the quantum confinement of Ge NCs as their size is large (>136 atoms). The current results help to better understand the experimental work on twinned Si/Ge NCs and guide the tuning of Si/Ge-NC structures for desired properties.

  18. 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.

  19. Multimer recognition and secretion by the non-classical secretion pathway in Bacillus subtilis

    PubMed Central

    Zhao, Liuqun; Chen, Jingqi; Sun, Jibin; Zhang, Dawei

    2017-01-01

    Non-classical protein secretion in bacteria is a common phenomenon. However, the selection principle for non-classical secretion pathways remains unclear. Here, our experimental data, to our knowledge, are the first to show that folded multimeric proteins can be recognized and excreted by a non-classical secretion pathway in Bacillus subtilis. We explored the secretion pattern of a typical cytoplasmic protein D-psicose 3-epimerase from Ruminococcus sp. 5_1_39BFAA (RDPE), and showed that its non-classical secretion is not simply due to cell lysis. Analysis of truncation variants revealed that the C- and N-terminus, and two hydrophobic domains, are required for structural stability and non-classical secretion of RDPE. Alanine scanning mutagenesis of the hydrophobic segments of RDPE revealed that hydrophobic residues mediated the equilibrium between its folded and unfolded forms. Reporter mCherry and GFP fusions with RDPE regions show that its secretion requires an intact tetrameric protein complex. Using cross-linked tetramers, we show that folded tetrameric RDPE can be secreted as a single unit. Finally, we provide evidence that the non-classical secretion pathway has a strong preference for multimeric substrates, which accumulate at the poles and septum region. Altogether, these data show that a multimer recognition mechanism is likely applicable across the non-classical secretion pathway. PMID:28276482

  20. An explanation for minor multimer species in endothelial cell-synthesized von Willebrand factor.

    PubMed Central

    Lynch, D C; Zimmerman, T S; Ling, E H; Browning, P J

    1986-01-01

    Initial synthesis of von Willebrand factor (vWf) by cultured human endothelial cells proceeds by formation of a dimer of pro-vWf subunits. These subunits are found only within the cell and have an apparent molecular weight of 240,000-260,000, as measured by electrophoresis in sodium dodecyl sulfate-polyacrylamide gels. Posttranslational modifications, including proteolytic cleavage, glycosylation, and sulfation, result in the appearance of two additional vWf subunits. The major one migrates with the subunit of plasma vWf at an apparent molecular weight of 220,000-225,000 and the other migrates more slowly than pro-vWf at an apparent molecular weight of 260,000-275,000. These subunits oligomerize to form a set of vWf multimers, which are subsequently secreted into the culture medium. We isolated individual vWf oligomer species from the agarose gel bands and show that vWf minor, or satellite, species differ from major species in subunit composition. Images PMID:3486890

  1. Formation and stability of cubic ice in water droplets.

    PubMed

    Murray, Benjamin J; Bertram, Allan K

    2006-01-07

    There is growing evidence that a metastable phase of ice, cubic ice, plays an important role in the Earth's troposphere and stratosphere. Cubic ice may also be important in diverse fields such as cryobiology and planetary sciences. Using X-ray diffraction, we studied the formation of cubic ice in pure water droplets suspended in an oil matrix as a function of droplet size. The results show that droplets of volume median diameter 5.6 microm froze dominantly to cubic ice with stacking faults. These results support previous suggestions that cubic ice is the crystalline phase that nucleates when pure water droplets freeze homogeneously at approximately 235 K. It is also shown that as the size of the water droplets increased from 5.6 to 17.0 microm, the formation of the stable phase of ice, hexagonal ice, was favoured. This size dependence can be rationalised with heat transfer calculations. We also investigated the stability of cubic ice that forms in water droplets suspended in an oil matrix. We observe cubic ice up to 243 K, much higher in temperature than observed in many previous studies. This result adds to the existing literature that shows bulk ice I(c) can persist up to approximately 240 K. The transformation of cubic ice to hexagonal ice also showed a complex time and temperature dependence, proceeding rapidly at first and then slowing down and coming to a halt. These combined results help explain why cubic ice forms in some experiments described in the literature and not others.

  2. LMI Based Robust Blood Glucose Regulation in Type-1 Diabetes Patient with Daily Multi-meal Ingestion

    NASA Astrophysics Data System (ADS)

    Mandal, S.; Bhattacharjee, A.; Sutradhar, A.

    2014-04-01

    This paper illustrates the design of a robust output feedback H ∞ controller for the nonlinear glucose-insulin (GI) process in a type-1 diabetes patient to deliver insulin through intravenous infusion device. The H ∞ design specification have been realized using the concept of linear matrix inequality (LMI) and the LMI approach has been used to quadratically stabilize the GI process via output feedback H ∞ controller. The controller has been designed on the basis of full 19th order linearized state-space model generated from the modified Sorensen's nonlinear model of GI process. The resulting controller has been tested with the nonlinear patient model (the modified Sorensen's model) in presence of patient parameter variations and other uncertainty conditions. The performance of the controller was assessed in terms of its ability to track the normoglycemic set point of 81 mg/dl with a typical multi-meal disturbance throughout a day that yields robust performance and noise rejection.

  3. [Determination of von Willebrand factor multimers in Mexican population].

    PubMed

    Hernández-Zamora, Edgar; Zavala-Hernández, Cesar; Viveros-Sandoval, Martha Eva; Ochoa-Rico, Angeles; Martínez-Murillo, Carlos; Reyes-Maldonado, Elba

    2014-01-01

    Antecedentes: la enfermedad de von Willebrand es un padecimiento hereditario en el que la estructura, función y concentración del factor de von Willebrand están alteradas y, en consecuencia, también la interacción plaqueta-factor de von Willebrand-endotelio. En México no hay registros epidemiológicos de la enfermedad, sólo se han efectuado algunos estudios aislados desde el punto de vista clínico y hematológico. Material y métodos: estudio retrospectivo efectuado en 155 mexicanos mestizos, 75 de ellos con diagnóstico presuntivo de enfermedad de von Willebrand, 15 con sospecha de hemofilia A y 65 donadores sanos (testigos). Se realizaron pruebas: básicas de coagulación, especiales y de clasificación: análisis de la composición multimérica. Resultados: 15 pacientes se diagnosticaron con hemofilia A; de los 75 sujetos con sospecha de enfermedad de von Willebrand se diagnosticaron 50 de la manera siguiente: tipo 1 (62%), tipo 2 (22%) [subtipos: 2A (14%), 2B (2%) y 2N (6%)] y tipo 3 (16%). Conclusión: el análisis de los multímeros del factor de von Willebrand es un método que cumple con las características adecuadas para el diagnóstico de la enfermedad de von Willebrand, por lo que es necesario implementar esta metodología para su estudio y mejorar su diagnóstico específico.

  4. Mechanochemical Approaches to Pharmaceutical Cocrystal Formation and Stability Analysis.

    PubMed

    Lin, Shan-Yang

    2016-01-01

    Solid-state mechanochemical grinding is important for promoting cocrystal formation, particularly in the design of new solids in the pharmaceutical industry. Pharmaceutical cocrystals are defined as crystalline materials comprising an active pharmaceutical ingredient (API) and one or more appropriate coformers in a definite stoichiometric ratio, formed via non-covalent interactions. Recently, both the US FDA (2013) and the EU EMA (2015) provided a Guidance for Industry and a Reflection Paper, respectively, emphasizing that cocrystals are a new type of substance with potential applications in the pharmaceutical industry. This paper contains a brief and systematic overview of pharmaceutical cocrystals prepared by four grinding processes: neat grinding, solvent-assisted grinding, thermal stress after neat grinding, and polymer-assisted grinding. The paper also highlights some examples of pharmaceutical cocrystals prepared by the above grinding approaches, and discusses the stability of cocrystals prepared by mechanical grinding. Also, an overview of cocrystals that are commercially available or undergoing clinical trials is given. A novel methodology for real-time and in situ monitoring of mechanochemical grinding reactions using various analytical techniques is addressed and can be expected to be applied in the near future.

  5. Speciation, formation, stability and analytical challenges of human arsenic metabolites

    PubMed Central

    Yehiayan, Lucy; Pattabiraman, Mahesh; Kavallieratos, Konstantinos; Wang, Xiaotang; Boise, Lawrence H.

    2012-01-01

    Human arsenic metabolism produces a number of species with varying toxicities; the presence of some has been identified while the existence of others has been postulated through indirect evidence. Speciation methods for the analysis of arsenite (AsIII), monomethylarsonous acid (MMAIII), dimethylarsinous acid (DMAIII), arsenate (AsV), monomethylarsonic acid (MMAV), dimethylarsinic acid (DMAV), arsino-glutathione (As(GS)3), monomethylarsino-glutathione (MMA(GS)2) and dimethylarsino-glutathione (DMA(GS)) were developed in this study through the use of cation exchange and reverse phase chromatography in a complementary manner. Electrospray ionization mass spectrometry (ESI-MS) was used for molecular identification of the arsenicals while inductively coupled plasma mass spectrometry (ICP-MS) was employed for quantitation purposes. Validation of the developed methods against each other for the quantitation of trivalent and pentavalent arsenicals was performed. The effect of reduced glutathione (GSH) concentration on the formation of arsenic-glutathione (As-GSH) complexes was studied. In the presence of glutathione, the occurrence of chromatographic artifacts on the cation exchange column was observed. The stability of trivalent arsenicals and As-GSH complexes was studied at various pH conditions. The results shed light on the importance of sample preparation, storage and proper choice of analytical column for the accurate identification of the As species. Reinvestigation of some of the previously reported As speciation studies of glutathione-rich biological samples needs to be performed for the verification of occurrence of As-GSH complexes and DMAIII. PMID:23495261

  6. Filamentous phage pIV multimer visualized by scanning transmission electron microscopy

    SciTech Connect

    Linderoth, N.A.; Russel, M.; Simon, M.N.

    1997-11-28

    A family of homomultimeric outer-membrane proteins termed secretins mediates the secretion of large macromolecules such as enzymes and filamentous bacteriophages across bacterial outer membranes to the extracellular millieu. The secretin encoded by filamentous phage f1 was purified. Mass determination of individual molecules by scanning transmission electron microscopy revealed two forms, a unit multimer composed of about 14 subunits and a multimer dimer. The secretin is roughly cylindrical and has an internal diameter of about 80 angstroms, which is large enough to accommodate filamentous phage (diameter of 65 angstroms). 21 refs., 3 figs., 1 tab.

  7. Structure of the filamentous phage pIV multimer by cryo-electron microscopy.

    PubMed

    Opalka, Natacha; Beckmann, Roland; Boisset, Nicolas; Simon, Martha N; Russel, Marjorie; Darst, Seth A

    2003-01-17

    The homo-multimeric pIV protein constitutes a channel required for the assembly and export of filamentous phage across the outer membrane of Escherichia coli. We present a 22 A-resolution three-dimensional reconstruction of detergent-solubilized pIV by cryo-electron microscopy associated with image analysis. The structure reveals a barrel-like complex, 13.5 nm in diameter and 24 nm in length, with D14 point-group symmetry, consisting of a dimer of unit multimers. Side views of each unit multimer exhibit three cylindrical domains named the N-ring, the M-ring and the C-ring. Gold labeling of pIV engineered to contain a single cysteine residue near the N or C terminus unambiguously identified the N-terminal region as the N-ring, and the C-terminal region was inferred to make up the C-ring. A large pore, ranging in inner diameter from 6.0 nm to 8.8 nm, runs through the middle of the multimer, but a central domain, the pore gate, blocks it. Moreover, the pore diameter at the N-ring is smaller than the phage particle. We therefore propose that the pIV multimer undergoes a large conformational change during phage transport, with reorganization of the central domain to open the pore, and widening at the N-ring in order to accommodate the 6.5 nm diameter phage particle.

  8. Formation and stability of polychlorinated biphenyl Pickering emulsions.

    PubMed

    Roy-Perreault, Andréanne; Kueper, Bernard H; Rawson, Jim

    2005-03-01

    An emulsion stabilized by colloidal suspensions of finely divided solids is known as a Pickering emulsion. The potential for polychlorinated biphenyls (PCBs) to form Pickering emulsions ex situ when in contact with powdered solids, such as clays and metal oxides, is investigated here. Bentonite, iron oxide and magnesium oxide dispersions proved to be robust Pickering emulsion stabilizers, whereas manganese oxide dispersions were not. Batch experiments revealed that emulsions can be formed using a moderately low energy input and can be stabilized with solid concentrations as low as 0.5 wt.%. For the base conditions (volumetric oil fraction (phi(oil))=30 vol.%; solid concentration (chi)=2 wt.%), the formed emulsions were indefinitely stable and the initial average droplet diameters varied from 80 to 258 mum, depending on the solid used in the colloidal dispersion. The average droplet size varied at early time, but for most conditions stabilized to a steady-state value 1 week after preparation. The effect of Ostwald ripening was limited. At greater than 0.5 wt.% concentration, the efficiency of the solid dispersion as a stabilizer was dependant on the volumetric oil fraction but not on the solid concentration. Generally, systems with volumetric oil fractions outside of the 20-70 vol.% range were unstable. The emulsions' droplet stability, average droplet size and size distribution were observed to vary as a function of the amount of energy provided to the system, the volumetric oil fraction, and the concentration of the solid in the aqueous dispersion. It is hypothesized that drilling through fractured rock in the immediate vicinity of dense, non-aqueous phase liquid (DNAPL) PCBs may provide both the energy and solid material necessary to form Pickering emulsions.

  9. 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.

  10. Formation and Stability of Impurity "snakes" in Tokamak Plasmas

    SciTech Connect

    L. Delgado-Aparicio, et. al.

    2013-01-28

    New observations of the formation and dynamics of long-lived impurity-induced helical "snake" modes in tokamak plasmas have recently been carried-out on Alcator C-Mod. The snakes form as an asymmetry in the impurity ion density that undergoes a seamless transition from a small helically displaced density to a large crescent-shaped helical structure inside q < 1, with a regularly sawtoothing core. The observations show that the conditions for the formation and persistence of a snake cannot be explained by plasma pressure alone. Instead, many features arise naturally from nonlinear interactions in a 3D MHD model that separately evolves the plasma density and temperature

  11. Pressure dependence of stabilized Criegee intermediate formation from a sequence of alkenes.

    PubMed

    Drozd, Greg T; Donahue, Neil M

    2011-05-05

    Ozonolysis is a key reaction in atmospheric chemistry, although important details of the behavior of the ozonolysis intermediates are not known. The key intermediate in ozonolysis, the Criegee intermeiate (CI), is known to quickly isomerize, with the favored unimolecular pathway depending on the relative barriers to isomerization. Stabilized Criegee intermediates (SCI), those with energy below any barriers to isomerization, may result from initial formation with low energy or collisional stabilization of high energy CI. Bimolecular reactions of SCI have been proposed to play a role in OH formation and nucleation of new particles, but unimolecular reactions of SCI may well be too fast for these to be significant. We present measurements of the pressure dependence of SCI formation for a set of alkenes utilizing a hexafluoroacetone scavenger. We studied four alkenes (2,3-dimethyl-2-butene (TME), trans-5-decene, cyclohexene, α-pinene) to characterize how size and cyclization (endo vs exo) affect the stability of Criegee intermediates formed in ozonolysis. SCI yields in ozonolysis were measured in a high pressure flow reactor within a range of 30-750 Torr. The linear alkenes show considerable stabilization with trans-5-decene showing 100% stabilization at ∼400 Torr and TME having 65% stabilization at 710 Torr. Extrapolation of the yields for linear alkenes to 0 Torr shows yields significantly above zero, indicating that a fraction of their CI are formed below the barrier to isomerization. CI from endocyclic alkenes show little to no stabilization and appear to have neglible stabilization at 0 Torr. Cyclohexene derived CI showed no stabilization even at 650 Torr, while α-pinene CI had ∼15% stabilization at 740 Torr. Our results show a strong dependence of SCI formation on carbon number; adding just 2 to 3 CI carbons in linear alkenes increases stabilization by a factor of 10. Stabilization for endocyclic alkenes, at atmospheric pressure, begins to occur at a carbon

  12. Opalescent and cloudy fruit juices: formation and particle stability.

    PubMed

    Beveridge, Tom

    2002-07-01

    Cloudy fruit juices, particularly from tropical fruit, are becoming a fast-growing part of the fruit juice sector. The classification of cloud as coarse and fine clouds by centrifugation and composition of cloud from apple, pineapple, orange, guava, and lemon juice are described. Fine particulate is shown to be the true stable cloud and to contain considerable protein, carbohydrate, and lipid components. Often, tannin is present as well. The fine cloud probably arises from cell membranes and appears not to be simply cell debris. Factors relating to the stability of fruit juice cloud, including particle sizes, size distribution, and density, are described and discussed. Factors promoting stable cloud in juice are presented.

  13. Formation and collapse of gels of sterically stabilized colloidal particles

    NASA Astrophysics Data System (ADS)

    Weeks, James R.; van Duijneveldt, Jeroen S.; Vincent, Brian

    2000-11-01

    Colloidal silica spheres (diameter 88 nm) with a thick steric stabilization layer of polystyrene (PS; Mw = 26 600 g mol-1) were prepared. In cyclohexane, a marginal solvent for PS, particle aggregation and gelation were observed on lowering the temperature. Near the gelation temperature and at particle concentrations of a few per cent by weight, the gels were sufficiently weak to slowly compact under gravity. On quenching to slightly lower temperatures, the gels still settled, but the top of the sediment did not become flat, as is usually the case. This seems to be related to an unusual mechanism for gel compaction, which starts by forming a more dense structure at the top of the sample. It is proposed that this is related to the entangled polymer chains on neighbouring particles resisting substantial rearrangement of the local structure. The transient gelation phenomenon, observed previously for mixtures of colloid and non-adsorbing polymer, has so far not been observed for our system.

  14. 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.

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

    PubMed Central

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

    2010-01-01

    The toxicity of the ubiquitous pollutant and endogenous metabolite, acrolein, is due in part to covalent protein modifications. Acrolein reacts readily with protein nucleophiles via Michael addition and Schiff base formation. Potential acrolein targets in protein include the nucleophilic side chains of cysteine, histidine, and lysine residues as well as the free amino terminus of proteins. Although cysteine is the most acrolein-reactive residue, cysteine-acrolein adducts are difficult to identify in vitro and in vivo. In this study, model peptides with cysteine, lysine, and histidine residues were used to examine the reactivity of acrolein. Results from these experiments show that acrolein reacts rapidly with cysteine residues through Michael addition to form M+56 Da adducts. These M+56 adducts are, however, not stable, even though spontaneous dissociation of the adduct is slow. Further studies demonstrated that when acrolein and model peptides are incubated at physiological pH and temperature, the M+56 adducts decreased gradually accompanied by the increase of M+38 adducts, which are formed from intra-molecular Schiff base formation. Adduct formation with the side chains of other amino acid residues (lysine and histidine) was much slower than cysteine and required higher acrolein concentration. When cysteine residues were blocked by reaction with iodoacetamide and higher concentrations of acrolein were used, adducts of the N-terminal amino group or histidyl residues were formed but lysine adducts were not detected. Collectively, these data demonstrate that acrolein reacts avidly with protein cysteine residues and that the apparent loss of protein-acrolein Michael adducts over time may be related to the appearance of a novel (M+38) adduct. These findings may be important in identification of in vivo adducts of acrolein with protein cysteine residues. PMID:19231900

  16. Tracking antigen-specific CD8⁺ T cells using MHC class I multimers.

    PubMed

    Alanio, Cécile; Bouvier, Isabelle; Jusforgues-Saklani, Hélène; Albert, Matthew L

    2013-01-01

    The tracking of epitope-specific T cells is a useful approach for the study of adaptive immune responses. This protocol describes how Major Histocompatibility Complex Class I (MHC-I) multimers can be used to stain, enrich, and enumerate (rare) populations of CD8(+) T cells specific for a given antigen. It provides the detailed steps for multimer labeling, magnetic enrichment, and cytometric analysis. Additionally, it provides informations for multiplexing experiments in order to achieve simultaneous detection of multiple antigenic specificities, and strategies for coupling the protocol with functional assays (e.g., intracellular cytokine staining). Future developments in cytometric systems (e.g., mass spectroscopy-based cytometry) and gene expression studies (e.g., single cell PCR) will extend these approaches and provide an unprecedented assessment of the immune repertoire.

  17. Formation and stability of Vitamin E enriched nanoemulsions stabilized by Octenyl Succinic Anhydride modified starch

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Vitamin E (VE) is highly susceptible to autoxidation; therefore, it requires systems to encapsulate and protect it from autoxidation.In this study,we developed VE delivery systems, which were stabilized by Capsul® (MS), a starch modified with octenyl succinic anhydride. Influences of interfacial ten...

  18. Formation and stability of high-spin alkali clusters.

    PubMed

    Schulz, C P; Claas, P; Schumacher, D; Stienkemeier, F

    2004-01-09

    Helium nanodroplet isolation has been applied to agglomerate alkali clusters at temperatures of 380 mK. The very weak binding to the surface of the droplets allows a selection of only weakly bound, high-spin states. Here we show that larger clusters of alkali atoms in high-spin states can be formed. The lack of strong bonds from pairing electrons makes these systems nonmetallic, van der Waals-like complexes of metal atoms. We find that sodium and potassium readily form such clusters containing up to 25 atoms. In contrast, this process is suppressed for rubidium and cesium. Apparently, for these heavy alkalis, larger high-spin aggregates are not stable and depolarize spontaneously upon cluster formation.

  19. Formation and Stability of High-Spin Alkali Clusters

    NASA Astrophysics Data System (ADS)

    Schulz, C. P.; Claas, P.; Schumacher, D.; Stienkemeier, F.

    2004-01-01

    Helium nanodroplet isolation has been applied to agglomerate alkali clusters at temperatures of 380mK. The very weak binding to the surface of the droplets allows a selection of only weakly bound, high-spin states. Here we show that larger clusters of alkali atoms in high-spin states can be formed. The lack of strong bonds from pairing electrons makes these systems nonmetallic, vanderWaals like complexes of metal atoms. We find that sodium and potassium readily form such clusters containing up to 25atoms. In contrast, this process is suppressed for rubidium and cesium. Apparently, for these heavy alkalis, larger high-spin aggregates are not stable and depolarize spontaneously upon cluster formation.

  20. Interface stability and defect formation during crystal growth

    SciTech Connect

    Fabietti, L.M.R.

    1991-01-08

    Unidirectional solidification experiments have been carried out in organic crystals with the aim of improving our knowledge on the effects of constraints on the interface morphology and to increase our understanding of the growth of anisotropic materials. The experimental information shows that lateral constraints such as a sharp change in the cross-sectional area in the solid liquid interface path, can produce important changes in the microstructure if the interface morphology is planar, cellular or dendritic. The study of anisotropic materials cover several topics. It is first shown that slight anisotropy does not influence the dendrite tip selection criterion. This conclusion is obtained from the analysis of the relationship between tip radius and velocity for dendrites growing under the steady state condition for two different materials, CBr{sub 4} and C{sub 2}Cl{sub 6}, which have different surface energy anisotropy values. The values of the dendrite operating parameters {sigma}* are compared with the predictions of the solvability theory and the morphological stability theory. The experiments show better agreement with the latter theory. Critical experiments have been designed and carried out to find the response functions which determine the composition and temperature of the interface as a function of velocity in faceted materials. The experiments, carried out in Napthalene-Camphor system, indicate a strong temperature dependence of the planar interface growth which can be correlated with the step growth mechanism. Experiments on the interface instability show an important dependence on the crystallographic orientation. Unidirectional solidification experiments in zone refined Napthalene confined in very thin cells (gap size {le} 50 {mu}m) have proven to be a good method to study the defect production at the solid liquid interface. 118 refs., 90 figs., 5 tabs.

  1. Formation of hydrothermal biochar and char stability in soils

    NASA Astrophysics Data System (ADS)

    Baumert, Julia; Gleixner, Gerd

    2010-05-01

    The use of charcoal as an artificial soil additive is suggested to beneficially modify degraded soil, reduce greenhouse gas emission and improve crop yields. So far research has been mainly done using pyrolysis chars which are produced by dry pyrolysis of biomass. Here we used hydrothermal carbonisation (HTC). In this process wet biomass is converted to char at moderate temperatures (~200°C). Due to the exothermal carbonisation reaction this process is almost energy neutral, i.e. the energy needed to start the carbonisation equals the energy released during carbonisation. Different process parameters have been used to modify the properties of the produced chars. We examined the chemical and morphological properties of hydrothermally synthesized biochar. Cellulose, yeast and sucrose were used as model substances for a range of parent material types like organic and garden waste as well as residues from biogas production. By modifying the process conditions of hydrothermal carbonisation concerning temperature (180°C to 220°C) and duration (6 hours to 24 hours) we produced a variety of different biochars. Our findings suggest that the elemental composition and the thermal stability of resulting chars depend on the feedstock and production conditions. Functional group chemistry determined by NMR shows that the aromaticity of the product increases as a function of temperature whereas the amount of O-alkylic compounds declines, concurrently. Our results show that the properties of the biochar can be manipulated by the modification of process conditions. This opens the opportunity to adjust the charcoal to a given soil type.

  2. Formation and stabilization of nanoemulsions using biosurfactants: Rhamnolipids.

    PubMed

    Bai, Long; McClements, David Julian

    2016-10-01

    Nanoemulsions are used in the food, cosmetics, personal care and pharmaceutical industries to provide desirable optical, textural, stability, and delivery characteristics. In many industrial applications, it is desirable to formulate nanoemulsions using natural ingredients so as to develop label-friendly products. Rhamnolipids are biosurfactants isolated from certain microorganisms using fermentation processes. They are glycolipids that have a polar head consisting of rhamnose units and a non-polar tail consisting of a hydrocarbon chain. In this study, the interfacial characteristics of this natural surfactant at medium chain triglyceride (MCT) oil-water interfaces were characterized, and its ability to form nanoemulsions was compared to that of another natural surfactant (quillaja saponins). The influence of rhamnolipid concentration, homogenization pressure, and oil type on the mean droplet diameter of emulsions produced by microfluidization was determined. Rhamnolipids were highly effective at forming small droplets (d32<0.15μm) at low surfactant-to-oil ratios (SOR<1:10) for MCT oil. Rhamnolipids could also be used to form small droplets using long chain triglyceride oils, such as corn and fish oil. Rhamnolipid-coated droplets were stable to aggregation over a range of pH values (5-9), salt concentrations (<100mM NaCl) and temperatures (20-90°C). However, droplet aggregation was observed at highly acidic (pH 2-4) and high ionic strength (200-500mM NaCl) conditions. These effects were attributed to a reduction in electrostatic repulsion at low pH and high salt levels. Rhamnolipid-coated droplets had a high negative charge at neutral pH that decreased in magnitude with decreasing pH. These results indicate that rhamnolipids are effective natural surfactants that may be able to replace synthetic surfactants in certain commercial applications.

  3. Food volatile compounds facilitating HII mesophase formation: solubilization and stability.

    PubMed

    Amar-Zrihen, Natali; Aserin, Abraham; Garti, Nissim

    2011-05-25

    Four lipophilic food volatile molecules of different chemical characteristics, phenylacetaldehyde, 2,6-dimethyl-5-heptenal, linalool, and trans-4-decenal, were solubilized into binary mixtures of monoolein/water, facilitating the formation of reverse hexagonal (H(II)) mesophases at room temperature without the need of solvents or triglycerides. Some of the flavor compounds are important building blocks of the hexagonal mesostructure, preventing phase transition with aging. The solubilization loads were relatively high: 12.6, 10.0, 12.6, and 10.0 wt % for phenylacetaldehyde, 2,6-dimethyl-5-heptenal, linalool, and trans-4-decenal, respectively. Phenylacetaldehyde formed mixtures of lamellar and cubic phases. Linalool, 2,6-dimethyl-5-heptenal, and trans-4-decenal induced structural shift from lamellar directly to H(II) mesophase, remaining stable at room temperature. Lattice parameters were found to increase with water content and to decrease with temperature and/or food volatile content. trans-4-Decenal produces more stable H(II) mesophase compared to linalool-loaded mesophase. At 40-60 °C, depending on the chemical structure and on the solubilization location of the food volatile compounds, the H(II) mesophase transforms to isotropic micellar phase, facilitating the release of the food volatile compounds. Molecular interactions suggest the existence of two consecutive stages in the solubilization process.

  4. Contribution of plant lignin to the soil organic matter formation and stabilization

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Lignin is the third most abundant plant constituent after cellulose and hemicellulose and thought to be one of the building blocks for soil organic matter formation. Lignin can be used as a predictor for long-term soil organic matter stabilization and C sequestration. Soils and humic acids from fo...

  5. ARHGAP18: an endogenous inhibitor of angiogenesis, limiting tip formation and stabilizing junctions

    PubMed Central

    Chang, Garry HK; Lay, Angelina J; Ting, Ka Ka; Zhao, Yang; Coleman, Paul R; Powter, Elizabeth E; Formaz-Preston, Ann; Jolly, Christopher J; Bower, Neil I; Hogan, Benjamin M; Rinkwitz, Silke; Becker, Thomas S; Vadas, Mathew A; Gamble, Jennifer R

    2014-01-01

    The formation of the vascular network requires a tightly controlled balance of pro-angiogenic and stabilizing signals. Perturbation of this balance can result in dysregulated blood vessel morphogenesis and drive pathologies including cancer. Here, we have identified a novel gene, ARHGAP18, as an endogenous negative regulator of angiogenesis, limiting pro-angiogenic signaling and promoting vascular stability. Loss of ARHGAP18 promotes EC hypersprouting during zebrafish and murine retinal vessel development and enhances tumor vascularization and growth. Endogenous ARHGAP18 acts specifically on RhoC and relocalizes to the angiogenic and destabilized EC junctions in a ROCK dependent manner, where it is important in reaffirming stable EC junctions and suppressing tip cell behavior, at least partially through regulation of tip cell genes, Dll4, Flk-1 and Flt-4. These findings highlight ARHGAP18 as a specific RhoGAP to fine tune vascular morphogenesis, limiting tip cell formation and promoting junctional integrity to stabilize the angiogenic architecture. PMID:25425145

  6. Conditions for circumstellar disc formation - II. Effects of initial cloud stability and mass accretion rate

    NASA Astrophysics Data System (ADS)

    Machida, Masahiro N.; Matsumoto, Tomoaki; Inutsuka, Shu-ichiro

    2016-12-01

    Disc formation in strongly magnetized cloud cores is investigated using a three-dimensional magnetohydrodynamic simulation with a focus on the effects of the initial cloud stability and the mass accretion rate. The initial cloud stability greatly alters the disc formation process even for prestellar clouds with the same mass-to-flux ratio. A high mass accretion rate on to the disc-forming region is realized in initially unstable clouds, and a large angular momentum is introduced into the circumstellar region in a short time. The region around the protostar has both a thin infalling envelope and a weak magnetic field, which both weaken the effect of magnetic braking. The growth of the rotation-supported disc is promoted in such unstable clouds. Conversely, clouds in an initially near-equilibrium state show lower accretion rates of mass and angular momentum. The angular momentum is transported to the outer envelope before protostar formation. After protostar formation, the circumstellar region has a thick infalling envelope and a strong magnetic field that effectively brakes the disc. As a result, disc formation is suppressed when the initial cloud is in a nearly stable state. The density distribution of the initial cloud also affects the disc formation process. Disc growth strongly depends on the initial conditions when the prestellar cloud has a uniform density, whereas there is no significant difference in the disc formation process in prestellar clouds with non-uniform densities.

  7. Comparison of different procedures to stabilize biogas formation after process failure in a thermophilic waste digestion system: influence of aggregate formation on process stability.

    PubMed

    Kleyböcker, A; Liebrich, M; Kasina, M; Kraume, M; Wittmaier, M; Würdemann, H

    2012-06-01

    Following a process failure in a full-scale biogas reactor, different counter measures were undertaken to stabilize the process of biogas formation, including the reduction of the organic loading rate, the addition of sodium hydroxide (NaOH), and the introduction of calcium oxide (CaO). Corresponding to the results of the process recovery in the full-scale digester, laboratory experiments showed that CaO was more capable of stabilizing the process than NaOH. While both additives were able to raise the pH to a neutral milieu (pH>7.0), the formation of aggregates was observed particularly when CaO was used as the additive. Scanning electron microscopy investigations revealed calcium phosphate compounds in the core of the aggregates. Phosphate seemed to be released by phosphorus-accumulating organisms, when volatile fatty acids accumulated. The calcium, which was charged by the CaO addition, formed insoluble salts with long chain fatty acids, and caused the precipitation of calcium phosphate compounds. These aggregates were surrounded by a white layer of carbon rich organic matter, probably consisting of volatile fatty acids. Thus, during the process recovery with CaO, the decrease in the amount of accumulated acids in the liquid phase was likely enabled by (1) the formation of insoluble calcium salts with long chain fatty acids, (2) the adsorption of volatile fatty acids by the precipitates, (3) the acid uptake by phosphorus-accumulating organisms and (4) the degradation of volatile fatty acids in the aggregates. Furthermore, this mechanism enabled a stable process performance after re-activation of biogas production. In contrast, during the counter measure with NaOH aggregate formation was only minor resulting in a rapid process failure subsequent the increase of the organic loading rate.

  8. Comparison of different procedures to stabilize biogas formation after process failure in a thermophilic waste digestion system: Influence of aggregate formation on process stability

    SciTech Connect

    Kleyboecker, A.; Liebrich, M.; Kasina, M.; Kraume, M.; Wittmaier, M.; Wuerdemann, H.

    2012-06-15

    Highlights: Black-Right-Pointing-Pointer Mechanism of process recovery with calcium oxide. Black-Right-Pointing-Pointer Formation of insoluble calcium salts with long chain fatty acids and phosphate. Black-Right-Pointing-Pointer Adsorption of VFAs by the precipitates resulting in the formation of aggregates. Black-Right-Pointing-Pointer Acid uptake and phosphate release by the phosphate-accumulating organisms. Black-Right-Pointing-Pointer Microbial degradation of volatile fatty acids in the aggregates. - Abstract: Following a process failure in a full-scale biogas reactor, different counter measures were undertaken to stabilize the process of biogas formation, including the reduction of the organic loading rate, the addition of sodium hydroxide (NaOH), and the introduction of calcium oxide (CaO). Corresponding to the results of the process recovery in the full-scale digester, laboratory experiments showed that CaO was more capable of stabilizing the process than NaOH. While both additives were able to raise the pH to a neutral milieu (pH > 7.0), the formation of aggregates was observed particularly when CaO was used as the additive. Scanning electron microscopy investigations revealed calcium phosphate compounds in the core of the aggregates. Phosphate seemed to be released by phosphorus-accumulating organisms, when volatile fatty acids accumulated. The calcium, which was charged by the CaO addition, formed insoluble salts with long chain fatty acids, and caused the precipitation of calcium phosphate compounds. These aggregates were surrounded by a white layer of carbon rich organic matter, probably consisting of volatile fatty acids. Thus, during the process recovery with CaO, the decrease in the amount of accumulated acids in the liquid phase was likely enabled by (1) the formation of insoluble calcium salts with long chain fatty acids, (2) the adsorption of volatile fatty acids by the precipitates, (3) the acid uptake by phosphorus-accumulating organisms and (4

  9. A Wellbore Stability Model for a Deviated Well in a Transversely Isotropic Formation Considering Poroelastic Effects

    NASA Astrophysics Data System (ADS)

    Liu, Ming; Jin, Yan; Lu, Yunhu; Chen, Mian; Hou, Bing; Chen, Wenyi; Wen, Xin; Yu, Xiaoning

    2016-09-01

    To analyse wellbore stability phenomena when drilling through a transversely isotropic formation such as shale, a wellbore stability model is developed based on the coordinate transformation method and complex variable elasticity theory. In order to comprehensively consider the anisotropies in the transversely isotropic formation, the model includes the followings: 1. the elastic anisotropy due to the sedimentation effect and naturally developed fractures and 2. the strength anisotropy due to the poor cementation between bedding planes and natural fractures. The model is further generalized by accounting for an arbitrary wellbore trajectory under an arbitrary in situ stress orientation. Next, the model is used in a parametric study that includes factors such as elastic anisotropy, strength anisotropy, multiple weak planes, in situ stress anisotropy, and poroelastic anisotropy, all of which can have a great influence on wellbore stability. Finally, a correction for a frequently used failure criterion has been made to ensure that the newly developed model is comprehensive and accurate for wellbore stability analyses in highly heterogeneous formations.

  10. Minimal transition state charge stabilization of the oxyanion during peptide bond formation by the ribosome.

    PubMed

    Carrasco, Nicolas; Hiller, David A; Strobel, Scott A

    2011-12-06

    Peptide bond formation during ribosomal protein synthesis involves an aminolysis reaction between the aminoacyl α-amino group and the carbonyl ester of the growing peptide via a transition state with a developing negative charge, the oxyanion. Structural and molecular dynamic studies have suggested that the ribosome may stabilize the oxyanion in the transition state of peptide bond formation via a highly ordered water molecule. To biochemically investigate this mechanistic hypothesis, we estimated the energetic contribution to catalytic charge stabilization of the oxyanion using a series of transition state mimics that contain different charge distributions and hydrogen bond potential on the functional group mimicking the oxyanion. Inhibitors containing an oxyanion mimic that carried a neutral charge and a mimic that preserved the negative charge but could not form hydrogen bonds had less than a 3-fold effect on inhibitor binding affinity. These observations argue that the ribosome provides minimal transition state charge stabilization to the oxyanion during peptide bond formation via the water molecule. This is in contrast to the substantial level of oxyanion stabilization provided by serine proteases. This suggests that the oxyanion may be neutralized via a proton shuttle, resulting in an uncharged transition state.

  11. Tuning the formation and stability of microcapsules by environmental conditions and chitosan structure.

    PubMed

    Ren, Ying; Xie, Hongguo; Liu, Xiaocen; Yang, Fan; Yu, Weiting; Ma, Xiaojun

    2016-10-01

    The goal of this work is to tune the formation and stability of the alginate-chitosan (AC) polyelectrolyte complexes (PECs) and microcapsules. Particularly, we explore the role of the conformation of chitosan on its interaction with alginate to understand the mechanism underpinning their interactions at the molecular level. Reducing the charge density by increasing pH will increase the compactness of chitosan, the values of the enthalpy (H) and stoichiometry (N) of binding between chitosan and alginate. Consequently, chitosan has advantage in being adsorbed on alginate beads to form microcapsules, including the binding rate and binding amount. Though the total heat release remain similar in the range of ionic strength, chitosan diffuses much easier into alginate hydrogels when in higher ionic strength. Increasing pH and ionic strength both help AC microcapsules to have higher stability. The results indicate that the formation and stability of AC microcapsules are related to the rigidity and conformations of chitosan molecules. After increasing acetylation degree (DA) of chitosan, the binding rate of chitosan and mechanical strength of AC microcapsules are both reduced. This work demonstrates the versatility and feasibility of tuning the formation and stability of polysaccharide microcapsules by physical factors and chitosan chemical structures.

  12. The diskmass survey. VIII. On the relationship between disk stability and star formation

    SciTech Connect

    Westfall, Kyle B.; Verheijen, Marc A. W.; Andersen, David R.; Bershady, Matthew A.; Martinsson, Thomas P. K.; Swaters, Robert A.

    2014-04-10

    We study the relationship between the stability level of late-type galaxy disks and their star-formation activity using integral-field gaseous and stellar kinematic data. Specifically, we compare the two-component (gas+stars) stability parameter from Romeo and Wiegert (Q {sub RW}), incorporating stellar kinematic data for the first time, and the star-formation rate estimated from 21 cm continuum emission. We determine the stability level of each disk probabilistically using a Bayesian analysis of our data and a simple dynamical model. Our method incorporates the shape of the stellar velocity ellipsoid (SVE) and yields robust SVE measurements for over 90% of our sample. Averaging over this subsample, we find a meridional shape of σ{sub z}/σ{sub R}=0.51{sub −0.25}{sup +0.36} for the SVE and, at 1.5 disk scale lengths, a stability parameter of Q {sub RW} = 2.0 ± 0.9. We also find that the disk-averaged star-formation-rate surface density ( Σ-dot {sub e,∗}) is correlated with the disk-averaged gas and stellar mass surface densities (Σ {sub e,} {sub g} and Σ {sub e,} {sub *}) and anti-correlated with Q {sub RW}. We show that an anti-correlation between Σ-dot {sub e,∗} and Q {sub RW} can be predicted using empirical scaling relations, such that this outcome is consistent with well-established statistical properties of star-forming galaxies. Interestingly, Σ-dot {sub e,∗} is not correlated with the gas-only or star-only Toomre parameters, demonstrating the merit of calculating a multi-component stability parameter when comparing to star-formation activity. Finally, our results are consistent with the Ostriker et al. model of self-regulated star-formation, which predicts Σ-dot {sub e,∗}/Σ{sub e,g}∝Σ{sub e,∗}{sup 1/2}. Based on this and other theoretical expectations, we discuss the possibility of a physical link between disk stability level and star-formation rate in light of our empirical results.

  13. Role of the crystal field stabilization energy in the formation of metal(II) formate mixed crystals

    NASA Astrophysics Data System (ADS)

    Balarew, Christo; Stoilova, Donka; Vassileva, Violeta

    A relationship between the distribution coefficient values and the factors determining the isomorphous substitution of some metal(II) formates (Mg, Mn, Fe, Co, Ni, Cu, Zn, Cd) has been found, given by D=[exp⁡{aṡf[ΔR/R]+bṡϕ(Δɛ)+cṡψ(Δs)}/{RT}, where Δ R/R is the relative difference in the ionic radii of the intersubstituting ions, Δɛ is the difference in the Me sbnd O bond energy, Δ s is the difference in the crystal field stabilization energy. The pre-exponential term represents the balance in bonding factors between the ions in the crystal and in the aqueous solution, in the case of ideally mixing in the solid state. The exponential term takes into account the enthalpy of mixing in the solid state. For the isostructural formate salts in which the substitution of a given cation by another one occurs in equivalent octahedral positions, the difference in the crystal field stabilization energy exerts the most important influence on the enthalpy of mixing.

  14. Rearrangement of MICU1 multimers for activation of MCU is solely controlled by cytosolic Ca2+

    PubMed Central

    Waldeck-Weiermair, Markus; Malli, Roland; Parichatikanond, Warisara; Gottschalk, Benjamin; Madreiter-Sokolowski, Corina T.; Klec, Christiane; Rost, Rene; Graier, Wolfgang F.

    2015-01-01

    Mitochondrial Ca2+ uptake is a vital process that controls distinct cell and organelle functions. Mitochondrial calcium uptake 1 (MICU1) was identified as key regulator of the mitochondrial Ca2+ uniporter (MCU) that together with the essential MCU regulator (EMRE) forms the mitochondrial Ca2+ channel. However, mechanisms by which MICU1 controls MCU/EMRE activity to tune mitochondrial Ca2+ signals remain ambiguous. Here we established a live-cell FRET approach and demonstrate that elevations of cytosolic Ca2+ rearranges MICU1 multimers with an EC50 of 4.4 μM, resulting in activation of mitochondrial Ca2+ uptake. MICU1 rearrangement essentially requires the EF-hand motifs and strictly correlates with the shape of cytosolic Ca2+ rises. We further show that rearrangements of MICU1 multimers were independent of matrix Ca2+ concentration, mitochondrial membrane potential, and expression levels of MCU and EMRE. Our experiments provide novel details about how MCU/EMRE is regulated by MICU1 and an original approach to investigate MCU/EMRE activation in intact cells. PMID:26489515

  15. ADAMTS13 content and VWF multimer and triplet structure in commercially available VWF/FVIII concentrates.

    PubMed

    Kannicht, Christoph; Fisseau, Claudine; Hofmann, Werner; Kröning, Mario; Fuchs, Birte

    2015-03-01

    ADAMTS13 is a metalloproteinase that cleaves von Willebrand factor (VWF) into smaller multimers in vivo. This cleavage creates both the typical multimeric size distribution and the characteristic triplet band distribution of VWF. Here we analysed ADAMTS13 content, VWF multimeric size distribution and VWF triplet structure in five commercial VWF/factor VIII (FVIII) concentrates. The relative distribution of ADAMTS13 activity values corresponded well to the ADAMTS13 antigen values for all examined concentrates except Haemate HS®, which had markedly higher ADAMTS13 antigen/activity ratio, with Fanhdi® and Haemate HS® displaying the most intense ADAMTS13 signal. Interestingly, ADAMTS13 levels did not correlate with the high molecular weight multimer content of the concentrates, but did correlate with VWF triplet distribution. Densitometric quantification showed that Wilate®, Immunate® and Willfact® displayed human plasma-like VWF triplet distribution, whereas Fanhdi® and Haemate HS® showed enhanced content of the faster migrating triplet band, which corresponded well to their higher ADAMTS13 content. In summary, Immunate®, Willfact® and Wilate® had lower levels of ADAMTS13 antigen and activity and exhibited a plasma-like VWF triplet structure. Fanhdi® and Haemate HS® had higher ADAMTS13 content and an altered triplet structure. The possible impact of these observations on function and clinical efficacy of VWF/FVIII concentrates is discussed.

  16. Defect formation and phase stability of Cu2ZnSnS4 photovoltaic material

    NASA Astrophysics Data System (ADS)

    Nagoya, Akihiro; Asahi, Ryoji; Wahl, Roman; Kresse, Georg

    2010-03-01

    First-principles studies of the phase stability of and defect formation in Cu2ZnSnS4 (CZTS) are performed. We show that CZTS is the thermodynamically stable phase for a rather small confined domain of chemical potentials. Even slight deviations from the optimal growth conditions will therefore result in the formation of other sulfidic precipitates, including ZnS, Cu2SnS3 , SnS, SnS2 , and CuS. In particular, under the prevalent experimental Cu-poor and Zn-rich growth conditions ZnS is the main competing phase. Furthermore, the calculations unambiguously predict that Cu at the Zn site is the most stable defect in the entire stability range of CZTS. This correlates with the experimental observation that CZTS is an intrinsic p -type semiconductor.

  17. Evaluation of the geological relationships to gas hydrate formation and stability

    SciTech Connect

    Not Available

    1986-01-01

    Although there are many publications pertaining to gas hydrates, their formation and stability in various geological conditions are poorly known. Therefore, for the same reasons and because of the very broad scope of our research, limited amount and extremely dispersed information, the study regions are very large. Moreover, almost without exception the geological environments controlling gas hydrates formation and stability of the studied regions are very complex. The regions studied (completed and partially completed - total 17 locations) during the reporting period, particularly the Gulf of Mexico and the Middle America Trench, are the most important in this entire research project. In the past, both of these regions have been extensively studied, the presence of gas hydrates confirmed and samples recovered. In our investigation it was necessary not only to review all previous data and interpretations, but to do a thorough analysis of the basins, and a critical evaluation of an previously reported and publicly available but not published information.

  18. Barrierless Cu-Ni-Mo Interconnect Films with High Thermal Stability Against Silicide Formation

    NASA Astrophysics Data System (ADS)

    Li, X. N.; Liu, L. J.; Zhang, X. Y.; Chu, J. P.; Wang, Q.; Dong, C.

    2012-12-01

    Cu-Ni-Mo alloys were investigated to increase thermal stability against silicide formation. The alloy compositions were chosen such that an insoluble element (Mo) solute was dissolved into Cu via a third element Ni which is soluble in both Cu and Ni. Thin-film Cu-Ni-Mo alloys were prepared by magnetron sputtering. The films with Mo/Ni ratio of 1/12 exhibited low electrical resistivities in combination with high thermal stabilities against silicide formation, in support of a tentative "cluster-plus-glue-atom" model for stable solid solutions. In particular, a (Mo1/13Ni12/13)0.3Cu99.7 sample reached a minimum resistivity of 2.6 μΩ cm after 400°C/1 h annealing and remained highly conductive with resistivities below 3 μΩ cm even after 400°C/40 h annealing. These alloys are promising candidates for future interconnect materials.

  19. Formation and Stability of Bulk Nanobubbles Generated by Ethanol-water Exchange.

    PubMed

    Zhang, Lijuan; Qiu, Jie; Wang, Shuo; Wang, Xingya; Wang, Lei; Zhao, Hongwei; Hu, Jun; Zou, Zhenglei; Dong, Yaming

    2017-03-04

    Bulk nanobubbles have unique properties and have found potential applications in many important processes. However, their stability or long lifetime still needs to further understand and draw much attention from researchers. In this letter, we generated bulk nanobubbles based on ethanol-water exchange, a method which is generally used in the studies of surface nanobubbles. The formation and stability of them was further studied by using "Nanosight" (a new type of dynamic light scattering). Our results showed that the concentration of the bulk nanobubbles produced by our method was about five times than those in the degassed group, which indicated the existence of the bulk gas nanobubbles. The effects of ethanol/water ratios and temperature on the stability of the bulk nanobubbles have also been studied and found that their numbers will reach to the maximum at the ratio of about 1:10 (v/v).

  20. Organic chloramines in drinking water: An assessment of formation, stability, reactivity and risk.

    PubMed

    How, Zuo Tong; Linge, Kathryn L; Busetti, Francesco; Joll, Cynthia A

    2016-04-15

    Although organic chloramines are known to form during the disinfection of drinking water with chlorine, little information is currently available on their occurrence or toxicity. In a recent in vitro study, some organic chloramines (e.g. N-chloroglycine) were found to be cytotoxic and genotoxic even at micromolar concentrations. In this paper, the formation and stability of 21 different organic chloramines, from chlorination of simple amines and amino acids, were studied, and the competition between 20 amino acids during chlorination was also investigated. For comparison, chlorination of two amides was also conducted. The formation and degradation of selected organic chloramines were measured using either direct UV spectroscopic or colorimetric detection. Although cysteine, methionine and tryptophan were the most reactive amino acids towards chlorination, they did not form organic chloramines at the chlorine to precursor molar ratios that were tested. Only 6 out of the 21 organic chloramines formed had a half-life of more than 3 h, although this group included all organic chloramines formed from amines. A health risk assessment relating stability and reactivity data from this study to toxicity and precursor abundance data from the literature indicated that only N-chloroglycine is likely to be of concern due to its stability, toxicity and abundance in water. However, given the stability of organic chloramines formed from amines, more information about the toxicity and precursor abundance for these chloramines is desirable.

  1. Use of Ramachandran plot for increasing thermal stability of bacterial formate dehydrogenase.

    PubMed

    Serov, A E; Odintzeva, E R; Uporov, I V; Tishkov, V I

    2005-07-01

    From analysis of Ramachandran plot for NAD+-dependent formate dehydrogenase from the methylotrophic bacterium Pseudomonas sp. 101 (FDH, EC 1.2.1.2), five amino acid residues with non-optimal values phi and psi have been located in beta- and pi-turns of the FDH polypeptide chain, e.g., Asn136, Ala191, Tyr144, Asn234, and His263. To clarify their role in the enzyme stability, the residues were replaced with Gly by means of site-directed mutagenesis. The His263Gly mutation caused FDH destabilization and a 1.3-fold increase in the monomolecular inactivation rate constant. The replacements Ala191Gly and Asn234Gly had no significant effect on the stability. The mutations Asn136Gly and Tyr144Gly resulted in higher thermal stability and decreased the inactivation rate by 1.2- and 1.4-fold, respectively. The stabilizing effect of the Tyr144Gly mutation was shown to be additive when introduced into the previously obtained mutant FDH with enhanced thermal stability.

  2. Fibulin-3, -4, and -5 Are Highly Susceptible to Proteolysis, Interact with Cells and Heparin, and Form Multimers*

    PubMed Central

    Djokic, Jelena; Fagotto-Kaufmann, Christine; Bartels, Rainer; Nelea, Valentin; Reinhardt, Dieter P.

    2013-01-01

    Extracellular short fibulins, fibulin-3, -4, and -5, are components of the elastic fiber/microfibril system and are implicated in the formation and homeostasis of elastic tissues. In this study, we report new structural and functional properties of the short fibulins. Full-length human short fibulins were recombinantly expressed in human embryonic kidney cells and purified by immobilized metal ion affinity chromatography. All three fibulins showed various levels of degradation after the purification procedure. N-terminal sequencing revealed that all three fibulins are highly susceptible to proteolysis within the N-terminal linker region of the first calcium-binding epidermal growth factor domain. Proteolytic susceptibility of the linker correlated with its length. Exposure of these fibulins to matrix metalloproteinase (MMP)-1, -2, -3, -7, -9, and -12 resulted in similar proteolytic fragments with MMP-7 and -12 being the most potent proteases. Fibulin-3 proteolysis was almost completely inhibited in cell culture by the addition of 25 μm doxycycline (a broad spectrum MMP inhibitor). Reducible fibulin-4 dimerization and multimerization were consistently observed by SDS-PAGE, Western blotting, and mass spectrometry. Atomic force microscopy identified monomers, dimers, and multimers in purified fibulin-4 preparations with sizes of ∼10–15, ∼20–25, and ∼30–50 nm, respectively. All short fibulins strongly adhered to human fibroblasts and smooth muscle cells. Although only fibulin-5 has an RGD integrin binding site, all short fibulins adhere at a similar level to the respective cells. Solid phase binding assays detected strong calcium-dependent binding of the short fibulins to immobilized heparin, suggesting that these fibulins may bind cell surface-located heparan sulfate. PMID:23782690

  3. Stability and pattern formation for competing populations with asymmetric nonlocal coupling.

    PubMed

    Tanzy, M C; Volpert, V A; Bayliss, A; Nehrkorn, M E

    2013-11-01

    We consider a model of two competing species with asymmetric nonlocal coupling in a competition for resources. The nonlocal coupling is via convolution integrals and the asymmetry is via convolution kernel functions which are not even functions of their arguments. The nonlocality is due to species mobility, so that at any fixed point in space the competition for resources depends not just on the populations at that point but on a suitably weighted average of the populations. We introduce two parameters, δ, describing the extent of the coupling, with δ=0 corresponding to local coupling, and α, describing the extent of the asymmetry, with α=0 corresponding to symmetric nonlocal interactions. We consider the case where the model admits a stable coexistence equilibrium solution. We perform a linear stability analysis and show that this solution can be destabilized by sufficient nonlocality, i.e., when δ increases beyond a critical value. We consider two specific kernel functions, (i) an asymmetric Gaussian and (ii) an asymmetric stepfunction. We compute the stability boundary as a function of α, and for δ beyond the stability boundary we determine unstable wavenumber bands. We compute nonlinear patterns for δ significantly beyond the stability boundary. Patterns consist of arrays of islands, regions of nonzero population, separated by either near-deadzones where the populations are small, but nonzero, or by deadzones where populations are exponentially small and essentially extinct. We find solutions consisting of propagating traveling waves of islands, solutions exhibiting colony formation, where a colony is formed just ahead of an island and eventually grows as the parent island decays, and modulated traveling waves, where competition between the two species allows propagation and inhibits colony formation. We explain colony formation and the modulated traveling waves as due to a positive feedback mechanism associated with small variations in the amplitude of

  4. Effects of mineral additives on biochar formation: carbon retention, stability, and properties.

    PubMed

    Li, Feiyue; Cao, Xinde; Zhao, Ling; Wang, Jianfei; Ding, Zhenliang

    2014-10-07

    Biochar is being recognized as a promising tool for long-term carbon sequestration, and biochar with high carbon retention and strong stability is supposed to be explored for that purpose. In this study, three minerals, including kaolin, calcite (CaCO3), and calcium dihydrogen phosphate [Ca(H2PO4)2], were added to rice straw feedstock at the ratio of 20% (w/w) for biochar formation through pyrolysis treatment, aiming to improve carbon retention and stabilization in biochar. Kaolin and CaCO3 had little effect on the carbon retention, whereas Ca(H2PO4)2 increased the carbon retention by up to 29% compared to untreated biochar. Although the carbon loss from the kaolin-modified biochar with hydrogen peroxide oxidation was enhanced, CaCO3 and Ca(H2PO4)2 modification reduced the carbon loss by 18.6 and 58.5%, respectively. Moreover, all three minerals reduced carbon loss of biochar with potassium dichromate oxidation from 0.3 to 38.8%. The microbial mineralization as CO2 emission in all three modified biochars was reduced by 22.2-88.7% under aerobic incubation and 5-61% under anaerobic incubation. Enhanced carbon retention and stability of biochar with mineral treatment might be caused by the enhanced formation of aromatic C, which was evidenced by cross-polarization magic angle spinning (13)C nuclear magnetic resonance spectra and Fourier transform infrared spectroscopy analysis. Our results indicated that the three minerals, especially Ca(H2PO4)2, were effective in increasing carbon retention and strengthening biochar stabilization, which provided a novel idea that people could explore and produce the designated biochar with high carbon sequestration capacity and stability.

  5. Magnetic microparticle-based multimer detection system for the detection of prion oligomers in sheep

    PubMed Central

    Lim, Kuntaek; Kim, Su Yeon; Lee, Byoungsub; Segarra, Christiane; Kang, Sungmin; Ju, Youngran; Schmerr, Mary Jo; Coste, Joliette; Kim, Sang Yun; Yokoyama, Takashi; An, Seong Soo A

    2015-01-01

    Transmissible spongiform encephalopathies (TSEs) are zoonotic fatal neurodegenerative diseases in animals and humans. TSEs are commonly known as bovine spongiform encephalopathy in cattle, scrapie in sheep and goats, chronic wasting disease in cervids, and Creutzfeldt–Jakob disease in humans. The putative transmissible agents are infectious prion proteins (PrPSc), which are formed by the conversion of the normal prion protein on the glycoprotein cell surface in the presence of other PrPSc. Reports of the transmission of TSEs through blood raised considerable concern about the safety of blood and blood products. To address this issue, many laboratories attempted to develop a sensitive and accurate blood diagnostic test to detect PrPSc. Previously, we reported that, compared to normal controls, the multimer detection system (MDS) was more efficient in detecting PrPSc in infected hamster brain homogenate, mouse plasma spiked with purified PrPSc from scrapie mouse brain, and scrapie-infected hamster plasmas. MDS differentiates prion multimers from the cellular monomer through the multimeric expression of epitopes on prion multimers, in contrast to the monomeric form. In this study, MDS detected PrPSc in plasma samples from scrapie-infected sheep expressing clinical symptoms, demonstrating 100% sensitivity and specificity in these samples. Plasma samples from asymptomatic lambs at the preclinical stage (8-month-old naturally infected offspring of scrapie-infected parents expressing a highly susceptible genotype) tested positive with 50% sensitivity and 100% specificity. In the first of two coded analyses using clinical scrapie-infected sheep and normal healthy samples, MDS successfully identified all but one of the clinical samples with 92% sensitivity and 100% specificity. Similar results were obtained in the second coded analysis using preclinical samples. MDS again successfully identified all but one of the samples with 87% sensitivity and 100% specificity. The

  6. Covalently linked multimers of gold nanoclusters Au102(p-MBA)44 and Au∼250(p-MBA)n.

    PubMed

    Lahtinen, Tanja; Hulkko, Eero; Sokołowska, Karolina; Tero, Tiia-Riikka; Saarnio, Ville; Lindgren, Johan; Pettersson, Mika; Häkkinen, Hannu; Lehtovaara, Lauri

    2016-11-10

    We present the synthesis, separation, and characterization of covalently-bound multimers of para-mercaptobenzoic acid (p-MBA) protected gold nanoclusters. The multimers were synthesized by performing a ligand-exchange reaction of a pre-characterized Au102(p-MBA)44 nanocluster with biphenyl-4,4'-dithiol (BPDT). The reaction products were separated using gel electrophoresis yielding several distinct bands. The bands were analyzed by transmission electron microscopy (TEM) revealing monomer, dimer, and trimer fractions of the nanocluster. TEM analysis of dimers in combination with molecular dynamics simulations suggest that the nanoclusters are covalently bound via a disulfide bridge between BPDT molecules. The linking chemistry is not specific to Au102(p-MBA)44. The same approach yields multimers also for a larger monodisperse p-MBA-protected cluster of approximately 250 gold atoms, Au∼250(p-MBA)n. While the Au102(p-MBA)44 is not plasmonic, the Au∼250(p-MBA)n nanocluster supports localized surface plasmon resonance (LSPR) at 530 nm. Multimers of the Au∼250(p-MBA)n exhibit additional transitions in their UV-vis spectrum at 630 nm and 810 nm, indicating the presence of hybridized LSPR modes. Well-defined structures and relatively small sizes make these systems excellent candidates for connecting ab initio theoretical studies and experimental quantum plasmonics. Moreover, our work opens new possibilities in the controlled synthesis of advanced monodisperse nanocluster superstructures.

  7. A model for the formation and stabilization of charged water clathrates

    NASA Technical Reports Server (NTRS)

    Holland, P. M.; Castleman, A. W., Jr.

    1980-01-01

    A model for the formation and stabilization of charged water clathrates is presented which accounts for observed anomalies in H(+)(H2O)n ion distributions. These anomalies are observed in both ion cluster and neutral expansions and are consistent with the sizes expected for clathrate ions. That the same sizes are observed in both ion cluster and neutral expansions strongly suggests that a rapid ionic process is responsible for their formation. The proposed model is based on the high mobility and bonding effects of the excess proton in water. Computer simulations suggest that excess proton movement in a water clathrate would be suitable for stabilizing the clathrate structure as well as giving it access to a large number of nearly degenerate proton configurations. The formation of clathrates in charged water clusters of proper size can be ascribed to the following: rapid excess proton movement, a strong preference of the H3O(+) for a three-coordinate bonding structure (which is compatible with hydrogen bonding), and finally, relatively slow processes leading to thermal disorder.

  8. Understanding soil organic matter formation and stabilization (Philippe Duchaufour Medal Lecture)

    NASA Astrophysics Data System (ADS)

    Kögel-Knabner, Ingrid

    2015-04-01

    During the biomass formation/decomposition cycle carbon dioxide (CO2), the main gas driving global warming, is either released from or stabilized in the organic matter of soils. One of the most fundamental functions of soil organic matter is the provision of metabolic energy which drives soil biological processes. In essence, it is the transformation of carbon by plant, micro- and macro-biological processes that provides energy and results in the establishment of a cycle that connects above- and belowground energy transformations. The amount and type of organic matter accumulated in soils is controlled, among other factors by intrinsic soil properties, specifically soil texture and the associated aggregate structures. Soil development leads to the formation of aggregated structures composed of a highly complex mixture of different mineral and organic constituents. The resulting soil type specific carbon sequestration can strongly be affected by soil management, varying greatly with the type and intensity of land use. The processes of formation and stabilization of organic matter through organo-mineral interactions in aggregated soil structures are controlled at the sub-µm scale. Understanding the binding of organic matter in these fine soil structures is thus key to elucidate the biogeochemical soil processes that are part of the carbon cycle as well as to evaluate the effects of soil management on the carbon cycle. I will discuss open questions for understanding these processes and how we can approach them by combining state-of-the-art analytical techniques with innovative experiments.

  9. Input-to-state stability of model-based spacecraft formation control systems with communication constraints

    NASA Astrophysics Data System (ADS)

    Liu, Xi; Kumar, K. D.

    2011-06-01

    This paper investigates the formation keeping problem for multiple spacecraft in the framework of networked control systems (NCSs). A continuous-time representation of the NCS is considered for the tracking control of relative translational motion between two spacecraft in a leader-follower formation in the presence of communication constraints and system uncertainties. Model-based control schemes are presented, which employ state feedback (when the relative position and velocity vectors are directly measurable) and output feedback (when velocity measurements are not available), respectively, to guarantee input-to-state stability (ISS) of the system. The stability conditions on network transfer intervals are derived as simple eigenvalue tests of a well-structured test matrix. The results are then extended to include network communication delay. Numerical simulations are presented to demonstrate the effectiveness of the control scheme ensuring high formation keeping precision and robustness to nonlinearities and system uncertainties. The proposed controllers are robust not only to structured uncertainties such as system parameter perturbations but also to unstructured uncertainties such as external disturbances and measurement noises.

  10. Particle stability in dilute fermented dairy drinks: formation of fluid gel and impact on rheological properties.

    PubMed

    Kiani, H; Mousavi, M E; Mousavi, Z E

    2010-12-01

    Fluid gels are known to be very shear-thinning materials with yield stress. In this study, the rheological properties of gellan and gellan-pectin fluid gels in fermented dairy drinks were evaluated using viscometric measurements. Both gellan- and gellan-pectin-containing solutions showed the rheological properties of fluid gels resulting in stabilization of particles; but no evidence of a fluid gel was observed for those with pectin alone and those with no hydrocolloid content. Unlike pectin, gellan gum was capable of creating significant values of yield stress and accordingly stabilized colloidal particles and extrinsic added solid particles in the fermented dairy drink. However, pectin improved the stability in combination with gellan. The origin of fluid gel formation was assumed to be both permanent interactions occurring between gellan and proteins, forming hairy particle gels and transient interactions between the particle gels. The significance of yield stress values for particle stability was demonstrated and two methods, including a noteworthy infinite apparent viscosity method and a conventional Bingham approach, were employed to calculate the values of yield stress. Both the methods showed a good application potential due to their simplicity, reasonable results and also wide availability of the instrument applied.

  11. High-Temperature Stability and Grain Boundary Complexion Formation in a Nanocrystalline Cu-Zr Alloy

    NASA Astrophysics Data System (ADS)

    Khalajhedayati, Amirhossein; Rupert, Timothy J.

    2015-12-01

    Nanocrystalline Cu-3 at.% Zr powders with ~20 nm average grain size were created with mechanical alloying and their thermal stability was studied from 550-950°C. Annealing drove Zr segregation to the grain boundaries, which led to the formation of amorphous intergranular complexions at higher temperatures. Grain growth was retarded significantly, with 1 week of annealing at 950°C, or 98% of the solidus temperature, only leading to coarsening of the average grain size to 54 nm. The enhanced thermal stability can be connected to both a reduction in grain boundary energy with doping as well as the precipitation of ZrC particles. High mechanical strength is retained even after these aggressive heat treatments, showing that complexion engineering may be a viable path toward the fabrication of bulk nanostructured materials with excellent properties.

  12. Quantifying tetrahedral adduct formation and stabilization in the cysteine and the serine proteases.

    PubMed

    Cleary, Jennifer A; Doherty, William; Evans, Paul; Malthouse, J Paul G

    2015-10-01

    Two new papain inhibitors have been synthesized where the terminal α-carboxyl groups of Z-Phe-Ala-COOH and Ac-Phe-Gly-COOH have been replaced by a proton to give Z-Phe-Ala-H and Ac-Phe-Gly-H. We show that for papain, replacing the terminal carboxylate group of a peptide inhibitor with a hydrogen atom decreases binding 3-4 fold while replacing an aldehyde or glyoxal group with a hydrogen atom decreases binding by 300,000-1,000,000 fold. Thiohemiacetal formation by papain with aldehyde or glyoxal inhibitors is shown to be ~10,000 times more effective than hemiacetal or hemiketal formation with chymotrypsin. It is shown using effective molarities, that for papain, thiohemiacetal stabilization is more effective with aldehyde inhibitors than with glyoxal inhibitors. The effective molarity obtained when papain is inhibited by an aldehyde inhibitor is similar to the effective molarity obtained when chymotrypsin is inhibited by glyoxal inhibitors showing that both enzymes can stabilize tetrahedral adducts by similar amounts. Therefore the greater potency of aldehyde and glyoxal inhibitors with papain is not due to greater thiohemiacetal stabilization by papain compared to the hemiketal and hemiacetal stabilization by chymotrypsin, instead it reflects the greater intrinsic reactivity of the catalytic thiol group of papain compared to the catalytic hydroxyl group of chymotrypsin. It is argued that while the hemiacetals and thiohemiacetals formed with the serine and cysteine proteases respectively can mimic the catalytic tetrahedral intermediate they are also analogues of the productive and non-productive acyl intermediates that can be formed with the cysteine and serine proteases.

  13. Formation, spin-up, and stability of field-reversed configurations

    DOE PAGES

    Omelchenko, Yuri A.

    2015-08-24

    Formation, spontaneous spin-up and stability of theta-pinch formed field-reversed configurations are studied self-consistently in three dimensions with a multiscale hybrid model that treats all plasma ions as full-orbit collisional macro-particles and the electrons as a massless quasineutral fluid. The end-to-end hybrid simulations for the first time reveal poloidal profiles of implosion-driven fast toroidal plasma rotation and demonstrate three well-known discharge regimes as a function of experimental parameters: the decaying stable configuration, the tilt unstable configuration and the nonlinear evolution of a fast growing tearing mode.

  14. Evaluation of the geological relationships to gas hydrate formation and stability

    SciTech Connect

    Krason, J.; Finley, P.

    1988-01-01

    The summaries of regional basin analyses document that potentially economic accumulations of gas hydrates can be formed in both active and passive margin settings. The principal requirement for gas hydrate formation in either setting is abundant methane. Passive margin sediments with high sedimentation rates and sufficient sedimentary organic carbon can generate large quantities of biogenic methane for hydrate formation. Similarly, active margin locations near a terrigenous sediment source can also have high methane generation potential due to rapid burial of adequate amounts of sedimentary organic matter. Many active margins with evidence of gas hydrate presence correspond to areas subject to upwelling. Upwelling currents can enhance methane generation by increasing primary productivity and thus sedimentary organic carbon. Structural deformation of the marginal sediments at both active and passive sites can enhance gas hydrate formation by providing pathways for migration of both biogenic and thermogenic gas to the shallow gas hydrate stability zone. Additionally, conventional hydrocarbon traps may initially concentrate sufficient amounts of hydrocarbons for subsequent gas hydrate formation.

  15. Rapid formation and selective stabilization of synapses for enduring motor memories

    PubMed Central

    Xu, Tonghui; Yu, Xinzhu; Perlik, Andrew J.; Tobin, Willie F.; Zweig, Jonathan A.; Tennant, Kelly; Jones, Theresa; Zuo, Yi

    2010-01-01

    Novel motor skills are learned through repetitive practice and, once acquired, persist long after training stops1,2. Earlier studies have shown that such learning induces an increase in the efficacy of synapses in the primary motor cortex, the persistence of which is associated with retention of the task3–5. However, how motor learning affects neuronal circuitry at the level of individual synapses and how long-lasting memory is structurally encoded in the intact brain remain unknown. Here we show that synaptic connections in the living mouse brain rapidly respond to motor-skill learning and permanently rewire. Training in a forelimb reaching task leads to rapid (within an hour) formation of postsynaptic dendritic spines on the output pyramidal neurons in the contralateral motor cortex. Although selective elimination of spines that existed before training gradually returns the overall spine density back to the original level, the new spines induced during learning are preferentially stabilized during subsequent training and endure long after training stops. Furthermore, we show that different motor skills are encoded by different sets of synapses. Practice of novel, but not previously learned, tasks further promotes dendritic spine formation in adulthood. Our findings reveal that rapid, but long-lasting, synaptic reorganization is closely associated with motor learning. The data also suggest that stabilized neuronal connections are the foundation of durable motor memory. PMID:19946267

  16. Kinetic simulations of the formation and stability of the field-reversed configuration

    SciTech Connect

    Omelchenko, Yu. A.

    2000-05-01

    The Field-Reversed Configuration (FRC) is a high-beta compact toroidal plasma confined primarily by poloidal fields. In the FRC the external field is reversed on axis by the diamagnetic current carried by thermal plasma particles. A three-dimensional, hybrid, particle-in-cell (zero-inertia fluid electrons, and kinetic ions), code FLAME, previously used to study ion rings [Yu. A. Omelchenko and R. N. Sudan, J. Comp. Phys. 133, 146 (1997)], is applied to investigate FRC formation and tilt instability. Axisymmetric FRC equilibria are obtained by simulating the standard experimental reversed theta-pinch technique. These are used to study the nonlinear tilt mode in the ''kinetic'' and ''fluid-like'' cases characterized by ''small'' ({approx}3) and ''large'' ({approx}12) ratios of the characteristic radial plasma size to the mean ion gyro-radius, respectively. The formation simulations have revealed the presence of a substantial toroidal (azimuthal) magnetic field inside the separatrix, generated due to the stretching of the poloidal field by a sheared toroidal electron flow. This is shown to be an important tilt-stabilizing effect in both cases. On the other hand, the tilt mode stabilization by finite Larmor radius effects has been found relatively insignificant for the chosen equilibria. (c) 2000 American Institute of Physics.

  17. The DYNAFLUX / DYNACOLD Network: Dynamics, Fluxes, Stability, Succession and Landscape Formation in Cold Climate Environments

    NASA Astrophysics Data System (ADS)

    Beylich, Achim A.

    2016-04-01

    There is a wide range of high-latitude and high-altitude cold climate landscapes in Europe, covering a significant proportion of the total land surface area. This spectrum of defined cold climate landscapes represents a variety of stages of deglaciation history and landscape formation. We can find landscapes at different levels of postglacial stabilization which is providing the opportunity to study the interactions between geo-, bio-, social and socio-economic systems at the land surface. The DYNAFLUX / DYNACOLD Network (2004-) bridges across the geo-, bio-, social and socio-economic sciences in order to analyze the complex dynamics of stabilization, succession and landscape formation during and after ice retreat and under ongoing human influences. The network provides a multidisciplinary forum where researchers come together. In addition, it is linking a number of networks, working groups and programs and creates an umbrella network and a forum for sharing knowledge. The scientific focus of this network is also relevant for different end users, including risk and vulnerability assessment, sustainable land use, land management and conservation. In addition, key questions related to Global Change like, e.g., hazards, permafrost degradation and loss of biodiversity are discussed.

  18. Iron hydroxy carbonate formation in zerovalent iron permeable reactive barriers: Characterization and evaluation of phase stability

    SciTech Connect

    Wilkin, Richard T.; Lee, T.R.

    2010-10-22

    Predicting the long-term potential of permeable reactive barriers for treating contaminated groundwater relies on understanding the endpoints of biogeochemical reactions between influent groundwater and the reactive medium. Iron hydroxy carbonate (chukanovite) is frequently observed as a secondary mineral precipitate in granular iron PRBs. Mineralogical characterization was carried out using X-ray diffraction, scanning electron microscopy, thermogravimetric analysis, and X-ray absorption spectroscopy on materials collected from three field-based PRBs in the US (East Helena, MT; Elizabeth City, NC; Denver Federal Center, CO). These PRBs were installed to treat a range of contaminants, including chlorinated organics, hexavalent chromium, and arsenic. Results obtained indicate that chukanovite is a prevalent secondary precipitate in the PRBs. Laboratory experiments on high-purity chukanovite separates were carried out to constrain the room-temperature solubility for this mineral. An estimated Gibbs energy of formation ({Delta}{sub f}G{sup o}) for chukanovite is - 1174.4 {+-} 6 kJ/mol. A mineral stability diagram is consistent with observations from the field. Water chemistry from the three reactive barriers falls inside the predicted stability field for chukanovite, at inorganic carbon concentrations intermediate to the stability fields of siderite and ferrous hydroxide. These new data will aid in developing better predictive models of mineral accumulation in zerovalent iron PRBs.

  19. Influence of PEG-12 Dimethicone addition on stability and formation of emulsions containing liquid crystal.

    PubMed

    Andrade, F F; Santos, O D H; Oliveira, W P; Rocha-Filho, P A

    2007-06-01

    Oil/water emulsions, containing liquid crystals, were developed employing Andiroba oil, PEG-12 Dimethicone and Crodafos CES. It was evaluated the influence of silicone surfactants on the emulsions stability and on the formation of liquid crystalline phases and therefore, physicochemical characteristics, such as rheology and zeta potential, were evaluated. Emulsions were prepared by the emulsions phase inversion method. All the formulations presented lamellar liquid crystalline phases. The PEG-12 Dimethicone addition did not change microscopically the liquid crystalline phases. The emulsions containing silicone demonstrated lower viscosity than those without the additive. This is an important feature, as the silicone did not change the rheological profile; however, the addition of silicone still can be used as a viscosity controller. The formulations had their viscosity increased 15 and 150 days after their preparation. This characteristic shows that the emulsions have their organization increased along the storing time. In the analysis of zeta potential, we could verify that all formulations presented negative values between -39.7 and -70.0 mV. Within this range of values, the emulsion physical stability is high (Fig. 10). It was concluded that the addition of PEG-12 Dimethicone kept the liquid crystalline phase of the emulsion obtained with Crodafos CES, influencing in a positive way in the system stability.

  20. A test of the transition-metal nanocluster formation and stabilization ability of the most common polymeric stabilizer, poly(vinylpyrrolidone), as well as four other polymeric protectants.

    PubMed

    Ott, Lisa Starkey; Hornstein, Brooks J; Finke, Richard G

    2006-10-24

    Following an introduction to the nanocluster stabilization literature and DLVO (Derjaugin-Landau-Verwey-Overbeek) theory of colloidal stability, the most common steric stabilizer of transition-metal nanoclusters, poly(vinylpyrrolidone) (PVP), has been examined for its efficacy in the formation, stabilization, and subsequent catalytic activity of prototype, test case Ir(0)n nanoclusters. First, the five criteria established previously for ranking nanocluster protectants for their nanocluster formation and stabilization ability were evaluated for 1 monomer equiv of 10000 average molecular weight (MWav) PVP in the absence, and then presence, of the traditionally weakly coordinating anion BF4- as well as the absence and presence of the strongly coordinating, superior anionic stabilizer P2W15Nb3O62(9-), all in propylene carbonate solvent. It is found that neither 1 equiv of BF4- in propylene carbonate nor 1 monomer equiv of (undried) PVP alone allows for isolable and redissolvable nanoclusters without bulk Ir(0)n metal formation. Careful predrying of the PVP, and by implication other polymers, is shown to be necessary for the formation and stabilization of the nanoclusters. Next, 40 monomer equiv of 10000 MWav PVP and 1 equiv of BF4- in propylene carbonate are shown to allow isolable, redissolvable nanoclusters. Control experiments reveal little difference on nanocluster stabilization by 3500 or 55000 (i.e., vs 10,000) MWav PVP, but yield interesting effects on nanocluster nucleation by the 3500 MWav PVP, as well as by the polymer poly(bis(ethoxy)phosphazene) (PBEP). Four other key polymers reported in the literature to be nanocluster stabilizers are tested by the five criteria method for their efficacy in the formation and stabilization of Ir0n nanoclusters (now in acetone due to the polymers' solubility) and in comparison to each other, specifically, poly(methyl methacrylate) (PMMA), poly(styrene) (PS), poly(methylhydrosilane) (PMHS), and PBEP. Only 40 monomer equiv

  1. Formation and Stabilization of Raphasatin and Sulforaphene from Radish Roots by Endogenous Enzymolysis

    PubMed Central

    Kim, Jae-Won; Kim, Mi-Bo; Lim, Sang-Bin

    2015-01-01

    The biologically active compounds raphasatin and sulforaphene are formed during the hydrolysis of radishes by an endogenous myrosinase. Raphasatin is very unstable, and it is generated and simultaneously degraded to less active compounds during hydrolysis in aqueous media. This study determined the hydrolysis conditions to maximize the formation of raphasatin and sulforaphene by an endogenous myrosinase and minimize their degradation during the hydrolysis of radish roots. The reaction parameters, such as the reaction medium, reaction time, type of mixing, and reaction temperature were optimized. A stability test for raphasatin and sulforaphene was also performed during storage of the hydrolyzed products at 25°C for 10 days. The formation and breakdown of raphasatin and sulforaphene in radish roots by endogenous enzymolysis was strongly influenced by the reaction medium, reaction time, and type of mixing. The production and stabilization of raphasatin in radishes was efficient in water and dichloromethane with shaking for 15 min at 25°C. For sulforaphene, the favorable condition was water as the reaction medium without shaking for 10 min at 25°C. The maximum yields of raphasatin and sulforaphene were achieved in a concurrent hydrolysis reaction without shaking in water for 10 min and then with shaking in dichloromethane for 15 min at 25°C. Under these conditions, the yields of raphasatin and sulforaphene were maximized at 12.89 and 1.93 μmol/g of dry radish, respectively. The stabilities of raphasatin and sulforaphene in the hydrolyzed products were 56.4% and 86.5% after 10 days of storage in water and dichloromethane at 25°C. PMID:26175999

  2. Studies on the formation and stability of triplex DNA using fluorescence correlation spectroscopy.

    PubMed

    Hu, Hongyan; Huang, Xiangyi; Ren, Jicun

    2016-05-01

    Triplex DNA has become one of the most useful recognition motifs in the design of new molecular biology tools, therapeutic agents and sophisticated DNA-based nanomaterials because of its direct recognition of natural double-stranded DNA. In this paper, we developed a sensitive and microscale method to study the formation and stability characterization of triplex DNA using fluorescence correlation spectroscopy (FCS). The principle of this method is mainly based on the excellent capacity of FCS for sensitively distinguishing between free single-strand DNA (ssDNA) fluorescent probes and fluorescent probe-double-strand DNA (dsDNA) hybridized complexes. First, we systematically investigated the experimental conditions of triplex DNA formation. Then, we evaluated the equilibrium association constants (K(a)) under different ssDNA probe lengths, composition and pH. Finally, we used FCS to measure the hybridization fraction of a 20-mer perfectly matched ssDNA probe and three single-base mismatched ssDNA probes with 146-mer dsDNA. Our data illustrated that FCS is a useful tool for the direct determination of the thermodynamic parameters of triplex DNA formation and discrimination of a single-base mismatch of triplex DNA without denaturation. Compared with current methods, our method is characterized by high sensitivity, good universality and small sample and reagent requirements. More importantly, our method has the potential to become a platform for triplex DNA research in vitro.

  3. Chondroitin 6-Sulfation Regulates Perineuronal Net Formation by Controlling the Stability of Aggrecan.

    PubMed

    Miyata, Shinji; Kitagawa, Hiroshi

    2016-01-01

    Perineuronal nets (PNNs) are lattice-like extracellular matrix structures composed of chondroitin sulfate proteoglycans (CSPGs). The appearance of PNNs parallels the decline of neural plasticity, and disruption of PNNs reactivates neural plasticity in the adult brain. We previously reported that sulfation patterns of chondroitin sulfate (CS) chains on CSPGs influenced the formation of PNNs and neural plasticity. However, the mechanism of PNN formation regulated by CS sulfation remains unknown. Here we found that overexpression of chondroitin 6-sulfotransferase-1 (C6ST-1), which catalyzes 6-sulfation of CS chains, selectively decreased aggrecan, a major CSPG in PNNs, in the aged brain without affecting other PNN components. Both diffuse and PNN-associated aggrecans were reduced by overexpression of C6ST-1. C6ST-1 increased 6-sulfation in both the repeating disaccharide region and linkage region of CS chains. Overexpression of 6-sulfation primarily impaired accumulation of aggrecan in PNNs, whereas condensation of other PNN components was not affected. Finally, we found that increased 6-sulfation accelerated proteolysis of aggrecan by a disintegrin and metalloproteinase domain with thrombospondin motif (ADAMTS) protease. Taken together, our results indicate that sulfation patterns of CS chains on aggrecan influenced the stability of the CSPG, thereby regulating formation of PNNs and neural plasticity.

  4. Polyphenylenepyridyl dendrimers as stabilizing and controlling agents for CdS nanoparticle formation.

    PubMed

    Kuchkina, Nina V; Morgan, David Gene; Stein, Barry D; Puntus, Lada N; Sergeev, Alexander M; Peregudov, Alexander S; Bronstein, Lyudmila M; Shifrina, Zinaida B

    2012-04-07

    Semiconductor nanoparticles (NPs) are being actively explored for applications in medical diagnostics and therapy and numerous electronic devices including solar cells. In this paper we demonstrate the influence of the third generation rigid polyphenylenepyridyl dendrimers (PPPDs) of a different architecture on the formation of well-defined CdS NPs. A high temperature approach to the synthesis of novel CdS/PPPD nanocomposites is feasible due to the high thermal stability of PPPDs. The PPPD architecture affects the CdS NP formation: larger NPs are obtained in the presence of dendrimers with 1,3,5-triphenylbenzene cores compared to those with tetrakis(4-ethynylphen-1-yl)methane cores. The reaction conditions such as concentrations of PPPDs and NP precursors and the temperature regime also influence the CdS NP sizes. For the first time, we elucidated a mechanism of CdS NP formation in a non-coordinating solvent through the CdO redispersion in the presence of PPPDs. Interesting optical properties of these CdS/PPPD nanocomposites make them promising candidates for imaging applications.

  5. Generalized Momentum Control of the Spin-Stabilized Magnetospheric Multiscale Formation

    NASA Technical Reports Server (NTRS)

    Queen, Steven Z.; Shah, Neerav; Benegalrao, Suyog S.; Blackman, Kathie

    2015-01-01

    The Magnetospheric Multiscale (MMS) mission consists of four identically instrumented, spin-stabilized observatories elliptically orbiting the Earth in a tetrahedron formation. The on-board attitude control system adjusts the angular momentum of the system using a generalized thruster-actuated control system that simultaneously manages precession, nutation and spin. Originally developed using Lyapunov control-theory with rate-feedback, a published algorithm has been augmented to provide a balanced attitude/rate response using a single weighting parameter. This approach overcomes an orientation sign-ambiguity in the existing formulation, and also allows for a smoothly tuned-response applicable to both a compact/agile spacecraft, as well as one with large articulating appendages.

  6. Microwave-induced formation of platinum nanostructured networks with superior electrochemical activity and stability.

    PubMed

    Jia, Falong; Wang, Fangfang; Lin, Yun; Zhang, Lizhi

    2011-12-16

    Platinum nanostructured networks (PNNs) can be synthesized through the chemical reduction of H(2)PtCl(6) by benzyl alcohol under microwave irradiation without the introduction of any surfactants, templates, or seeds. The synthesis route utilizes benzyl alcohol as both the reductant and the structure-directing agent, and thus, the process is particularly simple and highly repeatable. The formation of the PNN structure was ascribed to the collision-induced fusion of Pt nanocrystals owing to the cooperative functions of microwave irradiation and benzyl alcohol. Compared with a commercial Pt/C catalyst, the as-prepared PNNs possessed superior electrochemical activity and stability on the oxidation of methanol because of the unique 3D nanostructured networks and abundant defects formed during the assembly process. This study may provide a facile microwave-induced approach for the synthesis of other 3D nanostructured noble metals or their alloys.

  7. Comparative study of formation and stabilization of gold and silver clusters and nanoparticles in mordenites.

    PubMed

    Bogdanchikova, N; Tuzovskaya, I; Pestryakov, A; Susarrey-Arce, A

    2011-06-01

    Supporting silver and gold on mordenites by ion-exchange method with further reduction with H2 leads to formation of neutral and charged metal clusters inside zeolite channels as well as metal nanoparticles on external surface of mordenite. A portion of the cluster states of the metals and stability of the clusters depend strongly on acidity of zeolite (determined by SiO2/Al2O3 molar ratio) and nature of zeolite cation (H+, Na+, NH4+). The investigations of silver and gold samples after prolonged storage for 6 and 12 months revealed that silver clusters are comparatively stable while oxidation of gold clusters and nanoparticles by air is the probable cause of deactivation of gold catalysts. The comparison of the results for Au and Ag samples allow suggesting NaM15 and NaM24 mordenites for effective synthesis of complex Au-Ag clusters as active and stable species of catalytic reactions occurring at room temperature.

  8. Formation conditions, chloride content, and stability of passive films on an iron-chromium alloy

    SciTech Connect

    Hubschmid, C.; Landolt, D. . Dept. des Materiaux)

    1993-07-01

    Passive films were formed on a high purity Fe-23 Cr alloy in acid sulfate solutions in the presence and absence of chloride ion. The resulting film composition was investigated by Auger depth profiling. The passivated samples were exposed to a 1M NaCl solution at a constant potential slightly above the critical pitting potential, and the current-time transient was measured in order to compare the relative stability of the different films. The results obtained suggest that the formation conditions influence the chloride content of the passive film and the breakdown behavior. Passive films formed in the presence of chloride contain and are slightly less stable towards breakdown. No chloride was found in films formed in sulfate and subsequently exposed to chloride well below the pitting potential.

  9. Silicon nanowire degradation and stabilization during lithium cycling by SEI layer formation.

    PubMed

    Cho, Jeong-Hyun; Picraux, S Tom

    2014-06-11

    Silicon anodes are of great interest for advanced lithium-ion battery applications due to their order of magnitude higher energy capacity than graphite. Below a critical diameter, silicon nanowires enable the ∼300% volume expansion during lithiation without pulverization. However, their high surface-to-volume ratio is believed to contribute to fading of their capacity retention during cycling due to solid-electrolyte-interphase (SEI) growth on surfaces. To better understand this issue, previous studies have examined the composition and morphology of the SEI layers. Here we report direct measurements of the reduction in silicon nanowire diameter with number of cycles due to SEI formation. The results reveal significantly greater Si loss near the nanowire base. From the change in silicon volume we can accurately predict the measured specific capacity reduction for silicon nanowire half cells. The enhanced Si loss near the nanowire/metal current collector interface suggests new strategies for stabilizing nanowires for long cycle life performance.

  10. Nonlinear stability analyses of vegetative pattern formation in an arid environment

    PubMed Central

    Boonkorkuea, N.; Lenbury, Y.; Alvarado, F.J.; Wollkind, D.J.

    2009-01-01

    The development of spontaneous stationary vegetative patterns in an arid isotropic homogeneous environment is investigated by means of various weakly nonlinear stability analyses applied to the appropriate governing equation for this phenomenon. In particular, that process can be represented by a fourth-order partial differential time-evolution logistic equation for the total plant biomass per unit area divided by the carrying capacity of its territory and defined on an unbounded flat spatial domain. Those patterns that consist of parallel stripes, labyrinth-like mazes, rhombic arrays of rectangular patches, and hexagonal distributions of spots or gaps are generated by the balance between the effects of short-range facilitation and long-range competition. Then those theoretical predictions are compared with both relevant observational evidence and existing numerical simulations as well as placed in the context of the results from some recent nonlinear pattern formation studies. PMID:22881129

  11. Formation and stability of the self-consistent one-dimensional tail current sheet

    NASA Technical Reports Server (NTRS)

    Pritchett, P. L.; Coroniti, F. V.

    1992-01-01

    The paper investigates the formation, the structure, and the stability of self-consistent one-dimensional current sheets in which the ions carry most of the current and momentum (the occurrence of which was suggested by observations of Mitchell et al., 1990; and Sergeev et al., 1990). Results of the analysis showed that, for the case of a cold current sheet, the characteristic thickness lamba equals to about (Bz/B0) exp 4/3 c/omega(p0), where Bz is the normal field component, B0 is the asymptotic magnitude of the reversing field, and c/omega(p0)is the collisionless ion skin depth based on lobe density. A two-dimensional self-consistent dynamical simulation model is developed, which demonstrates that these idealized current sheets are unstable to kink perturbations driven by the anisotropic pressure distribution produced by the chaotic nature of the particle orbits in a field-reversal region.

  12. Insights into hydrate formation and stability of morphinanes from a combination of experimental and computational approaches.

    PubMed

    Braun, Doris E; Gelbrich, Thomas; Kahlenberg, Volker; Griesser, Ulrich J

    2014-09-02

    Morphine, codeine, and ethylmorphine are important drug compounds whose free bases and hydrochloride salts form stable hydrates. These compounds were used to systematically investigate the influence of the type of functional groups, the role of water molecules, and the Cl(-) counterion on molecular aggregation and solid state properties. Five new crystal structures have been determined. Additionally, structure models for anhydrous ethylmorphine and morphine hydrochloride dihydrate, two phases existing only in a very limited humidity range, are proposed on the basis of computational dehydration modeling. These match the experimental powder X-ray diffraction patterns and the structural information derived from infrared spectroscopy. All 12 structurally characterized morphinane forms (including structures from the Cambridge Structural Database) crystallize in the orthorhombic space group P212121. Hydrate formation results in higher dimensional hydrogen bond networks. The salt structures of the different compounds exhibit only little structural variation. Anhydrous polymorphs were detected for all compounds except ethylmorphine (one anhydrate) and its hydrochloride salt (no anhydrate). Morphine HCl forms a trihydrate and dihydrate. Differential scanning and isothermal calorimetry were employed to estimate the heat of the hydrate ↔ anhydrate phase transformations, indicating an enthalpic stabilization of the respective hydrate of 5.7 to 25.6 kJ mol(-1) relative to the most stable anhydrate. These results are in qualitative agreement with static 0 K lattice energy calculations for all systems except morphine hydrochloride, showing the need for further improvements in quantitative thermodynamic prediction of hydrates having water···water interactions. Thus, the combination of a variety of experimental techniques, covering temperature- and moisture-dependent stability, and computational modeling allowed us to generate sufficient kinetic, thermodynamic and structural

  13. X Chromosome Crossover Formation and Genome Stability in Caenorhabditis elegans Are Independently Regulated by xnd-1

    PubMed Central

    McClendon, T. Brooke; Mainpal, Rana; Amrit, Francis R. G.; Krause, Michael W.; Ghazi, Arjumand; Yanowitz, Judith L.

    2016-01-01

    The germ line efficiently combats numerous genotoxic insults to ensure the high fidelity propagation of unaltered genomic information across generations. Yet, germ cells in most metazoans also intentionally create double-strand breaks (DSBs) to promote DNA exchange between parental chromosomes, a process known as crossing over. Homologous recombination is employed in the repair of both genotoxic lesions and programmed DSBs, and many of the core DNA repair proteins function in both processes. In addition, DNA repair efficiency and crossover (CO) distribution are both influenced by local and global differences in chromatin structure, yet the interplay between chromatin structure, genome integrity, and meiotic fidelity is still poorly understood. We have used the xnd-1 mutant of Caenorhabditis elegans to explore the relationship between genome integrity and crossover formation. Known for its role in ensuring X chromosome CO formation and germ line development, we show that xnd-1 also regulates genome stability. xnd-1 mutants exhibited a mortal germ line, high embryonic lethality, high incidence of males, and sensitivity to ionizing radiation. We discovered that a hypomorphic allele of mys-1 suppressed these genome instability phenotypes of xnd-1, but did not suppress the CO defects, suggesting it serves as a separation-of-function allele. mys-1 encodes a histone acetyltransferase, whose homolog Tip60 acetylates H2AK5, a histone mark associated with transcriptional activation that is increased in xnd-1 mutant germ lines, raising the possibility that thresholds of H2AK5ac may differentially influence distinct germ line repair events. We also show that xnd-1 regulated him-5 transcriptionally, independently of mys-1, and that ectopic expression of him-5 suppressed the CO defects of xnd-1. Our work provides xnd-1 as a model in which to study the link between chromatin factors, gene expression, and genome stability. PMID:27678523

  14. Study of formation, stabilization and properties of porous silicon and porous silica

    NASA Astrophysics Data System (ADS)

    Hecini, Mouna; Khelifa, Abdellah; Bouzid, Bachir; Drouiche, Nadjib; Aoudj, Salaheddine; Hamitouche, Houria

    2013-09-01

    The large specific surface area of porous silicon (PS) gives it a high degree of chemical surface reactivity. Formation of silicon oxide (silica, SiO2), via different oxidation methods (thermal or electrochemical) within the porous matrix turns out to be an additional factor of PS stability and an improvement of its chemical, structural, morphological, crystalline and optical properties. In this work, PS reactivity is justified by the presence of siloxane (SiOSi) and silanol (SiOH) free and bound sites. Oxidation and densification effects on mesoporous silicon layers properties were investigated. The influence of operating parameters (current density, electrolyte concentration, treatment time, temperature, and oxidizing gas) on PS morphology and oxide quality were assessed. Sample characterization was performed using FTIR, SEM, EDS, XRD and UV-Visible spectrophotometry. Our results showed that oxidation provides stabilization and chemical modification of PS specific surface by creation of SiOH and SiOSi active sites. The optical and crystalline properties are dependent on oxidation temperature. Wet thermal oxidation, preceded by a short dry oxidation under O2, followed by densification under N2, with an oxidation rate of greater than 62%, improves PS properties for a functionalization via silanization.

  15. The hypoparathyroidism-associated mutation in Drosophila Gcm compromises protein stability and glial cell formation

    PubMed Central

    Xi, Xiao; Lu, Lu; Zhuge, Chun-Chun; Chen, Xuebing; Zhai, Yuanfen; Cheng, Jingjing; Mao, Haian; Yang, Chang-Ching; Tan, Bertrand Chin-Ming; Lee, Yi-Nan; Chien, Cheng-Ting; Ho, Margaret S.

    2017-01-01

    Differentiated neurons and glia are acquired from immature precursors via transcriptional controls exerted by factors such as proteins in the family of Glial Cells Missing (Gcm). Mammalian Gcm proteins mediate neural stem cell induction, placenta and parathyroid development, whereas Drosophila Gcm proteins act as a key switch to determine neuronal and glial cell fates and regulate hemocyte development. The present study reports a hypoparathyroidism-associated mutation R59L that alters Drosophila Gcm (Gcm) protein stability, rendering it unstable, and hyperubiquitinated via the ubiquitin-proteasome system (UPS). GcmR59L interacts with the Slimb-based SCF complex and Protein Kinase C (PKC), which possibly plays a role in its phosphorylation, hence altering ubiquitination. Additionally, R59L causes reduced Gcm protein levels in a manner independent of the PEST domain signaling protein turnover. GcmR59L proteins bind DNA, functionally activate transcription, and induce glial cells, yet at a less efficient level. Finally, overexpression of either wild-type human Gcmb (hGcmb) or hGcmb carrying the conserved hypoparathyroidism mutation only slightly affects gliogenesis, indicating differential regulatory mechanisms in human and flies. Taken together, these findings demonstrate the significance of this disease-associated mutation in controlling Gcm protein stability via UPS, hence advance our understanding on how glial formation is regulated. PMID:28051179

  16. Design and expression of recombinant antihypertensive peptide multimer gene in Escherichia coli BL21.

    PubMed

    Rao, Shengqi; Su, Yujie; Li, Junhua; Xu, Zhenzhen; Yang, Yanjun

    2009-12-01

    The design and expression of an antihypertensive peptide multimer (AHPM), a common precursor of 11 kinds of antihypertensive peptides (AHPs) tandemly linked up according to the restriction sites of gastrointestinal proteases, were explored. The DNA fragment encoding the AHPM was chemically synthesized and cloned into expression vector pGEX-3X. After an optimum induction with IPTG, the recombinant AHPM fused with glutathione S-transferase (GST-AHPM) was expressed mostly as inclusion body in Escherichia coli BL21 and reached the maximal production, 35% of total intracellular protein. The inclusion body was washed, dissolved, and purified by cation exchange chromatography under denaturing conditions, followed by refolding together with size exclusion chromatography and gradual dialysis. The resulting yield of the soluble GST-AHPM (34 kDa) with a purity of 95% reached 399 mg/l culture. The release of high active fragments from the AHPM was confirmed by the simulated gastrointestinal digestion. The results suggest that the design strategy and production method of the AHPM will be useful to obtain a large quantity of recombinant AHPs at a low cost.

  17. Shear-Induced Unfolding and Enzymatic Cleavage of Full-Length VWF Multimers

    PubMed Central

    Lippok, Svenja; Radtke, Matthias; Obser, Tobias; Kleemeier, Lars; Schneppenheim, Reinhard; Budde, Ulrich; Netz, Roland R.; Rädler, Joachim O.

    2016-01-01

    Proteolysis of the multimeric blood coagulation protein von Willebrand Factor (VWF) by ADAMTS13 is crucial for prevention of microvascular thrombosis. ADAMTS13 cleaves VWF within the mechanosensitive A2 domain, which is believed to open under shear flow. In this study, we combine fluorescence correlation spectroscopy (FCS) and a microfluidic shear cell to monitor real-time kinetics of full-length VWF proteolysis as a function of shear stress. For comparison, we also measure the Michaelis-Menten kinetics of ADAMTS13 cleavage of wild-type VWF in the absence of shear but partially denaturing conditions. Under shear, ADAMTS13 activity on full-length VWF arises without denaturing agent as evidenced by FCS and gel-based multimer analysis. In agreement with Brownian hydrodynamics simulations, we find a sigmoidal increase of the enzymatic rate as a function of shear at a threshold shear rate γ˙1/2 = 5522/s. The same flow-rate dependence of ADAMTS13 activity we also observe in blood plasma, which is relevant to predict hemostatic dysfunction. PMID:26840720

  18. Formation, stability, and crystal structure of σ phase in Mo-Re-Si alloys

    SciTech Connect

    Bei, Hongbin; Yang, Ying; Viswanathan, G.; Rawn, Claudia J; George, Easo P; Tiley, Jaimie; Chang, Y. Austin

    2010-01-01

    The formation, stability and crystal structure of the {sigma} phase in Mo-Re-Si alloys were investigated. Guided by thermodynamic calculations, six critically selected alloys were arc melted and annealed at 1600 C for 150 h. Their as-cast and annealed microstructures, including phase fractions and distributions, the compositions of the constituent phases and the crystal structure of the {sigma} phase were analyzed by thermodynamic modeling coupled with experimental characterization by scanning electron microscopy, electron probe microanalysis, X-ray diffraction and transmission electron microscopy. Two key findings resulted from this work. One is the large homogeneity range of the {sigma} phase region, extending from binary Mo-Re to ternary Mo-Re-Si. The other is the formation of a {sigma} phase in Mo-rich alloys either through the peritectic reaction of liquid + Mo{sub ss} {yields} {sigma} or primary solidification. These findings are important in understanding the effects of Re on the microstructure and providing guidance on the design of Mo-Re-Si alloys.

  19. Enhanced enteric properties and stability of shellac films through composite salts formation.

    PubMed

    Limmatvapirat, Sontaya; Limmatvapirat, Chutima; Puttipipatkhachorn, Satit; Nuntanid, Jurairat; Luangtana-Anan, Manee

    2007-11-01

    The objective of this study was to improve the properties of shellac by composite salts formation. The shellac samples were prepared in various salt forms by dissolving them with 2-amino-2-methyl-1-propanol (AMP) and ammonium hydroxide (AMN) at various ratios of AMP:AMN. The results demonstrated that aqueous solubility of the shellac salts was improved as the ratio of AMP:AMN increased. The absorbance ratio of the FTIR peaks assigned to CO stretching of carboxylate and carboxylic acid (ABS1556/ABS1716) was increased with the increase of the AMP fraction, suggesting that the solubility enhancement was due to more ionization of AMP salts. Moisture adsorption studies indicated that shellac salts were more hygroscopic as AMP content increased. After storage at 40 degrees C, 75% RH, the acid value and insoluble solid of AMP salts were relatively constant even after storage of up to 180 days, suggesting that AMP should protect polymerization. The ABS1556/ABS1716 values of the shellac salts were rapidly decreased after storage, especially for those consisting of a high percentage of AMN. Thus, AMP should bind much tighter at the carboxylate binding site as compared with AMN, resulting in more solubility and stability. In conclusion, optimized shellac properties could be easily accomplished by composite salts formation.

  20. Formation and stability of ridge-ridge-ridge triple junctions in rheologically realistic lithosphere model

    NASA Astrophysics Data System (ADS)

    Gerya, Taras; Burov, Evgueni

    2015-04-01

    Triple junctions are probably the most remarkable features of plate boundaries since their presence constitutes one of the major demonstrations of plate tectonics theory. Divergent (R-R-R) triple junctions (at 120° and T junctions) are particular ones since their stability depends on the exact values of the relative velocities of plate divergence and hence is strongly affected by plate rheology and processes of crustal accretion. The mechanisms of their formation and long-term steadiness are not well understood even though it is commonly accepted, generally based on common sense, that the geometry and stability of triple junctions should be related to the intuitively acceptable geometric considerations that 3-branch configurations should be "stable" over the time on a 3D Earth surface. That said, most plate boundaries are in fact 2D in terms that they involve only two plates, while junctions with 3 and more branches, if even mechanically not excluded, are generally short-lived and hence rarely observed at tectonic scale. Indeed, it has been long-time suggested that triple junctions result from evolution of short-lived quadruple junctions, yet, without providing a consistent mechanical explanation or experimental demonstration of this process, due to the rheological complexity of the lithosphere and that of strain localization and crustal accretion processes. For example, it is supposed that R-R-R junctions form as result of axisymmetric mantle upwellings. However, impingement of buoyant fluid on a non-pre-stressed lithosphere should result in multiple radial cracks, as is well known from previous analog and numerical experiments. In case of uni-directionally pre-stressed lithosphere, it has also shown that linear 2D rift structures should be formed. Therefore, a complete 3D thermos-mechanically consistent approach is needed to understand the processes of formation of multi-branch junctions. With this goal we here reproduce and study the processes of multi

  1. Protein kinase D promotes plasticity-induced F-actin stabilization in dendritic spines and regulates memory formation

    PubMed Central

    Bencsik, Norbert; Szíber, Zsófia; Liliom, Hanna; Tárnok, Krisztián; Borbély, Sándor; Gulyás, Márton; Rátkai, Anikó; Szűcs, Attila; Hazai-Novák, Diána; Ellwanger, Kornelia; Rácz, Bence; Pfizenmaier, Klaus; Hausser, Angelika

    2015-01-01

    Actin turnover in dendritic spines influences spine development, morphology, and plasticity, with functional consequences on learning and memory formation. In nonneuronal cells, protein kinase D (PKD) has an important role in stabilizing F-actin via multiple molecular pathways. Using in vitro models of neuronal plasticity, such as glycine-induced chemical long-term potentiation (LTP), known to evoke synaptic plasticity, or long-term depolarization block by KCl, leading to homeostatic morphological changes, we show that actin stabilization needed for the enlargement of dendritic spines is dependent on PKD activity. Consequently, impaired PKD functions attenuate activity-dependent changes in hippocampal dendritic spines, including LTP formation, cause morphological alterations in vivo, and have deleterious consequences on spatial memory formation. We thus provide compelling evidence that PKD controls synaptic plasticity and learning by regulating actin stability in dendritic spines. PMID:26304723

  2. Effect of the structure of lipids favoring disordered domain formation on the stability of cholesterol-containing ordered domains (lipid rafts): identification of multiple raft-stabilization mechanisms.

    PubMed

    Bakht, Omar; Pathak, Priyadarshini; London, Erwin

    2007-12-15

    Despite the importance of lipid rafts, commonly defined as liquid-ordered domains rich in cholesterol and in lipids with high gel-to-fluid melting temperatures (T(m)), the rules for raft formation in membranes are not completely understood. Here, a fluorescence-quenching strategy was used to define how lipids with low T(m), which tend to form disordered fluid domains at physiological temperatures, can stabilize ordered domain formation by cholesterol and high-T(m) lipids (either sphingomyelin or dipalmitoylphosphatidylcholine). In bilayers containing mixtures of low-T(m) phosphatidylcholines, cholesterol, and high-T(m) lipid, the thermal stability of ordered domains decreased with the acyl-chain structure of low-T(m) lipids in the following order: diarachadonyl > diphytanoyl > 1-palmitoyl 2-docosahexenoyl = 1,2 dioleoyl = dimyristoleoyl = 1-palmitoyl, 2-oleoyl (PO). This shows that low-T(m) lipids with two acyl chains having very poor tight-packing propensities can stabilize ordered domain formation by high-T(m) lipids and cholesterol. The effect of headgroup structure was also studied. We found that even in the absence of high-T(m) lipids, mixtures of cholesterol with PO phosphatidylethanolamine (POPE) and PO phosphatidylserine (POPS) or with brain PE and brain PS showed a (borderline) tendency to form ordered domains. Because these lipids are abundant in the inner (cytofacial) leaflet of mammalian membranes, this raises the possibility that PE and PS could participate in inner-leaflet raft formation or stabilization. In bilayers containing ternary mixtures of PO lipids, cholesterol, and high-T(m) lipids, the thermal stability of ordered domains decreased with the polar headgroup structure of PO lipids in the order PE > PS > phosphatidylcholine (PC). Analogous experiments using diphytanoyl acyl chain lipids in place of PO acyl chain lipids showed that the stabilization of ordered lipid domains by acyl chain and headgroup structure was not additive. This implies

  3. Formation, stability, and solubility of metal oxide nanoparticles: Surface entropy, enthalpy, and free energy of ferrihydrite

    NASA Astrophysics Data System (ADS)

    Hiemstra, Tjisse

    2015-06-01

    Ferrihydrite (Fh) is an excellent model for understanding nanoparticle behavior in general. Moreover, Fh is one of the most important Fe (hydr) oxides in nature. Fh particles can be extremely small leading to a very high reactive surface area that changes its chemical potential, strongly affecting the solubility, nucleation, and stability. These characteristics can be coupled to the interfacial Gibbs free energy, being γ = 0.186 ± 0.01 J m-2 for Fh. The surface free energy has a relatively large contribution of surface entropy (-TSsurf = +0.079 ± 0.01 J m-2). The surface entropy is primarily related to the formation of surface groups by chemisorption of water (-17.1 J mol-1 K-1), for Fh equivalent with +0.064 ± 0.002 J m-2 at a surface loading NH2O = 12.6 μmol m-2. The entropy contribution of physisorbed water has been estimated by analyzing, as model, the surface enthalpy, entropy, and Gibbs free energy of the principal interfaces of H2O, i.e. ice-water-gas. It is about 20% of the contribution of chemisorbed water. The surface enthalpy of Fh is exceptionally low (Hsurf = +0.107 ± 0.01 J m-2), which can be explained by surface depletion (SD) of relatively unstable Fe polyhedra, or similarly, by additional surface loading of the non-depleted mineral core with specific Fe polyhedra for stabilization. The experimental enthalpy of Fh formation varies linearly with the surface area and correctly predicts the enthalpy value for the mineral core (-405.2 ± 1.2 kJ mol FeO3/2), being similar to the literature value for Fh as virtual bulk material (-406.7 ± 1.5 kJ mol FeO3/2) obtained with MO/DFT computations. The thermochemical quantities of the mineral core and surface are essentially the same for the entire range of Fh samples, in line with the SD model. The solubility of Fh suspensions as a whole may differ from the behavior of individual particles due to polydispersity. For 2-line Fh, the overall solubility is log Kso ∼ -38.5 ± 0.1 and for prolongedly aged 6

  4. Evidence for formation of a PAN analogue of pinonic structure and investigation of its thermal stability

    NASA Astrophysics Data System (ADS)

    NozièRe, Barbara; Barnes, Ian

    1998-10-01

    The first evidence and laboratory study of a peroxyacetyl nitrate (PAN) analogue produced by the photooxidation of a terpene, α-pinene, is presented. This PAN analogue, assigned to 3-acetyl-2,2-dimethyl-cyclobutane-acetyl peroxynitrate and referred to as "α-pinonyl peroxynitrate" (αP-PAN) was synthesized in the gas phase from the radical (OH, Cl, Br, or NO3) initiated oxidation of pinonaldehyde (3-acetyl-2,2-dimethyl-cyclobutyl-ethanal) in the presence of excess NO2 and evidenced by Fourier transform-infrared (FT-IR) spectroscopy. Another reaction channel producing PAN was also observed for some of the radical initiators. Of particular atmospheric interest, the experiments with OH radicals demonstrated that αP-PAN is the main product of pinonaldehyde under NOx-rich conditions with a yield of (81.3±16)%, while an upper limit of the PAN yield for this reaction is around 8%. The further photooxidation of αP-PAN was also observed to produce PAN directly. The thermal stability of αP-PAN was studied between 303 and 281 K. The rate constant of thermal dissociation was found to be k-1 = 10(9.25±0.33) × exp [-(72.0±1.9)/RT] where the activation energy is in kJ mol-1. Distortions of the kinetic profiles attributed to aerosol formation were observed and led to large errors in the above estimation of k-1. Within the uncertainties, the observed thermal stability of αP-PAN is comparable to that of PAN. The tropospheric importance of pinonaldehyde and of αP-PAN are discussed.

  5. Partial reactivation of a huge deep-seated ancient rock slide: recognition, formation mechanism, and stability

    NASA Astrophysics Data System (ADS)

    Tang, Minggao; Xu, Qiang; Li, Yusheng; Huang, Runqiu; Rengers, Niek; Zhu, Xing

    2016-08-01

    About 18 years ago, a large-scale discontinuous layer in properties and colour was found in the new Fengjie town at the shore of the Three Gorges Reservoir area in China. There are many resettled residents and buildings on the sloping area, the safety of which is potentially affected by this layer, so it has become the focus of attention. Before this study started there were two viewpoints regarding the origin of this layer. One was that is was from a huge ancient slide and the other was that is was from a fault graben. In order to find out how it was formed and to be able to carry out a stability analysis of the slope the authors have carried out a research program, including geological field investigations and mapping, a deep drilling hole, a geotechnical centrifuge model test, and a simulation analysis. The results of the research led to the conclusion that the layer is the sliding plane of a huge deep-seated ancient rock slide, which we called the Sanmashan landslide. An important argument for the conclusion is the recognition of a regional compressive tectonic stress field in this area, which cannot lead to the formation of a fault graben because it needs a tensional tectonic stress field. Moreover, numerous unique geological features, sliding marks, and other relics of the ancient slide have been discovered in the field. The formation process of the ancient slide could be repeated in a large geotechnical centrifuge model test. The test shows that a deformation and failure process of "creep-crack-cut" has occurred. The type of the ancient slide can be classified as a "successive rotational rock slide". Finally, the role of seepage in the stability of the Sanmashan landslide has been analysed. Our final conclusions are that, during rainfall and filling-drawdown cycles in the Three Gorges Reservoir, the Sanmashan landslide as a whole is dormant and stable and the secondary landslides in the toe area of the slope are presently stable but can be reactivated. This

  6. 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

  7. Nitrate photochemistry in NaY zeolite: product formation and product stability under different environmental conditions.

    PubMed

    Gankanda, Aruni; Grassian, Vicki H

    2013-03-14

    In the atmosphere, mineral dust particles are often associated with adsorbed nitrate from heterogeneous reactions with nitrogen oxides (N2O5, HNO3, NO3, and NO2). Nitrate ions associated with mineral dust particles can undergo further reactions including those initiated by solar radiation. Although nitrate photochemistry in aqueous media is fairly well studied, much less is known about the photochemistry of nitrate adsorbed on mineral dust particles. In this study, the photochemistry of nitrate from HNO3 adsorption in NaY zeolite under different environmental conditions has been investigated using transmission FTIR spectroscopy. NaY zeolite is used as a model zeolite for studying reactions that can occur in confined space such as those found in porous materials including naturally occurring zeolites and clays. Upon nitrate photolysis under dry conditions (relative humidity, RH, < 1%), surface nitrite is formed as the major adsorbed product. Although nitrite has been proposed as a product in the photochemistry of nitrate adsorbed on metal oxide particle surfaces, such as on alumina, it has not been previously detected. The stability of adsorbed nitrite in NaY is attributed to the confined three-dimensional structure of the porous zeolite, which contains a charge compensating cation that can stabilize the nitrite ion product. Besides adsorbed nitrite, small amounts of gas phase nitrogen-containing products are observed as well including NO2, NO, and N2O at long irradiation times. The amount of nitrite formed via nitrate photochemistry decreases with increasing relative humidity, whereas gas phase NO and N2O become the only detectable products. Gas-phase NO2 does not observe at RH > 1%. In the presence of gas phase ammonia, ammonium nitrate is formed in NaY zeolite. Photochemistry of ammonium nitrate yields gas phase N2O as the sole gas phase product. Evidence for an NH2 intermediate in the formation of N2O is identified with FTIR spectroscopy for HNO3 adsorption and

  8. Zinc promotes clot stability by accelerating clot formation and modifying fibrin structure.

    PubMed

    Henderson, Sara J; Xia, Jing; Wu, Huayin; Stafford, Alan R; Leslie, Beverly A; Fredenburgh, James C; Weitz, David A; Weitz, Jeffrey I

    2016-03-01

    Zinc released from activated platelets binds fibrin(ogen) and attenuates fibrinolysis. Although zinc also affects clot formation, the mechanism and consequences are poorly understood. To address these gaps, the effect of zinc on clot formation and structure was examined in the absence or presence of factor (F) XIII. Zinc accelerated a) plasma clotting by 1.4-fold, b) fibrinogen clotting by 3.5- and 2.3-fold in the absence or presence of FXIII, respectively, c) fragment X clotting by 1.3-fold, and d) polymerisation of fibrin monomers generated with thrombin or batroxobin by 2.5- and 1.8-fold, respectively. Whereas absorbance increased up to 3.3-fold when fibrinogen was clotted in the presence of zinc, absorbance of fragment X clots was unaffected by zinc, consistent with reports that zinc binds to the αC-domain of fibrin(ogen). Scanning electron microscopic analysis revealed a two-fold increase in fibre diameter in the presence of zinc and in permeability studies, zinc increased clot porosity by 30-fold with or without FXIII. Whereas FXIII increased clot stiffness from 128 ± 19 Pa to 415 ± 27 Pa in rheological analyses, zinc reduced clot stiffness by 10- and 8.5-fold in the absence and presence of FXIII, respectively. Clots formed in the presence of zinc were more stable and resisted rupture with or without FXIII. Therefore, zinc accelerates clotting and reduces fibrin clot stiffness in a FXIII-independent manner, suggesting that zinc may work in concert with FXIII to modulate clot strength and stability.

  9. Modeling the influence of storms on sand wave formation: A linear stability approach

    NASA Astrophysics Data System (ADS)

    Campmans, G. H. P.; Roos, P. C.; de Vriend, H. J.; Hulscher, S. J. M. H.

    2017-04-01

    We present an idealized process-based morphodynamic model to study the effect of storms on sand wave formation. To this end, we include wind waves, wind-driven flow and, in addition to bed load transport, suspended load sediment transport. A linear stability analysis is applied to systematically study the influence of wave and wind conditions on growth and migration rates of small-amplitude wavy bed undulations. The effects of the wind and waves of various magnitudes and directions are investigated. Waves turn out to decrease the growth rate of sand waves, because their effect on the downhill gravitational transport component is stronger than their growth-enhancing effect. The wind wave effect is strongest for wind waves perpendicular to the tidal current. In the case of a symmetrical tidal current, wind-driven flow tends to breach the symmetry, thus causing sand wave migration. Wind effects on sand wave behavior are strongly influenced by the Coriolis effect, in magnitude as well as direction. Stirring due to wind waves enhances sand wave migration. Next to bed load transport, suspended load also has a growing and a decaying mechanism, being the perturbed flow and the perturbed suspended sediment concentration respectively. The decaying mechanism outcompetes the growing mechanism for bed forms with shorter wavelengths, resulting in an increase in the preferred wavelength. Wind waves increase the growth rate due to suspended load, but this is outcompeted by the reduction in growth rate by wind waves due to bed load transport. We conclude that storms significantly influence sand wave dynamics in their formation stage.

  10. Green rust nanoparticle formation, stability and oxidation, and its role in natural and engineered systems

    NASA Astrophysics Data System (ADS)

    Shaw, S.; Benning, L.; Ahmed, I.; Kakonyi, G.; Sumoondur, A.; Terrill, N.

    2009-12-01

    Highly reactive green rust (GR) nanoparticles are believed to play an important role in the geochemistry of water saturated sediments (e.g. hydromorphic soils) and engineered systems where zero-valent iron is used for decontaminating polluted sites (e.g. permeable reactive barriers). The presence of structural Fe2+ within GR and its high specific surface area make it an effective reductant for many inorganic (e.g. Cr, U, Se) and organic substances (e.g. tetrachloroethene (TCE)). These reduction processes can lead to breakdown of organic molecules or the formation of insoluble reduced inorganic phases (e.g., UO2(s)), thus reducing the bioavailability of these toxic compounds. Understanding the formation and geochemical stability of GR is key to assessing its potential role in natural sediments and engineered environments. However, characterizing GR is difficult due to the rapid oxidation (seconds - minutes) of structural Fe2+ in the presence of air. Thus, to obtain detailed information about the mechanism and kinetics of GR formation, stabilisation and oxidative breakdown, novel synchrotron-based methods have been developed which combine in situ and time-resolved X-ray diffraction/scattering (XRD/SAXS) analysis with controlled anaerobic chemical synthesis. This system allowed the simultaneous quantification of several chemical parameters in the aqueous solution (i.e., pH, Eh) with detailed analysis of the changes in the solid phase crystal structure. In conjunction with this X-ray Absorption Spectroscopy (XAS) was used to characterise the speciation of trace elements (i.e. U, Zn and Se) associated with GR as it crystallised and/or transformed. The formation of green rust (Fe2+/Fe3+ > 1.2) from solution occurs via a 3 stage process. The first stage is the nucleation and growth of ferric hydroxysulfate (schwertmannite) nanoparticles (~5 nm). With increasing pH the schwertmannite transforms into nanogoethite particles (< 50 nm). This process is catalyzed by adsorbed Fe

  11. Microsolvated and chelated butylzinc cations: formation, relative stability, and unimolecular gas-phase chemistry.

    PubMed

    Fleckenstein, Julia E; Koszinowski, Konrad

    2009-11-23

    Solutions of butylzinc iodide in tetrahydrofuran, acetonitrile, and N,N-dimethylformamide were analyzed by electrospray ionization mass spectrometry. In all cases, microsolvated butylzinc cations [ZnBu(solvent)(n)](+), n=1-3, were detected. The parallel observation of the butylzincate anion [ZnBuI(2)](-) suggests that these ions result from disproportionation of neutral butylzinc iodide in solution. In the presence of simple bidentate ligands (1,2-dimethoxyethane, N,N-dimethyl-2-methoxyethylamine, and N,N,N',N'-tetramethylethylenediamine), chelate complexes of the type [ZnBu(ligand)](+) form quite readily. The relative stabilities of these complexes were probed by competition experiments and analysis of their unimolecular gas-phase reactivity. Fragmentation of mass-selected [ZnBu(ligand)](+) leads to the elimination of butene and formation of [ZnH(ligand)](+). In marked contrast, the microsolvated cations [ZnBu(solvent)(n)](+) lose the attached solvent molecules upon gas-phase fragmentation to produce bare [ZnBu](+), which subsequently dissociates into [C(4)H(9)](+) and Zn. This difference in reactivity resembles the situation in organozinc solution chemistry, in which chelating ligands are needed to activate dialkylzinc compounds for the nucleophilic addition to aldehydes.

  12. Enigmatic Isovaline: Investigating the Stability, Racemization, and Formation of a Non-biological Meteoritic Amino Acid

    NASA Technical Reports Server (NTRS)

    Hudson, Reggie; Moore, Marla; Lewis, Ariel; Dworkin, Jason

    2008-01-01

    Among the Murchison meteoritic amino acids, isovaline stands out as being both nonbiological (non-protein) and having a relatively high abundance. While approximately equal amounts of D- and L-isovaline have been reported in Murchison and other CM meteorites, the molecule's structure appears to prohibit its racemization in aqueous solutions. We recently have investigated the low-temperature solid-phase chemistry of both isovaline and valine with an eye toward each molecule's formation, stability, and possible interconversions of D and L enantiomers. Ion-irradiated isovaline- and valinecontaining ices were examined by IR spectroscopy and highly-sensitive liquid chromatography/time-of-flight mass spectral methods to assess both amino acid destruction and racemization. Samples were studied in the presence and in the absence of water-ice, and the destruction of both isovaline and valine was measured as a function of radiation dose. In addition, we have undertaken experiments to synthesize isovaline, valine, and their amino acid isomers by solid-phase radiation-chemical pathways other than the oft-invoked Strecker process. This presentation will review and summarize some of our recent findings. -- Our work has been supported by a grant to the Goddard Center for Astrobiology through the NASA Astrobiology Institute. Experiments were performed in the Cosmic Ice Laboratory (RLH, MHM, AL) and the Astrobiology Analytical Laboratory (JPD, DPG) at the NASA Goddard Space Flight Center.

  13. Septin9 is involved in septin filament formation and cellular stability.

    PubMed

    Füchtbauer, Annette; Lassen, Louise B; Jensen, Astrid B; Howard, Jennifer; Quiroga, Adán de Salas; Warming, Søren; Sørensen, Annette B; Pedersen, Finn S; Füchtbauer, Ernst-Martin

    2011-08-01

    Septin9 (Sept9) is a member of the filament-forming septin family of structural proteins and is associated with a variety of cancers and with hereditary neuralgic amyotrophy. We have generated mice with constitutive and conditional Sept9 knockout alleles. Homozygous deletion of Sept9 results in embryonic lethality around day 10 of gestation whereas mice homozygous for the conditional allele develop normally. Here we report the consequences of homozygous loss of Sept9 in immortalized murine embryonic fibroblasts. Proliferation rate was not changed but cells without Sept9 had an altered morphology compared to normal cells, particularly under low serum stress. Abnormal, fragmented, and multiple nuclei were more frequent in cells without Sept9. Cell migration, as measured by gap-filling and filter-invasion assays, was impaired, but individual cells did not move less than wild-type cells. Sept9 knockout cells showed a reduced resistance to hypo-osmotic stress. Stress fiber and vinculin staining at focal adhesion points was less prominent. Long septin filaments stained for Sept7 disappeared. Instead, staining was found in short, often curved filaments and rings. Furthermore, Sept7 was no longer localized to the mitotic spindle. Together, these data reveal the importance of Sept9 for septin filament formation and general cell stability.

  14. 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.

  15. Src and cortactin promote lamellipodia protrusion and filopodia formation and stability in growth cones

    PubMed Central

    He, Yingpei; Ren, Yuan; Wu, Bingbing; Decourt, Boris; Lee, Aih Cheun; Taylor, Aaron; Suter, Daniel M.

    2015-01-01

    Src tyrosine kinases have been implicated in axonal growth and guidance; however, the underlying cellular mechanisms are not well understood. Specifically, it is unclear which aspects of actin organization and dynamics are regulated by Src in neuronal growth cones. Here, we investigated the function of Src2 and one of its substrates, cortactin, in lamellipodia and filopodia of Aplysia growth cones. We found that up-regulation of Src2 activation state or cortactin increased lamellipodial length, protrusion time, and actin network density, whereas down-regulation had opposite effects. Furthermore, Src2 or cortactin up-regulation increased filopodial density, length, and protrusion time, whereas down-regulation promoted lateral movements of filopodia. Fluorescent speckle microscopy revealed that rates of actin assembly and retrograde flow were not affected in either case. In summary, our results support a model in which Src and cortactin regulate growth cone motility by increasing actin network density and protrusion persistence of lamellipodia by controlling the state of actin-driven protrusion versus retraction. In addition, both proteins promote the formation and stability of actin bundles in filopodia. PMID:26224308

  16. Drosophila BTB/POZ domains of "ttk group" can form multimers and selectively interact with each other.

    PubMed

    Bonchuk, Artem; Denisov, Stepan; Georgiev, Pavel; Maksimenko, Oksana

    2011-09-23

    The BTB (bric-a-brac, tramtrack and broad complex)/POZ (poxvirus and zinc finger) domain is a conserved protein-protein interaction motif contained in a variety of transcription factors involved in development, chromatin remodeling, insulator activity, and carcinogenesis. All well-studied mammalian BTB domains form obligate homodimers and, rarely, tetramers. Only the BTB domain of the Drosophila GAGA factor (GAF) has been shown to exist as higher-order multimers. The BTB domain of GAF belongs to the "ttk group" that contains several highly conserved sequences not found in other BTB domains. Here, we have shown by size-exclusion chromatography, chemical cross-linking, and nondenaturing PAGE that four additional BTB domains of the ttk group-Batman, Mod(mdg4), Pipsqueak, and Tramtrack-can form multimers, like GAF. Interestingly, the BTB domains of GAF and Batman have formed a wide range of complexes and interacted in the yeast two-hybrid assay with other BTB domains tested. In contrast, the BTB domains of Mod(mdg4), Pipsqueak, and Tramtrack have formed stable high-order multimer complexes and failed to interact with each other. The BTB domain of Drosophila CP190 protein does not belong to the ttk group. This BTB domain has formed stable dimers and has not interacted with domains of the ttk group. Previously, it was suggested that GAF oligomerization into higher-order complexes facilitates long-range activation by providing a protein bridge between an enhancer and a promoter. Unexpectedly, experiments in the Drosophila model system have not supported the role of GAF in organization of long-distance interaction between the yeast GAL4 activator and the white promoter.

  17. 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].

  18. Miscibility behavior and formation mechanism of stabilized felodipine-polyvinylpyrrolidone amorphous solid dispersions.

    PubMed

    Karavas, Evangelos; Ktistis, Georgios; Xenakis, Aristotelis; Georgarakis, Emmanouel

    2005-07-01

    In the present study, solid dispersion systems of felodipine (FEL) with polyvinylpyrrolidone (PVP) were developed, in order to enhance solid state stability and release kinetics. The prepared systems were characterized by using Differential Scanning Calorimetry, X-Ray Diffraction, and Scanning Electron Microscopy techniques, while the interactions which take place were identified by using Fourier Transformation-Infrared Spectroscopy. Due to the formation of hydrogen bonds between the carbonyl group of PVP and the amino groups of FEL, transition of FEL from crystalline to amorphous state was achieved. The dispersion of FEL was found to be in nano-scale particle sizes and dependent on the FEL/PVP ratio. This modification leads to partial miscibility of the two components, as it was verified by DSC and optimal glass dispersion of FEL into the polymer matrix since no crystalline structure was detected with XRD. The above deformation has a significant effect on the dissolution enhancement and the release kinetics of FEL, as it causes the pattern to change from linear to logarithmic. An impressive optimization of the dissolution profile is observed corresponding to a rapid release of FEL in the system containing 10% w/w of FEL, releasing 100% in approximately 20 min. The particle size of dispersed FEL into PVP matrix could be classified as the main parameter affecting dissolution optimization. The mechanism of such enhancement consists of the lower energy required for the dissolution due to the amorphous transition and the fine dispersion, which leads to an optimal contact surface of the drug substance with the dissolution media. The prepared systems are stable during storage at 40 +/- 1 degrees C and relative humidity of 75 +/- 5%. Addition of sodium docusate as surfactant does not affect the release kinetics, but only the initial burst due to its effect on the surface tension and wettability of the systems.

  19. Preliminary protein corona formation stabilizes gold nanoparticles and improves deposition efficiency

    NASA Astrophysics Data System (ADS)

    Luby, Alexandra O.; Breitner, Emily K.; Comfort, Kristen K.

    2016-08-01

    Due to their advantageous characteristics, gold nanoparticles (AuNPs) are being increasingly utilized in a vast array of biomedical applications. However, the efficacy of these procedures are highly dependent upon strong interactions between AuNPs and the surrounding environment. While the field of nanotechnology has grown exponentially, there is still much to be discovered with regards to the complex interactions between NPs and biological systems. One area of particular interest is the generation of a protein corona, which instantaneously forms when NPs encounter a protein-rich environment. Currently, the corona is viewed as an obstacle and has been identified as the cause for loss of application efficiency in physiological systems. To date, however, no study has explored if the protein corona could be designed and advantageously utilized to improve both NP behavior and application efficacy. Therefore, we sought to identify if the formation of a preliminary protein corona could modify both AuNP characteristics and association with the HaCaT cell model. In this study, a corona comprised solely of epidermal growth factor (EGF) was successfully formed around 10-nm AuNPs. These EGF-AuNPs demonstrated augmented particle stability, a modified corona composition, and increased deposition over stock AuNPs, while remaining biocompatible. Analysis of AuNP dosimetry was repeated under dynamic conditions, with lateral flow significantly disrupting deposition and the nano-cellular interface. Taken together, this study demonstrated the plausibility and potential of utilizing the protein corona as a means to influence NP behavior; however, fluid dynamics remains a major challenge to progressing NP dosimetry.

  20. Formation of Inclusions in Ti-Stabilized 17Cr Austenitic Stainless Steel

    NASA Astrophysics Data System (ADS)

    Yin, Xue; Sun, Yanhui; Yang, Yindong; Bai, Xuefeng; Barati, Mansoor; Mclean, Alex

    2016-12-01

    The behavior and formation mechanisms of inclusions in Ti-stabilized, 17Cr Austenitic Stainless Steel produced by the ingot casting route were investigated through systematic sampling of liquid steel and rolled products. Analysis methods included total oxygen and nitrogen contents, optical microscopy, scanning electron microscopy, and energy-dispersive X-ray spectroscopy. The results indicate that the composition of inclusions was strongly dependent on the types of added alloying agents. During the AOD refining process, after the addition of ferrosilicon alloy and electrolytic manganese, followed by aluminum, the composition of inclusions changed from manganese silicate-rich inclusions to alumina-rich inclusions. After tapping and titanium wire feeding, pure TiN particles and complex inclusions with Al2O3-MgO-TiO x cores containing TiN were found to be the dominant inclusions when [pct Ti] was 0.307 mass pct in the molten steel. These findings were confirmed by thermodynamic calculations which indicated that there was a driving force for TiN inclusions to be formed in the liquid phase due to the high contents of [Ti] and [N] in the molten steel. From the start of casting through to the rolled bar, there was no further change in the composition of inclusions compared to the titanium addition stage. Stringer-shaped TiN inclusions were observed in the rolled bar. These inclusions were elongated along the rolling direction with lengths varying from 17 to 84 µm and could have a detrimental impact on the corrosion resistance as well as the mechanical properties of the stainless steel products.

  1. Stability of mass transfer from massive giants: double black hole binary formation and ultraluminous X-ray sources

    NASA Astrophysics Data System (ADS)

    Pavlovskii, K.; Ivanova, N.; Belczynski, K.; Van, K. X.

    2017-02-01

    Mass transfer in binaries with massive donors and compact companions, when the donors rapidly evolve after their main sequence, determines the formation rates of merging double stellar-mass black hole (BH) binaries formed outside clusters. This mass transfer was previously postulated to be unstable and was expected to lead to a common envelope event. The common envelope event then ends with either the merger of the two stars or formation of a binary that eventually may become a merging double BH. We revisit the stability of this mass transfer and find an unanticipated third outcome: for a large range of binary orbital separations, this mass transfer is stable. This newly found stability allows us to reconcile the empirical rate obtained by LIGO, 9-240 Gpc-3 yr-1, with the theoretical rate for double BH binary mergers predicted by population synthesis studies by excluding a channel that predicts a merger rate above 1000 Gpc-3 yr-1. Furthermore, the stability of the mass transfer leads to the formation of ultraluminous X-ray sources. The theoretically predicted formation rates of bright ultraluminous X-ray sources powered by a stellar-mass BH are high enough to explain the number of observed bright ultraluminous X-ray sources.

  2. Influence of I - anions on the formation and stabilization of copper nanoparticles

    NASA Astrophysics Data System (ADS)

    Kapoor, S.; Joshi, R.; Mukherjee, T.

    2002-03-01

    Copper nanoparticles have been prepared by the reduction of copper(II) sulfate in an aerated water using sodium borohydride at room temperature and stabilized by inorganic anion. Mechanistic steps for the stabilization provided by iodide anion was studied using pulse radiolysis technique. Various inorganic anions have been used to stabilize Cu nanoparticles and compared for their stabilization efficiency. The synthesized nanoparticles exhibit a distinct absorption maximum in the region 560-565 nm. The average size as estimated from TEM micrographs has been found to be in the range 8-10 nm.

  3. The function of ultra-large von Willebrand factor multimers in high shear flow controlled by ADAMTS13.

    PubMed

    Reininger, A J

    2015-01-01

    The paradigm that platelet aggregation, which contributes to bleeding arrest and also to thrombovascular disorders, initiates after signaling-induced platelet activation has been refuted in past recent years. Platelets can form aggregates independently of activation when soluble von Willebrand factor (VWF) is present and the shear rate exceeds a certain threshold where active A1 domains become exposed in soluble VWF multimers and can bind to platelet glycoprotein Ib. Subsequently - fostering each other - VWF can self-assemble into large nets combining with platelets into large conglomerates, which are entirely reversible when they enter a flow region with shear rates below the threshold. In addition the threshold changes from approximately 20 000 s⁻¹ in wall parallel flow to approximately 10 000 s⁻¹ in stagnation point flow. VWF containing ultra-large multimers - as when just released from endothelial storage sites - has been shown to have the highest binding potential to platelets and to each other, thus facilitating rapid platelet accrual to sites of vessel injury and exposed subendothelial structures, i.e. collagen. The VWF nets as well as the platelet-VWF conglomerates are controlled by the cleaving protease ADAMTS13 within minutes under high shear flow. Therewith the hemostatic potential is delivered where needed and the thrombogenic potential is highly controlled twofold: by flow and enzymatic proteolytic cleavage.

  4. Thermodynamics of formation of the insulin hexamer: metal-stabilized proton-coupled assembly of quaternary structure.

    PubMed

    Carpenter, Margaret C; Wilcox, Dean E

    2014-03-04

    The thermodynamics of formation of the insulin hexamer, which is stabilized by two Zn(2+) ions, were quantified by isothermal titration calorimetry (ITC). Because the insulin monomer is unstable to aggregation (fibrillation) during ITC measurements, an original method involving EDTA chelation of Zn(2+) from the hexamer was employed. The two metal ions are chelated sequentially, reflecting stepwise Zn(2+) binding and stabilization of the quaternary structure. Analysis of the ITC data reveals that two to three H(+) bind to the hexamer upon its formation at pH 7.4, which is both enthalpically and entropically favored. The former is due to Zn(2+) coordination to His residues from three subunits, and the latter is associated with desolvation that accompanies the protonation and the packing of the subunits in the hexamer.

  5. High-frequency detection of the formation and stabilization of a radiation-induced defect cluster in semiconductor structures

    SciTech Connect

    Puzanov, A. S.; Obolenskiy, S. V. Kozlov, V. A.; Volkova, E. V.; Paveliev, D. G.

    2015-12-15

    The processes of the formation and stabilization of a radiation-induced defect cluster upon the arrival of a fast neutron to the space-charge region of a semiconductor diode are analyzed. The current pulse formed by secondary electrons is calculated and the spectrum of the signal generated by the diode (detector) under the action of an instantaneous neutron flux of the fission spectrum is determined. The possibility of experimental detection of the picosecond radiation-induced transition processes is discussed.

  6. Effects of temperature dependent pre-amorphization implantation on NiPt silicide formation and thermal stability on Si(100)

    SciTech Connect

    Ozcan, Ahmet S.; Wall, Donald; Jordan-Sweet, Jean; Lavoie, Christian

    2013-04-29

    Using temperature controlled Si and C ion implantation, we studied the effects of pre-amorphization implantation on NiPt alloy silicide phase formation. In situ synchrotron x-ray diffraction and resistance measurements were used to monitor phase and morphology evolution in silicide films. Results show that substrate amorphization strongly modulate the nucleation of silicide phases, regardless of implant species. However, morphological stability of the thin films is mainly enhanced by C addition, independently of the amorphization depth.

  7. Inquiring the mechanism of formation, encapsulation, and stabilization of gold nanoparticles by poly(vinyl pyrrolidone) molecules in 1-butanol

    NASA Astrophysics Data System (ADS)

    Behera, M.; Ram, S.

    2013-02-01

    We present a plausible mechanism of formation, encapsulation, and stabilization of gold nanoparticles (GNPs) in presence of poly(vinyl pyrrolidone) (PVP) in 1-butanol in support of UV-visible, Raman, Fourier transform infrared spectroscopy (FTIR), zetapotential, X-ray photoelectron spectrum (XPS), and transmission electron microscopy. A surface plasmon resonance band at 533 nm in the UV-visible spectrum reveals formation of ~20 nm spherical GNPs in the non-hydrocolloid. In the FTIR spectrum, selective enhancement in the intensity of C-H stretching and red-shift in the C=O band suggests that PVP encapsulate GNP by an interaction between PVP and GNP that occurs via O-atom of pyrrolidone ring. Raman and XPS spectrum well supports the findings of FTIR spectrum. Zeta potential of -15.22 mV at 7.5 pH found in PVP-capped GNP strongly recommends the role of electrosteric effect towards the observed colloidal stability. Microscopic image demonstrates a thin coating of amorphous PVP layer around GNPs in a core-shell structure. Probing the mechanism of formation, encapsulation, and stabilization of GNP could provide essential information for development of bimetallic NPs for catalytic applications.

  8. Ion Mobility Measurements of Nondenatured 12-150 kDa Proteins and Protein Multimers by Tandem Differential Mobility Analysis-Mass Spectrometry (DMA-MS)

    NASA Astrophysics Data System (ADS)

    Hogan, Christopher J.; de la Mora, Juan Fernández

    2011-01-01

    The mobilities of electrosprayed proteins and protein multimers with molecular weights ranging from 12.4 kDa (cytochrome C monomers) to 154 kDa (nonspecific concanavalin A hexamers) were measured in dry air by a planar differential mobility analyzer (DMA) coupled to a time-of-flight mass spectrometer (TOF-MS). The DMA determines true mobility at atmospheric pressure, without perturbing ion structure from that delivered by the electrospray. A nondenaturing aqueous 20 mM triethylammonium formate buffer yields compact ions with low charge states, moderating polarization effects on ion mobility. Conversion of mobilities into cross-sections involves a reduction factor ξ for the actual mobility relative to that associated with elastic specular collisions with smooth surfaces. ξ is known to be 1.36 in air from Millikan's oil drop experiments. A similar enhancement effect ascribed to atomic-scale surface roughness has been found in numerical simulations. Adopting Millikan's value ξ = 1.36 and assuming a spherical geometry yields a gas-phase protein density ρ p = 0.949 ± 0.053 g cm-3 for all our protein data. This is substantially higher than the 0.67 g cm-3 found in recent low-resolution DMA measurements of singly charged proteins. DMA-MS can distinguish nonspecific protein aggregates formed during the electrospray process from those formed preferentially in solution. The observed charge versus diameter relation is compatible with a protein charge reduction mechanism based on the evaporation of triethylammonium ions from electrosprayed drops.

  9. Analysis of K-Area core samples for K-Area formation stabilization work

    SciTech Connect

    Langton, C.A.

    1992-05-27

    Foundation stabilization work in K-Area has been recently completed by Bechtel Inc. This effort involved pumping cement and cement-sand grout into unconsolidated sediments under K-Area. Subsequent to stabilization, core samples were collected to document the extent of grout flow in the area. Samples of this core were examined by SRTC personnel in support of the grouting program at the request of Bechtel personnel. This report summarizes the results of the SRTC study.

  10. The Stability and Formation of Native Proteins from Unfolded Monomers Is Increased through Interactions with Unrelated Proteins

    PubMed Central

    Rodríguez-Almazán, Claudia; Torner, Francisco J.; Costas, Miguel; Pérez-Montfort, Ruy; de Gómez-Puyou, Marieta Tuena; Puyou, Armando Gómez

    2007-01-01

    The intracellular concentration of protein may be as high as 400 mg per ml; thus it seems inevitable that within the cell, numerous protein-protein contacts are constantly occurring. A basic biochemical principle states that the equilibrium of an association reaction can be shifted by ligand binding. This indicates that if within the cell many protein-protein interactions are indeed taking place, some fundamental characteristics of proteins would necessarily differ from those observed in traditional biochemical systems. Accordingly, we measured the effect of eight different proteins on the formation of homodimeric triosephosphate isomerase from Trypanosoma brucei (TbTIM) from guanidinium chloride unfolded monomers. The eight proteins at concentrations of micrograms per ml induced an important increase on active dimer formation. Studies on the mechanism of this phenomenon showed that the proteins stabilize the dimeric structure of TbTIM, and that this is the driving force that promotes the formation of active dimers. Similar data were obtained with TIM from three other species. The heat changes that occur when TbTIM is mixed with lysozyme were determined by isothermal titration calorimetry; the results provided direct evidence of the weak interaction between apparently unrelated proteins. The data, therefore, are strongly suggestive that the numerous protein-protein interactions that occur in the intracellular space are an additional control factor in the formation and stability of proteins. PMID:17551578

  11. A BENCHMARKING ANALYSIS FOR FIVE RADIONUCLIDE VADOSE ZONE MODELS (CHAIN, MULTIMED_DP, FECTUZ, HYDRUS, AND CHAIN 2D) IN SOIL SCREENING LEVEL CALCULATIONS

    EPA Science Inventory

    Five radionuclide vadose zone models with different degrees of complexity (CHAIN, MULTIMED_DP, FECTUZ, HYDRUS, and CHAIN 2D) were selected for use in soil screening level (SSL) calculations. A benchmarking analysis between the models was conducted for a radionuclide (99Tc) rele...

  12. Stability constants for the formation of rare earth-inorganic complexes as a function of ionic strength

    NASA Astrophysics Data System (ADS)

    Millero, Frank J.

    1992-08-01

    Recent studies have been made on the distribution of the rare earths (La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu) in natural waters relative to their concentration in shales. These metals have also been used as models for the behavior of the trivalent actinides. The speciation of the rare earths in natural waters is modelled by using ionic interaction models which require reliable stability constants. In this paper the stability constants for the formation of lanthanide complexes ( k mx∗) with Cl -, NO 3-, SO 42-, OH -, HCO 3-, H 2PO 4-, HPO 42-, and CO 32- determined in NaClO 44 at various ionic strengths have been extrapolated to infinite dilution using the Pitzer interaction model. The activity coefficients for free ions ( γM, γx) needed for this extrapolation have been estimated from the Pitzer equations. The thermodynamic stability constants ( KMX) and activity coefficients of the various ion pairs ( γMX) were determined from In ( solK MX∗/γ Mγ x) = In K mx+ In (γ MX). The activity coefficients of the ion pairs have been used to determine Pitzer parameters ( BMX) for the rare earth complexes. The values of BMX were found to be the same for complexes of the same charge. These results make it possible to estimate the stability constants for the formation of rare earth complexes over a wide range of ionic strengths. The stability constants have been used to determine the speciation of the lanthanides in seawater and in brines. The carbonate complexes dominate for all natural waters where the carbonate alkalinity is greater than 0.001 eq/L at a pH near 8.

  13. Prevention of Gordonia and Nocardia Stabilized Foam Formation by Using Bacteriophage GTE7▿†

    PubMed Central

    Petrovski, Steve; Seviour, Robert J.; Tillett, Daniel

    2011-01-01

    Most activated sludge treatment plants suffer from the presence of foams on the surfaces of their aeration reactors. These are often stabilized by hydrophobic mycolic acid-synthesizing actinobacterial species. A polyvalent Siphoviridae phage, GTE7, which lysed several Gordonia and Nocardia species, is described here. Its genome has a modular structure similar to that described for Rhodococcus phage ReqiDocB7. In laboratory-scale experiments, we showed that GTE7 prevents stabilization of foams by these Gordonia and Nocardia species. PMID:21926218

  14. The Formation and Stability of Carbonic Acid on Outer Solar System Bodies

    NASA Technical Reports Server (NTRS)

    Peeters, Z.; Hudson, R. L.; Moore, M. H.; Lewis, Ariel

    2009-01-01

    The radiation chemistry, thermal stability, and vapor pressure of solid-phase carbonic acid (H2CO3) have been studied with mid-infrared spectroscopy. A new procedure for measuring this molecule's radiation stability has been used to obtain intrinsic IR band strengths and half-lives for radiolytic destruction. Results are compared to literature values. We report, for the first time, measurements of carbonic acid's vapor pressure and its heat of sublimation. We also report the first observation of a chemical reaction involving solid-phase carbonic acid. Possible applications of these findings are discussed, with an emphasis on the outer Solar System.

  15. Ultrasonic assisted formation and stability of mustard oil in water nanoemulsion: Effect of process parameters and their optimization.

    PubMed

    Carpenter, Jitendra; Saharan, Virendra Kumar

    2017-03-01

    The present work reports the ultrasound assisted preparation of mustard oil in water nanoemulsion stabilized by Span 80 and Tween 80 at different operating conditions. Effects of various operating parameters such as HLB (Hydrophilic Lipophilic Balance) value, surfactant volume fraction (φS), oil volume fraction (φO) and power amplitude were investigated and optimized on the basis of droplet size and stability of nanoemulsions. It was observed that minimum droplet size of about 87.38nm was obtained within 30min of ultrasonication at an optimum HLB value of 10, φS of 0.08 (8%, v/v), φO of 0.1 (10%, v/v) and ultrasonic power amplitude of 40%. The stability of the nanoemulsion was measured through visual observation and it was found that the unstable emulsions got separated within 24h whereas, stable emulsions never showed any separation until 90days. In addition to that, the kinetic stability of the prepared nanoemulsions was also assessed under centrifuge and thermal stress conditions. The emulsion stability was found to be unaffected by these forces as the droplet size remained unchanged. The ultrasound prepared emulsion was found to be long term stable even after 3months of storage at ambient conditions without any visual evidence of creaming and phase separation and also remained kinetically stable. FTIR analysis of the emulsions at different sonication conditions was carried out to examine the possible impact of ultrasonically induced chemical effects on oil structure during emulsification and it was found that the oil molecular structure was unaffected by ultrasonication process. The present work illustrates the formation and stability of mustard oil in water nanoemulsion using ultrasound cavitation which may be useful in food and cosmetic based applications.

  16. The biologically active form of the sea urchin egg receptor for sperm is a disulfide-bonded homo-multimer

    PubMed Central

    1994-01-01

    Since many cell surface receptors exist in their active form as oligomeric complexes, we have investigated the subunit composition of the biologically active sperm receptor in egg plasma membranes from Strongylocentrotus purpuratus. Electrophoretic analysis of the receptor without prior reduction of disulfide bonds revealed that the surface receptor exists in the form of a disulfide-bonded multimer, estimated to be a tetramer. These findings are in excellent agreement with the fact that the NH2-terminus of the extracellular domain of the sperm receptor is rich in cysteine residues. Studies with cross-linking agents of various length and hydrophobicity suggest that no other major protein is tightly associated with the receptor. Given the multimeric structure of the receptor, we investigated the effect of disulfide bond reduction on its biological activity. Because in quantitative bioassays fertilization was found to be inhibited by treatment of eggs with 5 mM dithiothreitol, we undertook more direct studies of the effect of reduction on properties of the receptor. First, we studied the effect of addition of isolated, pure receptor on fertilization. Whereas the non-reduced, native receptor complex inhibited fertilization in a dose- dependent manner, the reduced and alkylated receptor was inactive. Second, we tested the ability of the isolated receptor to mediate binding of acrosome-reacted sperm to polystyrene beads. Whereas beads coated with native receptor bound sperm, those containing reduced and alkylated receptor did not. Thus, these results demonstrate that the biologically active form of the sea urchin sperm receptor consists only of 350 kD subunits and that these must be linked as a multimer via disulfide bonds to produce a complex that is functional in sperm recognition and binding. PMID:8188748

  17. Evidence that TSH Receptor A-Subunit Multimers, Not Monomers, Drive Antibody Affinity Maturation in Graves' Disease

    PubMed Central

    Aliesky, Holly A.; Chen, Chun-Rong; McLachlan, Sandra M.

    2015-01-01

    Context: The TSH receptor (TSHR) A-subunit shed from the cell surface contributes to the induction and/or affinity maturation of pathogenic TSHR autoantibodies in Graves' disease. Objective: This study aimed to determine whether the quaternary structure (multimerization) of shed A-subunits influences pathogenic TSHR autoantibody generation. Design: The isolated TSHR A-subunit generated by transfected mammalian cells exists in two forms; one (active) is recognized only by Graves' TSHR autoantibodies, the second (inactive) is recognized only by mouse monoclonal antibody (mAb) 3BD10. Recent evidence suggests that both Graves' TSHR autoantibodies and mAb 3BD10 recognize the A-subunit monomer. Therefore, if the A-subunit monomer is an immunogen, Graves' sera should have antibodies to both active and inactive A-subunits. Conversely, restriction of TSHR autoantibodies to active A-subunits would be evidence of a role for shed A-subunit multimers, not monomers, in the pathogenesis of Graves' disease. Therefore, we tested a panel of Graves' sera for their relative recognition of active and inactive A-subunits. Results: Of 34 sera from unselected Graves' patients, 28 were unequivocally positive in a clinical TSH binding inhibition assay. None of the latter sera, as well as 8/9 sera from control individuals, recognized inactive A-subunits on ELISA. In contrast to Graves' sera, antibodies induced in mice, not by shedding from the TSHR holoreceptor, but by immunization with adenovirus expressing the free human A-subunit, were directed to both the active and inactive A-subunit forms. Conclusions: The present study supports the concept that pathogenic TSHR autoantibody affinity maturation in Graves' disease is driven by A-subunit multimers, not monomers. PMID:25856215

  18. Diagnostic Differentiation of von Willebrand Disease Types 1 and 2 by von Willebrand Factor Multimer Analysis and DDAVP Challenge Test.

    PubMed

    Michiels, Jan Jacques; Smejkal, Petr; Penka, Miroslav; Batorova, Angelika; Pricangova, Tatiana; Budde, Ulrich; Vangenechten, Inge; Gadisseur, Alain

    2016-01-01

    The European Clinical Laboratory and Molecular (ECLM) classification of von Willebrand disease (vWD) is based on the splitting approach which uses sensitive and specific von Willebrand factor (vWF) assays with regard to the updated molecular data on structure and function of vWF gene and protein defects. A complete set of FVIII:C and vWF ristocetine cofactor, collagen binding, and antigen, vWF multimeric analysis in low- and medium-resolution gels, and responses to desmopressin (DDAVP) of FVIII:C and vWF parameters are mandatory. The ECLM classification distinguishes recessive types 1 and 3 vWD from recessive vWD 2C due to mutations in the D1 and D2 domains and vWD 2N due to mutations in the D'-FVIII-binding domain of vWF. The ECLM classification differentiates between mild vWD type 1 with variable penetrance of bleedings from symptomatic dominant type 1 vWD secretion defect and/or clearance defect with normal vWF multimers versus vWD 1M and 2M with normal or smeary vWF multimers in low- and medium-resolution gels. High-quality multimeric analysis of vWF in medium-resolution gels based on a DDAVP challenge test clearly delineates and distinguishes each of the dominant type 2 vWDs 1/2E, 2M, 2B, 2A, and 2D caused by vWF gene mutations in the D3 multimerization domain, loss or gain-of-function mutations in the glycoprotein Ib receptor A1 domain, gene mutations in the A2 proteolytic domain, and the C-terminal dimerization domain, respectively.

  19. Effects of freeze-thaw cycling on metal-phosphate formation and stability in single and multi-metal systems.

    PubMed

    Hafsteinsdóttir, Erla G; White, Duanne A; Gore, Damian B

    2013-04-01

    Freeze-thaw cycling may influence the chemistry, mineral stability and reaction rate during metal orthophosphate fixation. This study assessed the formation and stability of Cu-, Pb-, and Zn-phosphates in chemically simple laboratory systems during 240 freeze-thaw cycles (120 days) from +10 to -20 °C, using X-ray diffractometry. In single heavy metal systems, chloro- and hydroxy-pyromorphite (Pb(5)(PO(4))(3)(Cl,OH)), sodalite (Na(6)Zn(6)(PO(4))(6)·8H(2)O), chiral zincophosphate (Na(12)(Zn(12)P(12)O(48))·12H(2)O), and copper phosphate hydrate (Cu(3)(PO(4))(2)·3H(2)O) were the primary phosphate minerals that formed, and were typically stable during the experiment. Zinc and Cu-phosphate formation was reduced in multi heavy metal systems, and was substantially lower in abundance than chloropyromorphite. Successful Cu-, Pb- and Zn-phosphate formation can be expected in cold and freezing environments like the polar regions. However, field implementation of orthophosphate fixation needs to consider competing ion effects, concentration of the phosphate source, and the amount of free-water.

  20. Taxol-stabilized microtubules promote the formation of filaments from unmodified full-length Tau in vitro.

    PubMed

    Duan, Aranda R; Goodson, Holly V

    2012-12-01

    Tau is a neuronal protein that stabilizes the microtubule (MT) network, but it also forms filaments associated with Alzheimer's disease. Understanding Tau-MT and Tau-Tau interactions would help to establish Tau function in health and disease. For many years, literature reports on Tau-MT binding behavior and affinity have remained surprisingly contradictory (e.g., 10-fold variation in Tau-MT affinity). Tau-Tau interactions have also been investigated, but whether MTs might affect Tau filament formation is unknown. We have addressed these issues through binding assays and microscopy. We assessed Tau-MT interactions via cosedimentation and found that the measured affinity of Tau varies greatly, depending on the experimental design and the protein concentrations used. To investigate this dependence, we used fluorescence microscopy to examine Tau-MT binding. Strikingly, we found that Taxol-stabilized MTs promote Tau filament formation without characterized Tau-filament inducers. We propose that these novel Tau filaments account for the incongruence in Tau-MT affinity measurements. Moreover, electron microscopy reveals that these filaments appear similar to the heparin-induced Alzheimer's model. These observations suggest that the MT-induced Tau filaments provide a new model for Alzheimer's studies and that MTs might play a role in the formation of Alzheimer's-associated neurofibrillary tangles.

  1. The impact of thermal treatment on the stability of freeze dried amorphous pharmaceuticals: I. Dimer formation in sodium ethacrynate.

    PubMed

    Wang, Bingquan; Pikal, Michael J

    2010-02-01

    The objective of this study was to investigate the impact of heat treatment (annealing) on the molecular mobility and chemical stability of dried sodium ethacrynate (ECA). ECA was lyophilized with sucrose or trehalose, and some samples were held as control while others were annealed at temperatures below T(g). Enthalpy recovery was studied with DSC and free volume was estimated based on density measurements. Global mobility was measured by the thermal activity monitor (TAM), and fast local mobility was studied with neutron backscattering. Formation of ECA dimer was measured by reverse phase HPLC. Maximum enthalpy recovery and minimum fictive temperature were observed at about T(g)-15 degrees C for both ECA/saccharide formulations. Annealing ECA in amorphous solids improved chemical stability, as shown by the decrease in degradation rate constant relative to the control. Annealed samples exhibited larger structural relaxation time than the control, and thus annealing decreased global mobility in the system. However, annealing does not significantly impact the local mobility. Chemical stability correlates with structural relaxation time, fictive temperature, and free volume, which suggests that improved stability is mainly a result of the reduced global mobility upon annealing.

  2. Role of stabilized Criegee Intermediate in secondary organic aerosol formation from the ozonolysis of α-cedrene

    NASA Astrophysics Data System (ADS)

    Yao, Lei; Ma, Yan; Wang, Lin; Zheng, Jun; Khalizov, Alexei; Chen, Mindong; Zhou, Yaoyao; Qi, Lu; Cui, Fenping

    2014-09-01

    Atmospheric ozonolysis of sesquiterpenes is an important source of secondary organic aerosols (SOA). The mechanisms by which Criegee Intermediates (CIs) react to form SOA precursors and the influence of environmental conditions, however, remain unclear. On the basis of environmental chamber experiments coupled with detailed characterization of gas-phase and particle-phase products, we present evidence that a significant fraction of CIs from ozonolysis of α-cedrene are stabilized and bimolecular reactions of these stabilized CIs (SCIs) play a key role in the formation of SOA precursors. Ozonolysis experiments were conducted in a 4.5 m3 collapsible fluoropolymer chamber under various conditions in the presence of the OH radical and SCI scavengers. The size and mass of SOA particles produced during ozonolysis were measured directly and used for calculation of particle effective density and mass yield. Gaseous and particulate products were analyzed by several mass spectrometry methods. A total of 14 compounds in gas phase and 17 compounds in particle phase were tentatively identified. The major gas-phase products are secondary ozonides (SOZ) from intramolecular reactions of SCIs. Multifunctional organic acids are dominant particle-phase products. The measured density of aerosol particles is 1.04 ± 0.03 to 1.38 ± 0.03 g/cm3, and the aerosol mass yield is (23.7 ± 0.4)% to (46.4 ± 6.5)%, depending on reaction conditions. The presence of acetic acid, an SCI scavenger, inhibits new particle formation, but leads to increased aerosol mass yield. In contrast, the addition of SO2 dramatically enhances new particle formation and total aerosol yield. The calculated OH formation yield decreases from (62.4 ± 4.9)% to (9.0 ± 1.6)% upon addition of SCI scavengers CH3COOH and SO2, indicating that a large fraction of excited CIs are collisionally stabilized and unimolecular decomposition of SCIs via the hydroperoxide channel can be suppressed by bimolecular reactions. The

  3. Formation and stability analysis of parabolic pulses through specialty microstructured optical fibers at 2.1 μm

    NASA Astrophysics Data System (ADS)

    Biswas, P.; Adhikary, P.; Biswas, A.; Ghosh, S. N.

    2016-10-01

    We report a numerical study on formation and stability of parabolic pulses during their propagation through highly nonlinear specialty optical fibers. Here, we have formed a parabolic pulse at wavelength of 2.1 μm from a Gaussian input pulse with 1.9 ps FWHM and 75 W peak power after traveling through only 20 cm length from the input end of a 1 m long chalcogenide glass based microstructured optical fiber (MOF). Dependence on input pulse shapes towards most efficient conversion into self-similar states is reported. The stability in terms of any deviation from dissipative self-similar nature of such pulses has been analyzed by introducing a variable longitudinal loss profile within the spectral loss window of the MOF, and detailed pulse shapes are captured. Moreover, three different dispersion regimes of propagation have been considered to study the suitability to support most stable propagation of the pulse.

  4. Formation and stabilization of anionic metal complexes in concentrated aqueous quaternary ammonium salt solutions

    SciTech Connect

    Aronson, F.L.; Hwang, L.L.Y.; Ronca, N.; Solomon, N.A.; Steigman, J.

    1985-02-04

    Anionic complexes of transition metals were stabilized in aqueous solutions containing high concentrations of various short-chain quaternary ammonium salts. Compounds with longer paraffin chains were effective in much less concentrated solution. Complex ions were detected spectrophotometrically. FeCl/sub 4//sup -/, which is usually formed in concentrated HCl, was the predominant Fe(III) complex in 30 m choline chloride containing only 0.12 M HCl. A yellow transitory Tc(VII) chloro-addition intermediate, formed in the reduction of TcO/sub 4//sup -/ by concentrated HCl, was stabilized when the solution also contained 25 m choline chloride. Its spectrum, as well as the isolation of an already known Tc(VII) bipyridyl complex, is reported. Concentrated organic electrolytes also stabilized Tc(V) oxide halides against disproportionation and Tc(IV) hexahalides against hydrolysis. Halochromates of Cr(VI) were formed and stabilized in dilute acid containing quaternary ammonium salts. Their UV spectra showed the well-resolved vibronic fine structure associated with the symmetric chromium-to-oxygen charge-transfer band. It is known that these progressions are resolved in aprotic solvents, but not in aqueous acidic solution alone, and that the loss of fine structure in aqueous media is due to hydrogen bonding. The stabilization of anionic metal complexes and the resolution of vibronic structure in halochromates are probably consequences of water-structure-enforced ion paring. The present work suggests that the water molecules in immediate contact with the complex anions are more strongly hydrogen bonded to each other than to the complex. 21 references, 4 figures.

  5. Artificial soil formation and stabilization of material cycles in closed ecological systems for Mars habitats

    NASA Astrophysics Data System (ADS)

    Borchardt, Joshua D.

    Scientists are increasingly pressured to investigate novel ways in which to feed astronauts for the first mission to Mars in the 2030s. It is the aim of this thesis to conduct a preliminary investigation for soil formation of NASA JSC Mars-1A Regolith Simulant in an environmentally closed ecosystem to simulate plant growth within these initial habitats, and the prospect of soil formation from a Mars parent material for agricultural purposes. The rhizosphere and plant stress will be the main regions of research focus. It is hypothesized rhizosphere activity will determine the rate of stable soil formation adequate to support the agricultural needs of Mars's first human inhabitants. A Brassica rapa (Wisconsin FastPlant(TM)) was grown on several different substrates, and evaluated for plant stress, elemental analysis, soil fertility, and mineralogical analysis to identify the biogeochemical factors related to areas inside and outside of the rhizosphere, which affect soil formation. In addition, multiple plant generations were grown to investigate bioavailability of nutrients within the system, and lay down preliminary approaches for mathematical model development in order to predict & evaluate future conditions and applications under reduced resource availability situations. Overall, the story of early soil formation from a Mars regolith simulant is further defined to aid in the success of our first human adventurers to the red planet.

  6. Efficient CO2 capture by tertiary amine-functionalized ionic liquids through Li+-stabilized zwitterionic adduct formation

    PubMed Central

    Yang, Zhen-Zhen

    2014-01-01

    Summary Highly efficient CO2 absorption was realized through formation of zwitterionic adducts, combining synthetic strategies to ionic liquids (ILs) and coordination. The essence of our strategy is to make use of multidentate cation coordination between Li+ and an organic base. Also PEG-functionalized organic bases were employed to enhance the CO2-philicity. The ILs were reacted with CO2 to form the zwitterionic adduct. Coordination effects between various lithium salts and neutral ligands, as well as the CO2 capacity of the chelated ILs obtained were investigated. For example, the CO2 capacity of PEG150MeBu2N increased steadily from 0.10 to 0.66 (mol CO2 absorbed per mol of base) through the formation of zwitterionic adducts being stabilized by Li+. PMID:25246955

  7. Efficient CO2 capture by tertiary amine-functionalized ionic liquids through Li(+)-stabilized zwitterionic adduct formation.

    PubMed

    Yang, Zhen-Zhen; He, Liang-Nian

    2014-01-01

    Highly efficient CO2 absorption was realized through formation of zwitterionic adducts, combining synthetic strategies to ionic liquids (ILs) and coordination. The essence of our strategy is to make use of multidentate cation coordination between Li(+) and an organic base. Also PEG-functionalized organic bases were employed to enhance the CO2-philicity. The ILs were reacted with CO2 to form the zwitterionic adduct. Coordination effects between various lithium salts and neutral ligands, as well as the CO2 capacity of the chelated ILs obtained were investigated. For example, the CO2 capacity of PEG150MeBu2N increased steadily from 0.10 to 0.66 (mol CO2 absorbed per mol of base) through the formation of zwitterionic adducts being stabilized by Li(+).

  8. Solid-stabilized emulsion formation using stearoyl lactylate coated iron oxide nanoparticles

    NASA Astrophysics Data System (ADS)

    Vengsarkar, Pranav S.; Roberts, Christopher B.

    2014-10-01

    Iron oxide nanoparticles can exhibit highly tunable physicochemical properties that are extremely important in applications such as catalysis, biomedicine and environmental remediation. The small size of iron oxide nanoparticles can be used to stabilize oil-in-water Pickering emulsions due to their high energy of adsorption at the interface of oil droplets in water. The objective of this work is to investigate the effect of the primary particle characteristics and stabilizing agent chemistry on the stability of oil-in-water Pickering emulsions. Iron oxide nanoparticles were synthesized by the co-precipitation method using stoichiometric amounts of Fe2+ and Fe3+ salts. Sodium stearoyl lactylate (SSL), a Food and Drug Administration approved food additive, was used to functionalize the iron oxide nanoparticles. SSL is useful in the generation of fat-in-water emulsions due to its high hydrophilic-lipophilic balance and its bilayer-forming capacity. Generation of a monolayer or a bilayer coating on the nanoparticles was controlled through systematic changes in reagent concentrations. The coated particles were then characterized using various analytical techniques to determine their size, their crystal structure and surface functionalization. The capacity of these bilayer coated nanoparticles to stabilize oil-in-water emulsions under various salt concentrations and pH values was also systematically determined using various characterization techniques. This study successfully demonstrated the ability to synthesize iron oxide nanoparticles (20-40 nm) coated with SSL in order to generate stable Pickering emulsions that were pH-responsive and resistant to significant destabilization in a saline environment, thereby lending themselves to applications in advanced oil spill recovery and remediation.

  9. Computational assessment of non-heteroatom-stabilized carbene complexes reactivity: formation of oxazine derivatives.

    PubMed

    Funes-Ardoiz, Ignacio; Sampedro, Diego

    2014-12-05

    A complete DFT-level mechanism elucidation of the two-step reaction of non-heteroatom-stabilized carbenes with imines, followed by addition of alkynes to yield oxazine derivatives, is presented. These compounds show different reactivity than the equivalent Fischer carbene complexes. A rationale of the experimental outcome is presented together with some suggestion for increasing the scope of the reaction, with special attention to the solvent effects in the regioselectivity.

  10. Spinel formation for stabilizing simulated nickel-laden sludge with aluminum-rich ceramic precursors.

    PubMed

    Shih, Kaimin; White, Tim; Leckie, James O

    2006-08-15

    The feasibility of stabilizing nickel-laden sludge from commonly available Al-rich ceramic precursors was investigated and accomplished with high nickel incorporation efficiency. To simulate the process, nickel oxide was mixed alternatively with gamma-alumina, corundum, kaolinite, and mullite and was sintered from 800 to 1480 degrees C. The nickel aluminate spinel (NiAl2O4) was confirmed as the stabilization phase for nickel and crystallized with efficiencies greater than 90% for all precursors above 1250 degrees C and 3-h sintering. The nickel-incorporation reaction pathways with these precursors were identified, and the microstructure and spinel yield were investigated as a function of sintering temperature with fixed sintering time. This study has demonstrated a promising process for forming nickel spinel to stabilize nickel-laden sludge from a wide range of inexpensive ceramic precursors, which may provide an avenue for economically blending waste metal sludges via the building industry processes to reduce the environmental hazards of toxic metals. The correlation of product textures and nickel incorporation efficiencies through selection of different precursors also provides the option of tailoring property-specific products.

  11. Microfluidic EDGE emulsification: the importance of interface interactions on droplet formation and pressure stability

    NASA Astrophysics Data System (ADS)

    Sahin, Sami; Bliznyuk, Olesya; Rovalino Cordova, Ana; Schroën, Karin

    2016-05-01

    The fact that interactions of components with interfaces can influence processes is well-known; e.g. deposit accumulation on heat exchangers and membrane fouling lead to additional resistances against heat and mass transfer, respectively. In microfluidic emulsification, the situation is even more complex. Component accumulation at the liquid/liquid interface is necessary for emulsion stability, while undesired at the solid/liquid interface where it may change wettability. For successful emulsification both aspects need to be controlled, and that is investigated in this paper for o/w emulsification with microfluidic EDGE devices. These devices were characterised previously, and can be used to detect small wettability changes through e.g. the pressure stability of the device. We used various oil/emulsifier combinations (alkanes, vegetable oil, surfactants and proteins) and related droplet size and operational pressure stability to component interactions with the solid surface and liquid interface. Surfactants with a strong interaction with glass always favour emulsification, while surfactants that have week interactions with the surface can be replaced by vegetable oil that interacts strongly with glass, resulting in loss of emulsification. Our findings clearly show that an appropriate combination of construction material and emulsion components is needed to achieve successful emulsification in microfluidic EDGE devices.

  12. Microfluidic EDGE emulsification: the importance of interface interactions on droplet formation and pressure stability

    PubMed Central

    Sahin, Sami; Bliznyuk, Olesya; Rovalino Cordova, Ana; Schroën, Karin

    2016-01-01

    The fact that interactions of components with interfaces can influence processes is well-known; e.g. deposit accumulation on heat exchangers and membrane fouling lead to additional resistances against heat and mass transfer, respectively. In microfluidic emulsification, the situation is even more complex. Component accumulation at the liquid/liquid interface is necessary for emulsion stability, while undesired at the solid/liquid interface where it may change wettability. For successful emulsification both aspects need to be controlled, and that is investigated in this paper for o/w emulsification with microfluidic EDGE devices. These devices were characterised previously, and can be used to detect small wettability changes through e.g. the pressure stability of the device. We used various oil/emulsifier combinations (alkanes, vegetable oil, surfactants and proteins) and related droplet size and operational pressure stability to component interactions with the solid surface and liquid interface. Surfactants with a strong interaction with glass always favour emulsification, while surfactants that have week interactions with the surface can be replaced by vegetable oil that interacts strongly with glass, resulting in loss of emulsification. Our findings clearly show that an appropriate combination of construction material and emulsion components is needed to achieve successful emulsification in microfluidic EDGE devices. PMID:27230981

  13. Formation and Stability of Shear-Induced Shish-Kebab Structure in Highly Entangled Melts of UHMWPE/HDPE Blends

    SciTech Connect

    Keum,J.; Zuo, F.; Hsiao, B.

    2008-01-01

    The formation and stability of a shear-induced shish-kebab structure was investigated by in situ rheo-SAXS (small-angle X-ray scattering) and -WAXD (wide-angle X-ray diffraction) measurements of highly entangled polyethylene melts based on two polymer blends, containing small fractions (2 and 5 wt %) of ultra-high molecular weight polyethylene (UHMWPE) and high-density polyethylene (HDPE). Immediately after shear, the combined SAXS and WAXD results at 142 C confirmed the sole formation of shish without kebabs, indicating the interplay between the topological deformation of highly entangled UHMWPE chains and the extended-chain crystallization of stretched segments without the participation of coiled segments. The presence of HDPE chains influenced the entanglement of UHMWPE but they were not involved in the shish-kebab formation at the initial stage of crystallization. The final shish lengths in both blends were nearly identical at the same strain (e = 500), even though the UHMWPE concentration was different. When the temperature was cooled to 134 C, both sheared blends exhibited the kebab formation, following the diffusion-controlled growth process. Although the total kebab nucleation was higher in the 5/95 wt % UHMWPE/HDPE blend, the kebab density per shish was higher in the 2/98 wt % UHMWPE/HDPE blend. The thermal stability of the shish-kebab structure was also investigated by constrained melting. Both blends exhibited identical melting behavior of kebabs but different melting behavior of shish that is governed by the entanglement restraints of the stretched-chain network.

  14. Activity Dependent Protein Degradation Is Critical for the Formation and Stability of Fear Memory in the Amygdala

    PubMed Central

    Jarome, Timothy J.; Helmstetter, Fred J.

    2011-01-01

    Protein degradation through the ubiquitin-proteasome system [UPS] plays a critical role in some forms of synaptic plasticity. However, its role in memory formation in the amygdala, a site critical for the formation of fear memories, currently remains unknown. Here we provide the first evidence that protein degradation through the UPS is critically engaged at amygdala synapses during memory formation and retrieval. Fear conditioning results in NMDA-dependent increases in degradation-specific polyubiquitination in the amygdala, targeting proteins involved in translational control and synaptic structure and blocking the degradation of these proteins significantly impairs long-term memory. Furthermore, retrieval of fear memory results in a second wave of NMDA-dependent polyubiquitination that targets proteins involved in translational silencing and synaptic structure and is critical for memory updating following recall. These results indicate that UPS-mediated protein degradation is a major regulator of synaptic plasticity necessary for the formation and stability of long-term memories at amygdala synapses. PMID:21961035

  15. Evaluation of the geological relationships to gas hydrate formation and stability. Progress report, June 16--September 30, 1988

    SciTech Connect

    Krason, J.; Finley, P.

    1988-12-31

    The summaries of regional basin analyses document that potentially economic accumulations of gas hydrates can be formed in both active and passive margin settings. The principal requirement for gas hydrate formation in either setting is abundant methane. Passive margin sediments with high sedimentation rates and sufficient sedimentary organic carbon can generate large quantities of biogenic methane for hydrate formation. Similarly, active margin locations near a terrigenous sediment source can also have high methane generation potential due to rapid burial of adequate amounts of sedimentary organic matter. Many active margins with evidence of gas hydrate presence correspond to areas subject to upwelling. Upwelling currents can enhance methane generation by increasing primary productivity and thus sedimentary organic carbon. Structural deformation of the marginal sediments at both active and passive sites can enhance gas hydrate formation by providing pathways for migration of both biogenic and thermogenic gas to the shallow gas hydrate stability zone. Additionally, conventional hydrocarbon traps may initially concentrate sufficient amounts of hydrocarbons for subsequent gas hydrate formation.

  16. Pyromorphite Formation And Stability After Quick Lime Neutralisation In The Presence Of Soil And Clay Sorbents

    EPA Science Inventory

    Soluble Pb is immobilised in pure systems as pyromorphite by adding sources of P, but doubts remain about the efectiveness of this approach in natural soil systems, particularly given the ability of soil humic substances to interfere with Pb-mineral formation. In addition, recen...

  17. Formation and stability of Ni-Al hydroxide phases in soils.

    PubMed

    Peltier, Edward; Lelie, Daniel van der; Sparks, Donald L

    2010-01-01

    The formation of mixed metal-aluminum hydroxide surface precipitates is a potentially significant uptake route for trace metals (including Co, Ni, and Zn) in environmental systems. This paper investigates the effect of mixed Ni-Al hydroxide precipitate formation and aging on Ni solubility and bioavailability in laboratory contaminated soils. Two Delaware agricultural soils were reacted with a 3 mM Ni solution for 12 months at pH's above and below the threshold for mixed Ni-Al hydroxide formation. Ni speciation was determined at 1, 6, and 12 months using X-ray absorption spectroscopy (XAS). Precipitate solubility was examined through desorption experiments using HNO3 and EDTA as desorbing agents, whereas metal bioavailability was assessed using a Ni-specific bacterial biosensor. For both soils, the formation of Ni-Al hydroxide surface precipitates resulted in a reduction in the fraction of desorbed and bioavailable Ni. However, precipitate dissolution was greater, particularly with EDTA, than in published studies on isolated soil clay fractions, and less affected by aging processes. These results suggest that mixed Ni-Al hydroxide phases forming in real world environments may be both longer-lasting and more susceptible to ligand-promoted dissolution than previously expected.

  18. Formation and Stability of Ni-Al Hydroxide Phases in Soils

    SciTech Connect

    Peltier, E.; Van Der Lelie, D; Sparks, D

    2010-01-01

    The formation of mixed metal-aluminum hydroxide surface precipitates is a potentially significant uptake route for trace metals (including Co, Ni, and Zn) in environmental systems. This paper investigates the effect of mixed Ni-Al hydroxide precipitate formation and aging on Ni solubility and bioavailability in laboratory contaminated soils. Two Delaware agricultural soils were reacted with a 3 mM Ni solution for 12 months at pH's above and below the threshold for mixed Ni-Al hydroxide formation. Ni speciation was determined at 1, 6, and 12 months using X-ray absorption spectroscopy (XAS). Precipitate solubility was examined through desorption experiments using HNO{sub 3} and EDTA as desorbing agents, whereas metal bioavailability was assessed using a Ni-specific bacterial biosensor. For both soils, the formation of Ni-Al hydroxide surface precipitates resulted in a reduction in the fraction of desorbed and bioavailable Ni. However, precipitate dissolution was greater, particularly with EDTA, than in published studies on isolated soil clay fractions, and less affected by aging processes. These results suggest that mixed Ni-Al hydroxide phases forming in real world environments may be both longer-lasting and more susceptible to ligand-promoted dissolution than previously expected.

  19. The Role of Music Preferences in Early Adolescents' Friendship Formation and Stability

    ERIC Educational Resources Information Center

    Selfhout, Maarten H. W.; Branje, Susan J. T.; ter Bogt, Tom F. M.; Meeus, Wim H. J.

    2009-01-01

    The present study examines the role of similarity in music preferences in the formation and discontinuation of friendships over a 1-year period. Questionnaire data were gathered from 283 Dutch same-sex mutual best friends (mean age = 12.97) in two waves with a 1-year interval. Results show consistent evidence for high similarity in specific music…

  20. Silver-cemented frit formation for the stabilization of the packing structure in the microchannel of electrochromatographic microchips.

    PubMed

    Park, Jongman; Oh, Hyejin; Jeon, In-Sun

    2011-10-28

    A simple but effective frit formation technique was developed to stabilize the packing structure inside the microchannel of capillary electrochromatographic microchips, utilizing the electroless plating technique. A Ag(NH(3))(2)(+) solution was allowed to diffuse through the colloidal silica packing in the microchannel from the reservoir of the microchip for a limited amount of time, and then it was reduced by an excess amount of formaldehyde solution. A frit structure of ~70 μm in length was formed at the entrance of the microchannel without clogging when treated with 1mM Ag(NH(3))(2)(+) ion and formaldehyde for 30s and 150 s, respectively. The formation of the frit structure was confirmed by a scanning electron microscopy. The stability of the packing structure was tested rigorously and then confirmed by applying alternating electroosmotic flows back and forth with pulsed potential steps on both sides of the frit structure. The effect of the treatment on the electrochromatograms was evaluated after the microchips were repeatedly used and stored for a long period of time. The results indicated that the silver-cemented frit structure extended the lifetime of the fully packed CEC microchips distinctly.

  1. Formation and stability of D-limonene organogel-based nanoemulsion prepared by a high-pressure homogenizer.

    PubMed

    Zahi, Mohamed Reda; Wan, Pingyu; Liang, Hao; Yuan, Qipeng

    2014-12-31

    D-limonene organogel-based nanoemulsion was prepared by high-pressure homogenization technology. The organogelator type had a major role on the formation of the formulations, in which stearic acid has given nanoemulsions with the smallest droplet size. The surfactant type and concentration also had an appreciable effect on droplet formation, with Tween 80 giving a mean droplet diameter (d ≈ 112 nm) among a range of non-ionic surfactants (Tween 20, 40, 60, 80, and 85). In addition, high-pressure homogenization conditions played a key role in the nanoemulsion preparation. The stability of d-limonene organogel-based nanoemulsion was also investigated under two different temperatures (4 and 28 °C) through 2 weeks of storage. Results showed a good stability of the formulations, which is maybe due to the incorporation of D-limonene into the organogel prior to homogenization. This study may have a valuable contribution for the design and use of organogel-based nanoemulsion as a delivery system in food.

  2. Mechanism of oil bank formation, coalescence in porous media and emulsion stability. Annual report, June 1979-May 1980

    SciTech Connect

    Wasan, D.T.

    1981-02-01

    This report presents results of a basic study of coalescence phenomena, emulsion formation and stability, and dynamic interfacial properties when crude oils and pure hydrocarbons are contacted with aqueous solutions of surfactant/polymer and alkaline agents. These measurements are correlated with each other and with observations on oil bank formation and displacement and recovery efficiency by chemical flooding in microwave monitored laboratory core flooding experiments. The scope of this work includes three interrelated tasks: I - Caustic Flooding of Heavy Crude, II - Surfactant/Polymer Flooding, and III - Thin Liquid Films: drainage and stability of foam and emulsion films. Results obtained in each of these three tasks are summarized: Crude oils from Huntington Beach, Wilmington Field, Salem and El Dorado and the hydrocarbon, decane were used. The chemical agents employed were: n-hexanol, Dow Pusher 700, sodium lauryl sulfate, lauryl alcohol, petroleum sulfonate, TRS 10-80, TRS 10-410, iBuOH, NaCl brine, sodium orthosilicate, sodium hydroxide, Petrostep 465, and C/sub 3/ to C/sub 5/ alcohols.

  3. Effects of molecular weight of PVA on formation, stability and deformation of compound droplets for ICF polymer shells

    NASA Astrophysics Data System (ADS)

    Liu, Meifang; Zheng, Yueqing; Li, Jie; Chen, Sufen; Liu, Yiyang; Li, Jing; Li, Bo; Zhang, Zhanwen

    2017-01-01

    Sphericity and wall thickness uniformity are some of the hardest specifications to fulfill, as required by inertial confined fusion (ICF) research for polymer shells prepared by the microencapsulation technique. Driven by the need to control the deformation of compound droplets, the effects of the molecular weight of poly(vinyl alcohol) (PVA) on the formation and stability of the droplets, as well as the sphericity and wall thickness uniformity of the resulting shells, were investigated. On increasing the molecular weight of the PVA, the densities of the external water phases (W2) are almost the same, but the viscosity of the W2 phase increases more quickly than the interfacial tension. This makes the detaching force increase more quickly than the upward one, causing the formation of compound droplets and detachment from the oil tube. On the other hand, the increase in interfacial tension makes the maximum pressures ( P max) in the O phase (O) of the compound droplets increase, causing them to rupture easily and decreasing their stability. However, for PVA with the same molecular weight, the viscous shear force in the flowing field reduces the role of gravity and makes the inner water droplet move towards the center of the compound droplet, decreasing its P max in the flowing field and improving its stability. Moreover, during the solidifying process, the viscous shear force increases more quickly than the interfacial tension force due to the quicker increase in viscosity with an increase in the molecular weight of the PVA. The increase in the viscous shear force can make the droplets deform, resulting in a decrease in their sphericity. However, the appropriate viscous shear force can also center the compound droplet—although they become decentered when the viscous shear force is too large, leading to the wall thickness uniformity increasing at first before decreasing quickly. The results presented in this work provide a more in-depth understanding of the

  4. Nano-silver in drinking water and drinking water sources: stability and influences on disinfection by-product formation.

    PubMed

    Tugulea, A-M; Bérubé, D; Giddings, M; Lemieux, F; Hnatiw, J; Priem, J; Avramescu, M-L

    2014-10-01

    untreated Ottawa River water, with a dissolved organic carbon concentration of 6 mg/L, was significantly higher than the stability of the nano-silver dispersions in distilled, organic-free water. Nano-silver particles suspended in the groundwater agglomerated and were quickly and quantitatively removed from the solution. Our data confirm previous observations that natural dissolved organic matter stabilizes nano-silver particles, while the high-ionic strength of groundwater appears to favor their agglomeration and precipitation. As expected, nano-silver was not stable in Ottawa River water through the chlorination process, but survived for many days when added to the Ottawa River water after treatment with chlorine or chloramines. Stirring appeared to have minimal effect on nano-silver stability in untreated and treated Ottawa River water. The profile of DBPs formed in the presence of nAg differed significantly from the profile of DBPs formed in the absence of nAg only at the 1 mg/L nAg concentration. The differences observed consisted mainly in reduced formation of some brominated DBPs and a small increase in the formation of cyanogen chloride. The reduced formation of brominated congeners may be explained by the decrease in available bromide due to the presence of Ag(+) ions. It should be noted that a concentration of 1 mg/L is significantly higher than nAg concentrations that would be expected to be present in surface waters, but these results could be significant for the disinfection of some wastewaters with comparably high nano-silver concentrations.

  5. Site-directed mutagenesis reveals regions implicated in the stability and fiber formation of human λ3r light chains.

    PubMed

    Villalba, Miryam I; Canul-Tec, Juan C; Luna-Martínez, Oscar D; Sánchez-Alcalá, Rosalba; Olamendi-Portugal, Timoteo; Rudiño-Piñera, Enrique; Rojas, Sonia; Sánchez-López, Rosana; Fernández-Velasco, Daniel A; Becerril, Baltazar

    2015-01-30

    Light chain amyloidosis (AL) is a disease that affects vital organs by the fibrillar aggregation of monoclonal light chains. λ3r germ line is significantly implicated in this disease. In this work, we contrasted the thermodynamic stability and aggregation propensity of 3mJL2 (nonamyloidogenic) and 3rJL2 (amyloidogenic) λ3 germ lines. Because of an inherent limitation (extremely low expression), Cys at position 34 of the 3r germ line was replaced by Tyr reaching a good expression yield. A second substitution (W91A) was introduced in 3r to obtain a better template to incorporate additional mutations. Although the single mutant (C34Y) was not fibrillogenic, the second mutation located at CDR3 (W91A) induced fibrillogenesis. We propose, for the first time, that CDR3 (position 91) affects the stability and fiber formation of human λ3r light chains. Using the double mutant (3rJL2/YA) as template, other variants were constructed to evaluate the importance of those substitutions into the stability and aggregation propensity of λ3 light chains. A change in position 7 (P7D) boosted 3rJL2/YA fibrillogenic properties. Modification of position 48 (I48M) partially reverted 3rJL2/YA fibril aggregation. Finally, changes at positions 8 (P8S) or 40 (P40S) completely reverted fibril formation. These results confirm the influential roles of N-terminal region (positions 7 and 8) and the loop 40-60 (positions 40 and 48) on AL. X-ray crystallography revealed that the three-dimensional topology of the single and double λ3r mutants was not significantly altered. This mutagenic approach helped to identify key regions implicated in λ3 AL.

  6. Formation of a compound flux rope by the merging of two filament channels, the associated dynamics, and its stability

    SciTech Connect

    Joshi, Navin Chandra; Inoue, Satoshi; Magara, Tetsuya E-mail: njoshi98@gmail.com

    2014-11-01

    We present observations of compound flux rope formation, which occurred on 2014 January 1, via merging of two nearby filament channels, the associated dynamics, and its stability using multiwavelength data. We also discuss the dynamics of cool and hot plasma moving along the newly formed compound flux rope. The merging started after the interaction between the southern leg of the northward filament and the northern leg of the southward filament at ≈01:21 UT and continued until a compound flux rope formed at ≈01:33 UT. During the merging, the cool filament plasma heated up and started to move along both sides of the compound flux rope, i.e., toward the north (≈265 km s{sup –1}) and south (≈118 km s{sup –1}) from the point of merging. After traveling a distance of ≈150 Mm toward the north, the plasma cooled down and started to return back to the south (≈14 km s{sup –1}) after ≈02:00 UT. The observations provide a clear example of compound flux rope formation via merging of two different flux ropes and the occurrence of a flare through tether cutting reconnection. However, the compound flux rope remained stable in the corona and had a confined eruption. The coronal magnetic field decay index measurements revealed that both the filaments and the compound flux rope axis lie within the stability domain (decay index <1.5), which may be the possible cause for their stability. The present study also deals with the relationship between the filament's chirality (sinistral) and the helicity (positive) of the surrounding flux rope.

  7. Surface Adsorption of Oppositely Charged SDS:C(12)TAB Mixtures and the Relation to Foam Film Formation and Stability.

    PubMed

    Fauser, Heiko; Uhlig, Martin; Miller, Reinhard; von Klitzing, Regine

    2015-10-08

    The complexation, surface adsorption, and foam film stabiliztation of the oppositely charged surfactants, sodium dodecyl sulfate (SDS) and dodecyl trimethylammonium bromide (C12TAB), is analyzed. The SDS:C12TAB mixing ratio is systematically varied to investigate whether the adsorption of equimolar or irregular catanionic surfactant complexes, and thus a variation in surface charge (i.e., surface excess of either SDS or C12TAB), governs foam film properties. Surface tension measurements indicate that SDS and C12TAB interact electrostatically in order to form stoichometric catanionic surfactant complexes and enhance surface adsorption. On the other hand it can be demonstrated that the SDS:C12TAB mixing ratio and, thus, a change in surface charge and composition plays a decisive role in foam film stabilization. The present study demonstrates that varying the mixing ratio between SDS and C12TAB offers a tool for tailoring surface composition and foam film properties, which are therefore not exclusively mediated by the presence of equimolar catanionic surfactant complexes. The SDS:C12TAB net amount and mixing ratio determine the type, stability, and thinning behavior of the corresponding foam film. These observations indicate the formation of a mixed surface layer, composed of the catanionic surfactant species surrounded by either free SDS or C12TAB molecules in excess. Furthermore, a systematic variation in CBF-NBF transition kinetics is rationalized on the basis of a microscopic phase transition within the foam films. Fundamental knowlegde gained from this research gives insight into the surface adsorption and foam film formation of catanionic surfactant mixtures. The study helps researchers to understand basic mechanisms of foam film stabilization and to use resources more efficiently.

  8. Site-directed Mutagenesis Reveals Regions Implicated in the Stability and Fiber Formation of Human λ3r Light Chains

    SciTech Connect

    Villalba, Miryam I.; Canul-Tec, Juan C.; Luna-Martínez, Oscar D.; Sánchez-Alcalá, Rosalba; Olamendi-Portugal, Timoteo; Rudiño-Piñera, Enrique; Rojas, Sonia; Sánchez-López, Rosana; Fernández-Velasco, Daniel A.; Becerril, Baltazar

    2014-12-11

    Light chain amyloidosis (AL) is a disease that affects vital organs by the fibrillar aggregation of monoclonal light chains. λ3r germ line is significantly implicated in this disease. In this paper, we contrasted the thermodynamic stability and aggregation propensity of 3mJL2 (nonamyloidogenic) and 3rJL2 (amyloidogenic) λ3 germ lines. Because of an inherent limitation (extremely low expression), Cys at position 34 of the 3r germ line was replaced by Tyr reaching a good expression yield. A second substitution (W91A) was introduced in 3r to obtain a better template to incorporate additional mutations. Although the single mutant (C34Y) was not fibrillogenic, the second mutation located at CDR3 (W91A) induced fibrillogenesis. We propose, for the first time, that CDR3 (position 91) affects the stability and fiber formation of human λ3r light chains. Using the double mutant (3rJL2/YA) as template, other variants were constructed to evaluate the importance of those substitutions into the stability and aggregation propensity of λ3 light chains. A change in position 7 (P7D) boosted 3rJL2/YA fibrillogenic properties. Modification of position 48 (I48M) partially reverted 3rJL2/YA fibril aggregation. Finally, changes at positions 8 (P8S) or 40 (P40S) completely reverted fibril formation. These results confirm the influential roles of N-terminal region (positions 7 and 8) and the loop 40–60 (positions 40 and 48) on AL. X-ray crystallography revealed that the three-dimensional topology of the single and double λ3r mutants was not significantly altered. Finally, this mutagenic approach helped to identify key regions implicated in λ3 AL.

  9. Site-directed Mutagenesis Reveals Regions Implicated in the Stability and Fiber Formation of Human λ3r Light Chains

    DOE PAGES

    Villalba, Miryam I.; Canul-Tec, Juan C.; Luna-Martínez, Oscar D.; ...

    2014-12-11

    Light chain amyloidosis (AL) is a disease that affects vital organs by the fibrillar aggregation of monoclonal light chains. λ3r germ line is significantly implicated in this disease. In this paper, we contrasted the thermodynamic stability and aggregation propensity of 3mJL2 (nonamyloidogenic) and 3rJL2 (amyloidogenic) λ3 germ lines. Because of an inherent limitation (extremely low expression), Cys at position 34 of the 3r germ line was replaced by Tyr reaching a good expression yield. A second substitution (W91A) was introduced in 3r to obtain a better template to incorporate additional mutations. Although the single mutant (C34Y) was not fibrillogenic, themore » second mutation located at CDR3 (W91A) induced fibrillogenesis. We propose, for the first time, that CDR3 (position 91) affects the stability and fiber formation of human λ3r light chains. Using the double mutant (3rJL2/YA) as template, other variants were constructed to evaluate the importance of those substitutions into the stability and aggregation propensity of λ3 light chains. A change in position 7 (P7D) boosted 3rJL2/YA fibrillogenic properties. Modification of position 48 (I48M) partially reverted 3rJL2/YA fibril aggregation. Finally, changes at positions 8 (P8S) or 40 (P40S) completely reverted fibril formation. These results confirm the influential roles of N-terminal region (positions 7 and 8) and the loop 40–60 (positions 40 and 48) on AL. X-ray crystallography revealed that the three-dimensional topology of the single and double λ3r mutants was not significantly altered. Finally, this mutagenic approach helped to identify key regions implicated in λ3 AL.« less

  10. Site-directed Mutagenesis Reveals Regions Implicated in the Stability and Fiber Formation of Human λ3r Light Chains*

    PubMed Central

    Villalba, Miryam I.; Canul-Tec, Juan C.; Luna-Martínez, Oscar D.; Sánchez-Alcalá, Rosalba; Olamendi-Portugal, Timoteo; Rudiño-Piñera, Enrique; Rojas, Sonia; Sánchez-López, Rosana; Fernández-Velasco, Daniel A.; Becerril, Baltazar

    2015-01-01

    Light chain amyloidosis (AL) is a disease that affects vital organs by the fibrillar aggregation of monoclonal light chains. λ3r germ line is significantly implicated in this disease. In this work, we contrasted the thermodynamic stability and aggregation propensity of 3mJL2 (nonamyloidogenic) and 3rJL2 (amyloidogenic) λ3 germ lines. Because of an inherent limitation (extremely low expression), Cys at position 34 of the 3r germ line was replaced by Tyr reaching a good expression yield. A second substitution (W91A) was introduced in 3r to obtain a better template to incorporate additional mutations. Although the single mutant (C34Y) was not fibrillogenic, the second mutation located at CDR3 (W91A) induced fibrillogenesis. We propose, for the first time, that CDR3 (position 91) affects the stability and fiber formation of human λ3r light chains. Using the double mutant (3rJL2/YA) as template, other variants were constructed to evaluate the importance of those substitutions into the stability and aggregation propensity of λ3 light chains. A change in position 7 (P7D) boosted 3rJL2/YA fibrillogenic properties. Modification of position 48 (I48M) partially reverted 3rJL2/YA fibril aggregation. Finally, changes at positions 8 (P8S) or 40 (P40S) completely reverted fibril formation. These results confirm the influential roles of N-terminal region (positions 7 and 8) and the loop 40–60 (positions 40 and 48) on AL. X-ray crystallography revealed that the three-dimensional topology of the single and double λ3r mutants was not significantly altered. This mutagenic approach helped to identify key regions implicated in λ3 AL. PMID:25505244

  11. Formation, Stability, and Mobility of One-Dimensional Lipid Bilayer on High Curvature Substrates

    SciTech Connect

    Huang, J; Martinez, J; Artyukhin, A; Sirbuly, D; Wang, Y; Ju, J W; Stroeve, P; Noy, A

    2007-03-23

    Curved lipid membranes are ubiquitous in living systems and play an important role in many biological processes. To understand how curvature and lipid composition affect membrane formation and fluidity we have assembled and studied mixed 1,2-Dioleoyl-sn-Glycero-3-Phosphocholine (DOPC) and 1,2-Dioleoyl-sn-Glycero-3-Phosphoethanolamine (DOPE) supported lipid bilayers on amorphous silicon nanowires with controlled diameters ranging from 20 nm to 200 nm. Addition of cone-shaped DOPE molecules to cylindrical DOPC molecules promotes vesicle fusion and bilayer formation on smaller diameter nanowires. Our experiments demonstrate that nanowire-supported bilayers are mobile, exhibit fast recovery after photobleaching, and have low concentration of defects. Lipid diffusion coefficients in these high-curvature tubular membranes are comparable to the values reported for flat supported bilayers and increase with decreasing nanowire diameter.

  12. The role of music preferences in early adolescents' friendship formation and stability.

    PubMed

    Selfhout, Maarten H W; Branje, Susan J T; ter Bogt, Tom F M; Meeus, Wim H J

    2009-02-01

    The present study examines the role of similarity in music preferences in the formation and discontinuation of friendships over a 1-year period. Questionnaire data were gathered from 283 Dutch same-sex mutual best friends (mean age=12.97) in two waves with a 1-year interval. Results show consistent evidence for high similarity in specific music dimensions among friends at both waves. Moderate similarity was found in the overall patterning of preferences for music genres at both waves, even after controlling for similarity in social background. Specific music similarity in more non-mainstream music dimensions and overall music similarity at Wave 1 were related to selecting a new friend at Wave 2. However, similarity in music preferences was not related to the discontinuation of an existing friendship at Wave 2. Thus, results suggest that similarity in music preferences is related to friendship formation, and not to friendship discontinuation.

  13. Two Decades of Stability and Change in Age at First Union Formation.

    PubMed

    Manning, Wendy D; Brown, Susan L; Payne, Krista K

    2014-04-01

    The landscape of union formation has been shifting; Americans are now marrying at the highest ages on record and the majority of young adults have cohabited. Yet little attention has been paid to the timing of cohabitation relative to marriage. Using the National Survey of Families and Households and 4 cycles of the National Survey of Family Growth, the authors examined the timing of marriage, cohabitation, and unions over 20 years. As the median age at first marriage has climbed, the age at cohabitation has remained stable for men and women. The changes in the timing of union formation have been similar according to race/ethnicity. The marked delay in marriage among women and men with low educational attainment has resulted in a near-convergence in the age at first marriage according to education. The authors conclude that the rise in cohabitation has offset changes in the levels and timing of marriage.

  14. Abluminal stimulation of sphingosine 1-phosphate receptors 1 and 3 promotes and stabilizes endothelial sprout formation.

    PubMed

    Das, Anusuya; Lenz, Steven M; Awojoodu, Anthony O; Botchwey, Edward A

    2015-01-01

    Local delivery of lipid mediators has become a promising new approach for therapeutic angiogenesis and regenerative medicine. In this study, we investigated how gradient stimulation (either abluminal/distal or luminal/proximal) of engineered microvessels with sphingosine 1-phosphate (S1P) receptor-subtype-targeted molecules affects endothelial sprout growth using a microfluidic device. Our studies show that distal stimulation of microvessels with FTY720, an S1P1/3 selective agonist, promotes both arterial and venular sprout growth, whereas proximal stimulation does not. Using novel pharmacological antagonists of S1P receptor subtypes, we further show that S1P3 functionality is necessary for VEGF-induced sprouting, and confirmed these findings ex vivo using a murine aortic ring assay from S1P3-deficient mice. S1P3 agonist stimulation enhanced vascular stability in both cell types via upregulation of the interendothelial junction protein VE-cadherin. Lastly, S1P3 activation under flow promoted endothelial sprouting and branching while decreasing migratory cell fate in the microfluidic device. We used an in vivo murine dorsal skinfold window chamber model to confirm S1P3's role in neovascular branching. Together, these data suggest that a distal transendothelial gradient of S1P1/3-targeted drugs is an effective technique for both enhancing and stabilizing capillary morphogenesis in angiogenic applications.

  15. Effects of amphiphilic diblock copolymer on drug nanoparticle formation and stability.

    PubMed

    Zhu, Zhengxi

    2013-12-01

    This study systematically compares the effects of amphiphilic diblock copolymer (di-BCP) on stabilizing hydrophobic drug nanoparticles formed by flash nanoprecipitation (FNP), and provides a guideline on choosing suitable di-BCPs. Four widely used di-BCPs, i.e., polystyrene-block-poly(ethylene glycol) (PS-b-PEG), polycaprolactone-block-poly(ethylene glycol) (PCL-b-PEG), polylactide-block-poly(ethylene glycol) (PLA-b-PEG), and poly(lactic-co-glycolic acid) (PLGA-b-PEG), and β-carotene as a model drug were used. The study showed that PLGA-b-PEG was the most suitable one, whose hydrophobic block was biodegradable and noncrystallizable as well as had relatively high glass transition temperature (Tg) and a right solubility parameter (δ). The molecular weight of PLGA block over the range from 5k to 15k showed an insignificant effect on controlling the particle size. Amorphous drug particles with a high drug loading of over 83 wt% can be achieved. Much remarkable evidence supported the nanoparticles with kinetically frozen and non-equilibrium packing structures of polymer chains rather than either the micelles or micellar nanoparticles with two well segregated polymer blocks. The thermodynamic effects of the drug and BCP on the particle stability, size and structures were discussed by using solubility parameters.

  16. Effects of amphiphilic diblock copolymer on drug nanoparticle formation and stability

    PubMed Central

    Zhu, Zhengxi

    2013-01-01

    This study systematically compares the effects of amphiphilic diblock copolymer (di-BCP) on stabilizing hydrophobic drug nanoparticles formed by flash nanoprecipitation (FNP), and provides a guideline on choosing suitable di-BCPs. Four widely used di-BCPs, i.e., polystyrene-block-poly(ethylene glycol) (PS-b-PEG), polycaprolactone-block-poly(ethylene glycol) (PCL-b-PEG), polylactide-block-poly(ethylene glycol) (PLA-b-PEG), and poly(lactic-co-glycolic acid) (PLGA-b-PEG), and β-carotene as a model drug were used. The study showed that PLGA-b-PEG was the most suitable one, whose hydrophobic block was biodegradable and noncrystallizable as well as had relatively high glass transition temperature (Tg) and a right solubility parameter (δ). The molecular weight of PLGA block over the range from 5k to 15k showed an insignificant effect on controlling the particle size. Amorphous drug particles with a high drug loading of over 83 wt% can be achieved. Much remarkable evidence supported the nanoparticles with kinetically frozen and nonequilibrium packing structures of polymer chains rather than either the micelles or micellar nanoparticles with two well segregated polymer blocks. The thermodynamic effects of the drug and BCP on the particle stability, size and structures were discussed by using solubility parameters. PMID:24070569

  17. Dimer formation and conformational flexibility ensure cytoplasmic stability and nuclear accumulation of Elk-1.

    PubMed

    Evans, Emma L; Saxton, Janice; Shelton, Samuel J; Begitt, Andreas; Holliday, Nicholas D; Hipskind, Robert A; Shaw, Peter E

    2011-08-01

    The ETS (E26) protein Elk-1 serves as a paradigm for mitogen-responsive transcription factors. It is multiply phosphorylated by mitogen-activated protein kinases (MAPKs), which it recruits into pre-initiation complexes on target gene promoters. However, events preparatory to Elk-1 phosphorylation are less well understood. Here, we identify two novel, functional elements in Elk-1 that determine its stability and nuclear accumulation. One element corresponds to a dimerization interface in the ETS domain and the second is a cryptic degron adjacent to the serum response factor (SRF)-interaction domain that marks dimerization-defective Elk-1 for rapid degradation by the ubiquitin-proteasome system. Dimerization appears to be crucial for Elk-1 stability only in the cytoplasm, as latent Elk-1 accumulates in the nucleus and interacts dynamically with DNA as a monomer. These findings define a novel role for the ETS domain of Elk-1 and demonstrate that nuclear accumulation of Elk-1 involves conformational flexibility prior to its phosphorylation by MAPKs.

  18. Abluminal Stimulation of Sphingosine 1-Phosphate Receptors 1 and 3 Promotes and Stabilizes Endothelial Sprout Formation

    PubMed Central

    Lenz, Steven M.; Awojoodu, Anthony O.

    2015-01-01

    Local delivery of lipid mediators has become a promising new approach for therapeutic angiogenesis and regenerative medicine. In this study, we investigated how gradient stimulation (either abluminal/distal or luminal/proximal) of engineered microvessels with sphingosine 1-phosphate (S1P) receptor-subtype-targeted molecules affects endothelial sprout growth using a microfluidic device. Our studies show that distal stimulation of microvessels with FTY720, an S1P1/3 selective agonist, promotes both arterial and venular sprout growth, whereas proximal stimulation does not. Using novel pharmacological antagonists of S1P receptor subtypes, we further show that S1P3 functionality is necessary for VEGF-induced sprouting, and confirmed these findings ex vivo using a murine aortic ring assay from S1P3-deficient mice. S1P3 agonist stimulation enhanced vascular stability in both cell types via upregulation of the interendothelial junction protein VE-cadherin. Lastly, S1P3 activation under flow promoted endothelial sprouting and branching while decreasing migratory cell fate in the microfluidic device. We used an in vivo murine dorsal skinfold window chamber model to confirm S1P3's role in neovascular branching. Together, these data suggest that a distal transendothelial gradient of S1P1/3-targeted drugs is an effective technique for both enhancing and stabilizing capillary morphogenesis in angiogenic applications. PMID:25315888

  19. Stabilizing Surfactant Templated Cylindrical Mesopores in Polymer and Carbon Films through Composite Formation with Silica Reinforcement

    SciTech Connect

    Song, Lingyan; Feng, Dan; Lee, Hae-Jeong; Wang, Chengqing; Wu, Quanyan; Zhao, Dongyuan; Vogt, Bryan D.

    2010-10-22

    A facile approach to maintain the periodic mesostructure of cylindrical pores in polymer-resin and carbon films after thermal template removal is explored through the reactive coassembly of resol (carbon precursor) and tetraethylorthosilicate (silica precursor) with triblock copolymer Pluronic F127. Without silica, a low porosity, disordered film is formed after pyrolysis despite the presence of an ordered mesostructure prior to template removal. However for silica concentration greater than 25 wt %, pyrolysis at 350 C yields a mesoporous silica-polymer film with well-defined pore mesostructure. These films remain well ordered upon carbonization at 800 C. In addition to the mesostructural stability, the addition of silica to the matrix impacts other morphological characteristics. For example, the average pore size and porosity of the films increase from 3.2 to 7.5 nm and 12 to 45%, respectively, as the concentration of silica in the wall matrix increases from 0 to 32 wt %. The improved thermal stability of the ordered mesostructure with the addition of silica to the matrix is attributed to the reinforcement of the mechanical properties leading to resistance to stress induced collapse of the mesostructure during template removal.

  20. Solubilizing and Stabilizing Proteins in Anhydrous Ionic Liquids through Formation of Protein-Polymer Surfactant Nanoconstructs.

    PubMed

    Brogan, Alex P S; Hallett, Jason P

    2016-04-06

    Nonaqueous biocatalysis is rapidly becoming a desirable tool for chemical and fuel synthesis in both the laboratory and industry. Similarly, ionic liquids are increasingly popular anhydrous reaction media for a number of industrial processes. Consequently, the use of enzymes in ionic liquids as efficient, environment-friendly, commercial biocatalysts is highly attractive. However, issues surrounding the poor solubility and low stability of enzymes in truly anhydrous media remain a significant challenge. Here, we demonstrate for the first time that engineering the surface of a protein to yield protein-polymer surfactant nanoconstructs allows for dissolution of dry protein into dry ionic liquids. Using myoglobin as a model protein, we show that this method can deliver protein molecules with near native structure into both hydrophilic and hydrophobic anhydrous ionic liquids. Remarkably, using temperature-dependent synchrotron radiation circular dichroism spectroscopy to measure half-denaturation temperatures, our results show that protein stability increases by 55 °C in the ionic liquid as compared to aqueous solution, pushing the solution thermal denaturation beyond the boiling point of water. Therefore, the work presented herein could provide a platform for the realization of biocatalysis at high temperatures or in anhydrous solvent systems.

  1. Factors that Influence the Formation and Stability of Thin, Cryo-EM Specimens

    PubMed Central

    Glaeser, Robert M.; Han, Bong-Gyoon; Csencsits, Roseann; Killilea, Alison; Pulk, Arto; Cate, Jamie H.D.

    2016-01-01

    Poor consistency of the ice thickness from one area of a cryo-electron microscope (cryo-EM) specimen grid to another, from one grid to the next, and from one type of specimen to another, motivates a reconsideration of how to best prepare suitably thin specimens. Here we first review the three related topics of wetting, thinning, and stability against dewetting of aqueous films spread over a hydrophilic substrate. We then suggest that the importance of there being a surfactant monolayer at the air-water interface of thin, cryo-EM specimens has been largely underappreciated. In fact, a surfactant layer (of uncontrolled composition and surface pressure) can hardly be avoided during standard cryo-EM specimen preparation. We thus suggest that better control over the composition and properties of the surfactant layer may result in more reliable production of cryo-EM specimens with the desired thickness. PMID:26386606

  2. Cluster formation in binary charge-stabilized colloidal suspensions confined to a two-dimensional plane

    NASA Astrophysics Data System (ADS)

    Kumar, Sanat; Mukherjee, Manjori; Mishra, Pankaj

    2016-09-01

    Hypernetted chain (HNC) integral equation theory has been used to study the structural features of binary charged stabilized colloidal suspensions confined to a two-dimensional plane. The particles interact via purely repulsive Yukawa intermolecular potential, the inverse screening length scaled by the average distance between strongly interacting components of the mixture (dimensionless screening parameter) being 1, 3 and 5. Results of HNC theory for one-component systems are found to be in very good agreement with that of simulation, in the parameter range of our study. Binary Yukawa systems with dimensionless screening parameters 1 and 3 are found to exhibit diffuse clusters of the weakly interacting particles, marked by the emergence of a cluster peak in the corresponding partial structure factor curves. No cluster peak is found in the system with the screening parameter 5. For the entire range of mixture parameters, the strongly interacting particles remain homogeneously distributed.

  3. Beta-Barrel Scaffold of Fluorescent Proteins: Folding, Stability and Role in Chromophore Formation

    PubMed Central

    Stepanenko, Olesya V.; Stepanenko, Olga V.; Kuznetsova, Irina M.; Verkhusha, Vladislav V.; Turoverov, Konstantin K.

    2013-01-01

    This review focuses on the current view of the interaction between the β-barrel scaffold of fluorescent proteins and their unique chromophore located in the internal helix. The chromophore originates from the polypeptide chain and its properties are influenced by the surrounding protein matrix of the β-barrel. On the other hand, it appears that a chromophore tightens the β-barrel scaffold and plays a crucial role in its stability. Furthermore, the presence of a mature chromophore causes hysteresis of protein unfolding and refolding. We survey studies measuring protein unfolding and refolding using traditional methods as well as new approaches, such as mechanical unfolding and reassembly of truncated fluorescent proteins. We also analyze models of fluorescent protein unfolding and refolding obtained through different approaches, and compare the results of protein folding in vitro to co-translational folding of a newly synthesized polypeptide chain. PMID:23351712

  4. Post-Formation Shrinkage and Stabilization of Microfluidic Bubbles in Lipid Solution.

    PubMed

    Shih, Roger; Lee, Abraham P

    2016-03-01

    Medical ultrasound imaging often employs ultrasound contrast agents (UCAs), injectable microbubbles stabilized by shells or membranes. In tissue, the compressible gas cores can strongly scatter acoustic signals, resonate, and emit harmonics. However, bubbles generated by conventional methods have nonuniform sizes, reducing the fraction that resonates with a given transducer. Microfluidic flow-focusing is an alternative production method which generates highly monodisperse bubbles with uniform constituents, enabling more-efficient contrast enhancement than current UCAs. Production size is tunable by adjusting gas pressure and solution flow rate, but solution effects on downstream stable size and lifetime have not been closely examined. This study therefore investigated several solution parameters, including the DSPC/DSPE-PEG2000 lipid ratio, concentration, viscosity, and preparation temperature to determine their effects on stabilization. It was found that bubble lifetime roughly correlated with stable size, which in turn was strongly influenced by primary-lipid-to-emulsifier ratio, analogous to its effects on conventional bubble yield and Langmuir-trough compressibility in existing studies. Raising DSPE-PEG2000 fraction in solution reduced bubble surface area in proportion to its reduction of lipid packing density at low compression in literature. In addition, the surface area was found to increase proportionately with lipid concentration above 2.1 mM. However, viscosities above or below 2.3-3.3 mPa·s seemed to reduce bubble size. Finally, lipid preparation at room temperature led to smaller bubbles compared to preparation near or above the primary lipid's phase transition point. Understanding these effects will further improve on postformation control over microfluidic bubble production, and facilitate size-tuning for optimal contrast enhancement.

  5. The stability of elastically strained nanorings and the formation of quantum dot molecules

    NASA Astrophysics Data System (ADS)

    Gill, Simon P. A.

    2015-05-01

    Self-assembled nanorings have recently been identified in a number of heteroepitaxially strained material systems. Under some circumstances these rings have been observed to break up into ring-shaped quantum dot molecules. A general non-linear model for the elastic strain energy of non-axisymmetric epitaxially strained nanostructures beyond the small slope assumption is developed. This model is then used to investigate the stability of strained nanorings evolving via surface diffusion subject to perturbations around their circumference. An expression for the fastest growing mode is determined and related to experimental observations. The model predicts a region of stability for rings below a critical radius, and also a region for larger rings which have a proportionally small thickness. The predictions of the model are shown to be consistent with the available results. For the heteroepitaxial InP on In0.5Ga0.5P system investigated by Jevasuwan et al. (2013), the nanorings are found to be stable below a certain critical size. This is in good quantitative agreement with the model predictions. At larger sizes, the rings are unstable. The number of dots in the resulting quantum dot molecule is similar to the mode number for the fastest growing mode. Second order terms show that the number of dots is expected to reduce as the height of the ring increases in proportion to its thickness. The strained In0.4Ga0.6As on GaAs nanorings of Hanke et al. (2007) are always stable and this is in accordance with the findings of the analysis. The Au nanorings of Ruffino et al. (2011) are stable as well, even as they expand during annealing. This observation is also shown to be consistent with the proposed model, which is expected to be useful in the design and tailoring of heteroepitaxial systems for the self-organisation of quantum dot molecules.

  6. Silver nanoparticles in complex biological media: assessment of colloidal stability and protein corona formation

    NASA Astrophysics Data System (ADS)

    Argentiere, Simona; Cella, Claudia; Cesaria, Maura; Milani, Paolo; Lenardi, Cristina

    2016-08-01

    Engineered silver nanoparticles (AgNPs) are among the most used nanomaterials in consumer products, therefore concerns are raised about their potential for adverse effects in humans and environment. Although an increasing number of studies in vitro and in vivo are being reported on the toxicity of AgNPs, most of them suffer from incomplete characterization of AgNPs in the tested biological media. As a consequence, the comparison of toxicological data is troublesome and the toxicity evaluation still remains an open critical issue. The development of a reliable protocol to evaluate interactions of AgNPs with surrounding proteins as well as to assess their colloidal stability is therefore required. In this regard, it is of importance not only to use multiple, easy-to-access and simple techniques but also to understand limitations of each characterization methods. In this work, the morphological and structural behaviour of AgNPs has been studied in two relevant biological media, namely 10 % FBS and MP. Three different techniques (Dynamic Light Scattering, Transmission Electron Microscopy, UV-Vis spectroscopy) were tested for their suitability in detecting AgNPs of three different sizes (10, 40 and 100 nm) coated with either citrate or polyvinylpyrrolidone. Results showed that UV-Vis spectroscopy is the most versatile and informative technique to gain information about interaction between AgNPs and surrounding proteins and to determine their colloidal stability in the tested biological media. These findings are expected to provide useful insights in characterizing AgNPs before performing any further in vitro/in vivo experiment.

  7. Formation and Stabilization of Environmentally Persistent Free Radicals Induced by the Interaction of Anthracene with Fe(III)-Modified Clays.

    PubMed

    Jia, Hanzhong; Nulaji, Gulimire; Gao, Hongwei; Wang, Fu; Zhu, Yunqing; Wang, Chuanyi

    2016-06-21

    Environmentally persistent free radicals (EPFRs) are occasionally detected in Superfund sites but the formation of EPFRs induced by polycyclic aromatic hydrocarbons (PAHs) is not well understood. In the present work, the formation of EPFRs on anthracene-contaminated clay minerals was quantitatively monitored via electron paramagnetic resonance (EPR) spectroscopy, and surface/interface-related environmental influential factors were systematically explored. The obtained results suggest that EPFRs are more readily formed on anthracene-contaminated Fe(III)-montmorillonite than in other tested systems. Depending on the reaction condition, more than one type of organic radicals including anthracene-based radical cations with g-factors of 2.0028-2.0030 and oxygenic carbon-centered radicals featured by g-factors of 2.0032-2.0038 were identified. The formed EPFRs are stabilized by their interaction with interlayer surfaces, and such surface-bound EPFRs exhibit slow decay with 1/e-lifetime of 38.46 days. Transformation pathway and possible mechanism are proposed on the basis of experimental results and quantum mechanical simulations. Overall, the formation of EPFRs involves single-electron-transfer from anthracene to Fe(III) initially, followed by H2O addition on formed aromatic radical cation. Because of their potential exposure in soil and atmosphere, such clay surface-associated EPFRs might induce more serious toxicity than PAHs and exerts significant impacts on human health.

  8. Pyromorphite formation and stability after quick lime neutralisation in the presence of soil and clay sorbents

    SciTech Connect

    Chappell, Mark A.; Scheckel, Kirk G.

    2008-06-16

    Soluble Pb is immobilised in pure systems as pyromorphite by adding sources of P, but doubts remain about the effectiveness of this approach in natural soil systems, particularly given the ability of soil humic substances to interfere with Pb-mineral formation. In addition, recent thermodynamic modelling predicts that pyromorphite formed by the addition of phosphoric acid to Pb-contaminated soils, followed by neutralisation with quick lime (Ca(OH){sub 2}) will destabilise the mineral, reverting the Pb back to more soluble species such as cerussite or anglesite. In this paper, we describe experiments to form pyromorphite in the presence of two different sorbents: a reference smectite called Panther Creek Bentonite, and a commercially available, organically rich potting mixture. We present X-ray diffraction (XRD) evidence suggestive of pyromorphite formation, yet, like similar studies, the evidence is less than conclusive. Linear combination fits of Pb X-ray absorption fine-structure spectroscopy (XAFS) data collected at the Advanced Photon Source at Argonne National Laboratory show that pyromorphite is the major Pb species formed after the addition of phosphoric acid. Furthermore, XAFS data shows that neutralising with quick lime enhances (as opposed to reducing) pyromorphite content in these systems. These results call into question relying solely on XRD data to confirm or deny the existence of minerals like pyromorphite, whose complex morphology give less intense and more complicated diffraction patterns than some of the simpler Pb minerals.

  9. In situ formation of magnetite reactive barriers in soil for waste stabilization

    DOEpatents

    Moore, Robert C.

    2003-01-01

    Reactive barriers containing magnetite and methods for making magnetite reactive barriers in situ in soil for sequestering soil contaminants including actinides and heavy metals, organic materials, iodine and technetium are disclosed. According to one embodiment, a two-step reagent introduction into soil takes place. In the first step, free oxygen is removed from the soil by separately injecting into the soil aqueous solutions of iron (II) salt, for example FeCl.sub.2, and base, for example NaOH or NH.sub.3 in about a 1:1 volume ratio. Then, in the second step, similar reagents are injected a second time (however, according to about a 1:2 volume ratio, iron to salt) to form magnetite. The magnetite formation is facilitated, in part, due to slow intrusion of oxygen into the soil from the surface. The invention techniques are suited to injection of reagents into soil in proximity to a contamination plume or source allowing in situ formation of the reactive barrier at the location of waste or hazardous material. Mixing of reagents to form. precipitate is mediated and enhanced through movement of reagents in soil as a result of phenomena including capillary action, movement of groundwater, soil washing and reagent injection pressure.

  10. Effect of glycerol on formation, stability, and properties of vitamin-E enriched nanoemulsions produced using spontaneous emulsification.

    PubMed

    Saberi, Amir Hossein; Fang, Yuan; McClements, David Julian

    2013-12-01

    Oil-in-water nanoemulsions are finding increasing use as delivery systems to encapsulate lipophilic bioactive components in functional food, personal care, and pharmaceutical products. We investigated the influence of a water-soluble cosolvent (glycerol) on the formation, stability, and properties of vitamin E acetate-loaded nanoemulsions (VE-NEs) prepared by spontaneous emulsification. VE-NEs were formed by titration of a mixture of vitamin E acetate, carrier oil (MCT) and non-ionic surfactant (Tween 80) into an aqueous glycerol solution with continuous mixing. Cosolvent concentration had an appreciable effect on the particle size produced, with the smallest mean droplet diameters (d<50 nm) being formed at 40 and 50 wt% glycerol. Nanoemulsions (d<100 nm) containing 10% vitamin E acetate could be produced at relatively low surfactant concentrations (5%) using these high glycerol levels. The turbidity of the NEs decreased at high glycerol concentrations due to the reduction in droplet size and refractive index contrast. The long-term stability of the VE-NEs was strongly influenced by glycerol concentration and storage temperature. VE-NEs containing 40% glycerol were relatively stable to droplet growth when stored at 5 and 20°C, but a rapid increase in droplet size and turbidity occurred during storage at 37°C. Temperature scanning experiments (20-80-20°C) indicated that a steep and irreversible increase in turbidity occurred during heating, which was around 70°C in the absence of glycerol and 60°C in the presence of 40% glycerol. Droplet instability was attributed to an increase in the rate of Ostwald ripening and/or coalescence as the temperature was increased, associated with dehydration of the non-ionic surfactant head-group leading to a reduction in phase inversion temperature. Dilution (100×) of VE-NEs containing glycerol with water considerably improved their stability to droplet growth, especially at high storage temperatures. This study provides

  11. Formation and Stabilization of Single-Crystalline Metastable AuGe Phases in Ge Nanowires

    SciTech Connect

    Sutter, E.; Sutter, P.

    2011-07-22

    We use in situ observations by variable temperature transmission electron microscopy on AuGe alloy drops at the tips of Ge nanowires (NWs) with systematically varying composition to demonstrate the controlled formation of metastable solid phases integrated in NWs. The process, which operates in the regime of vapor-liquid-solid growth, involves a size-dependent depression of the alloy liquidus at the nanoscale that leads to extremely Ge-rich AuGe melts at low temperatures. During slow cooling, these liquid AuGe alloy drops show pronounced departures from equilibrium, i.e., a frustrated phase separation of Ge into the adjacent solid NW, and ultimately crystallize as single-crystalline segments of metastable {gamma}-AuGe. Our findings demonstrate a general avenue for synthesizing NW heterostructures containing stable and metastable solid phases, applicable to a wide range of materials of which NWs form by the vapor-liquid-solid method.

  12. Formation and stability of As-H bonds in H-implanted GaAs

    SciTech Connect

    Stein, H.J.

    1990-01-01

    The chemical bonding and isochronal annealing of H implanted into GaAs at 80 K has been investigated by infrared absorption measurements. Based upon the frequency shift when deuterium is substituted for H, and an equivalent band formation in InAs, assignment of a new band at 2029 cm{sup {minus}1} is made to As-H centers. Bonding of H at interstitial As of and As-vacancy pair which anneals between 150 and 250K is suggested as the structure for the defect. A previously-reported absorption band at 1834 cm{sup {minus}1} assigned to Ga-H centers in H-implanted GaAS increase in intensity when H is released from As-H centers. 15 refs., 5 figs.

  13. L-plastin nanobodies perturb matrix degradation, podosome formation, stability and lifetime in THP-1 macrophages.

    PubMed

    De Clercq, Sarah; Boucherie, Ciska; Vandekerckhove, Joël; Gettemans, Jan; Guillabert, Aude

    2013-01-01

    Podosomes are cellular structures acting as degradation 'hot-spots' in monocytic cells. They appear as dot-like structures at the ventral cell surface, enriched in F-actin and actin regulators, including gelsolin and L-plastin. Gelsolin is an ubiquitous severing and capping protein, whereas L-plastin is a leukocyte-specific actin bundling protein. The presence of the capping protein CapG in podosomes has not yet been investigated. We used an innovative approach to investigate the role of these proteins in macrophage podosomes by means of nanobodies or Camelid single domain antibodies. Nanobodies directed against distinct domains of gelsolin, L-plastin or CapG were stably expressed in macrophage-like THP-1 cells. CapG was not enriched in podosomes. Gelsolin nanobodies had no effect on podosome formation or function but proved very effective in tracing distinct gelsolin populations. One gelsolin nanobody specifically targets actin-bound gelsolin and was effectively enriched in podosomes. A gelsolin nanobody that blocks gelsolin-G-actin interaction was not enriched in podosomes demonstrating that the calcium-activated and actin-bound conformation of gelsolin is a constituent of podosomes. THP-1 cells expressing inhibitory L-plastin nanobodies were hampered in their ability to form stable podosomes. Nanobodies did not perturb Ser5 phosphorylation of L-plastin although phosphorylated L-plastin was highly enriched in podosomes. Furthermore, nanobody-induced inhibition of L-plastin function gave rise to an irregular and unstable actin turnover of podosomes, resulting in diminished degradation of the underlying matrix. Altogether these results indicate that L-plastin is indispensable for podosome formation and function in macrophages.

  14. Composition-dependent stability of the medium-range order responsible for metallic glass formation

    DOE PAGES

    Zhang, Feng; Ji, Min; Fang, Xiao-Wei; ...

    2014-09-18

    The competition between the characteristic medium-range order corresponding to amorphous alloys and that in ordered crystalline phases is central to phase selection and morphology evolution under various processing conditions. We examine the stability of a model glass system, Cu–Zr, by comparing the energetics of various medium-range structural motifs over a wide range of compositions using first-principles calculations. Furthermore, we focus specifically on motifs that represent possible building blocks for competing glassy and crystalline phases, and we employ a genetic algorithm to efficiently identify the energetically favored decorations of each motif for specific compositions. These results show that a Bergman-type motifmore » with crystallization-resisting icosahedral symmetry is energetically most favorable in the composition range 0.63 < xCu < 0.68, and is the underlying motif for one of the three optimal glass-forming ranges observed experimentally for this binary system (Li et al., 2008). This work establishes an energy-based methodology to evaluate specific medium-range structural motifs which compete with stable crystalline nuclei in deeply undercooled liquids.« less

  15. Composition-dependent stability of the medium-range order responsible for metallic glass formation

    SciTech Connect

    Zhang, Feng; Ji, Min; Fang, Xiao-Wei; Sun, Yang; Wang, Cai-Zhuang; Mendelev, Mikhail I.; Kramer, M. J.; Napolitano, Ralph E.; Ho, Kai-Ming

    2014-09-18

    The competition between the characteristic medium-range order corresponding to amorphous alloys and that in ordered crystalline phases is central to phase selection and morphology evolution under various processing conditions. We examine the stability of a model glass system, Cu–Zr, by comparing the energetics of various medium-range structural motifs over a wide range of compositions using first-principles calculations. Furthermore, we focus specifically on motifs that represent possible building blocks for competing glassy and crystalline phases, and we employ a genetic algorithm to efficiently identify the energetically favored decorations of each motif for specific compositions. These results show that a Bergman-type motif with crystallization-resisting icosahedral symmetry is energetically most favorable in the composition range 0.63 < xCu < 0.68, and is the underlying motif for one of the three optimal glass-forming ranges observed experimentally for this binary system (Li et al., 2008). This work establishes an energy-based methodology to evaluate specific medium-range structural motifs which compete with stable crystalline nuclei in deeply undercooled liquids.

  16. The change of the scFv into the Fab format improves the stability and in vivo toxin neutralization capacity of recombinant antibodies.

    PubMed

    Quintero-Hernández, Veronica; Juárez-González, Victor R; Ortíz-León, Mauricio; Sánchez, Rosalba; Possani, Lourival D; Becerril, Baltazar

    2007-02-01

    The antigen-binding fragment (Fab) has been considered a more functionally stable version of recombinant antibodies than single chain antibody fragments (scFvs), however this intuitive consideration has not been sufficiently proven in vivo. This communication shows that three out of four specific scFvs against a scorpion toxin, with different affinities and stabilities, become neutralizing in vivo when expressed as Fabs, despite the fact that they are not neutralizing in the scFv format. A scFv fragment previously obtained from a neutralizing mouse antibody (BCF2) was used to produce three derived scFvs by directed evolution. Only one of them was neutralizing, however when expressed as Fab, all of them became neutralizing fragments in vivo. The initial scFvBCF2 (earlier used for directed evolution) was not neutralizing in the scFv format. After expressing it as Fab did not become a neutralizing fragment, but did reduce the intoxication symptoms of experimental mice. The stability of the four Fabs derived from their respective scFvs was improved when tested in the presence of guanidinium chloride. The in vitro stability of the Fab format has been shown earlier, but the physiological consequences of this stability are shown in this communication. The present results indicate that improved functional stability conferred by the Fab format can replace additional maturation steps, when the affinity and stability are close to the minimum necessary to be neutralizing.

  17. A Kalman Filter for Mass Property and Thrust Identification of the Spin-Stabilized Magnetospheric Multiscale Formation

    NASA Technical Reports Server (NTRS)

    Queen, Steven Z.

    2015-01-01

    The Magnetospheric Multiscale (MMS) mission consists of four identically instrumented, spin-stabilized observatories, elliptically orbiting the Earth in a tetrahedron formation. For the operational success of the mission, on-board systems must be able to deliver high-precision orbital adjustment maneuvers. On MMS, this is accomplished using feedback from on-board star sensors in tandem with accelerometers whose measurements are dynamically corrected for errors associated with a spinning platform. In order to determine the required corrections to the measured acceleration, precise estimates of attitude, rate, and mass-properties are necessary. To this end, both an on-board and ground-based Multiplicative Extended Kalman Filter (MEKF) were formulated and implemented in order to estimate the dynamic and quasi-static properties of the spacecraft.

  18. Peroxisome-targeted and tandem repeat multimer expressions of human antimicrobial peptide LL37 in Pichia pastoris.

    PubMed

    Xiao, Siwei; Gao, Yanyun; Wang, Xiaolong; Shen, Wei; Wang, Jinjia; Zhou, Xiangshan; Cai, Menghao; Zhang, Yuanxing

    2017-03-16

    Although the human antimicrobial peptide LL37 has a broad spectrum of antimicrobial activities, it easily damages host cells following heterologous expressions. This study attempted two strategies to alleviate its damage to host cells when expressed in Pichia pastoris using the AOX1 promoter. Tandem repeat multimers of LL37 were first designed, and secretion expression strains GS115-9K-(DPLL37DP)n (n = 2, 4, 6 and 8) containing different copies of the LL37 gene were constructed. However, LL37 tandems still killed the cells after 96 hr of induction. Subsequently, peroxisome-targeted expression was performed by adding a peroxisomal targeting signal 1 (SKL) at the C-terminus of LL37. The LL37 expression strain GS115-3.5K-LL37-SKL showed no significant inhibition in the cells after induction. Antibacterial activity assays showed that the recombinant LL37 expressed in peroxisomes had good antimicrobial activities. Then, a strain GS115-3.5K-LL37-GFP-SKL producing LL37, green fluorescent protein, and SKL fusion proteins was constructed, and the fusion protein was confirmed to be targeting the peroxisomes. However, protein extraction analysis indicated that most of the fusion proteins were still located in the cell debris after cell disruption, and further studies are required to extract more proteins from the peroxisome membrane.

  19. Formation of copper aluminate spinel and cuprous aluminate delafossite to thermally stabilize simulated copper-laden sludge.

    PubMed

    Hu, Ching-Yao; Shih, Kaimin; Leckie, James O

    2010-09-15

    The study reported herein indicated the stabilization mechanisms at work when copper-laden sludge is thermally treated with gamma-alumina and kaolinite precursors, and evaluated the prolonged leachability of their product phases. Four copper-containing phases - copper oxide (CuO), cuprous oxide (Cu(2)O), copper aluminate spinel (CuAl(2)O(4)), and cuprous aluminate delafossite (CuAlO(2)) - were found in the thermal reactions of the investigated systems. These phases were independently synthesized for leaching by 0.1M HCl aqueous solution, and the relative leachabilities were found to be CuAl(2)O(4)formation mechanism employed to stabilize copper into CuAl(2)O(4) and CuAlO(2) are extensively discussed here. With a 3h of short sintering, it was found that CuAl(2)O(4) could be effectively formed between 850 and 950 degrees C by the gamma-alumina precursor. Although kaolinite had a lower incorporation capability than gamma-alumina, it was found to transform a considerable amount of copper into CuAl(2)O(4) between 950 and 1000 degrees C. At higher temperatures, CuAlO(2) was produced only in the gamma-alumina system as the occurrence of Cu(2)O-cristobalite solution in the kaolinite system precluded the production of CuAlO(2). The hypothesis that the spinel formation mechanism has two stages was supported by the results of the changing Cu/Al mole ratio in the system, and the rate-limiting step was identified as the diffusion process in the second stage.

  20. The Importance of Solid Electrolyte Interphase Formation for Long Cycle Stability Full-Cell Na-Ion Batteries

    SciTech Connect

    Li, Xiaolin; Yan, Pengfei; Engelhard, Mark H.; Crawford, Aladsair J.; Viswanathan, Vilayanur V.; Wang, Chong M.; Liu, Jun; Sprenkle, Vincent L.

    2016-07-30

    Na-ion battery, as an alternative high-efficiency and low-cost energy storage device to Li-ion battery, has attracted wide interest for electrical grid and vehicle applications. However, demonstration of a full-cell battery with high energy and long cycle life remains a significant challenge. Here, we investigated the role of solid electrolyte interphase (SEI) formation on both cathodes and anodes and revealed a potential way to achieve long-term stability for Na-ion battery full-cells. Pre-cycling of cathodes and anodes leads to preformation of SEI, and hence mitigates the consumption of Na ions in full-cells. The example full-cell of Na0.44MnO2-hard carbon with pre-cycled and capacity-matched electrodes can deliver a specific capacity of ~116 mAh/g based on Na0.44MnO2 at 1C rate (1C = 120 mA/g). The corresponding specific energy is ~313 Wh/kg. Excellent cycling stability with ~77% capacity retention over 2000 cycles was demonstrated at 2C rate. Our work represents a leap forward in Na-ion battery development.

  1. β-Lactamase Inhibition by 7-Alkylidenecephalosporin Sulfones: Allylic Transposition and Formation of an Unprecedented Stabilized Acyl-Enzyme

    PubMed Central

    Rodkey, Elizabeth A.; McLeod, David C.; Bethel, Christopher R.; Smith, Kerri M.; Xu, Yan; Chai, Weirui; Che, Tao; Carey, Paul R.; Bonomo, Robert A.; van den Akker, Focco; Buynak, John D.

    2014-01-01

    The inhibition of the class A SHV-1 β-lactamase by 7-(tert-butoxycarbonyl)methylidenecephalosporin sulfone was examined kinetically, spectroscopically, and crystallographically. An 1.14Å X-ray crystal structure shows that the stable acyl-enzyme, which incorporates an eight-membered ring, is a covalent derivative of Ser70 linked to the 7-carboxy group of 2-H-5,8-dihydro-1,1-dioxo-1,5-thiazocine-4,7-dicarboxylic acid. A cephalosporin-derived enzyme complex of this type is unprecedented and the rearrangement leading to its formation may offer new possibilities for inhibitor design. The observed acyl-enzyme derives its stability from the resonance stabilization conveyed by the β-aminoacrylate (i.e. vinylogous urethane) functionality as there is relatively little interaction of the eight-membered ring with active site residues. Two mechanistic schemes are proposed, differing in whether, subsequent to acylation of the active site serine and opening of the β-lactam, the resultant dihydrothiazine fragments on its own, or is assisted by an adjacent nucleophilic atom, in the form of the carbonyl oxygen of the C7 tert-butyloxycarbonyl group. This compound was also found to be a submicromolar inhibitor of the class C ADC-7 and PDC-3 β-lactamases. PMID:24219313

  2. Formation and Stabilization of Combustion-Generated, Environmentally Persistent Radicals on Ni(II)O Supported on a Silica Surface

    PubMed Central

    Vejerano, Eric; Lomnicki, Slawomir M.; Dellinger, Barry

    2013-01-01

    Previous studies have indicated Environmentally Persistent Free Radicals (EPFRs) are formed when hydroxyl- and chlorine-substituted aromatics chemisorbed on Cu(II)O and Fe(III)2O3 surfaces and were stabilized through their interactions with the surface metal cation. The current study reports our laboratory investigation on the formation and stabilization of EPFRs on an Ni(II)O surface. The EPFRs were produced by the chemisorption of adsorbates on the supported metal oxide surface and transfer of an electron from the adsorbate to the metal center, resulting in reduction of the metal cation. Depending on the temperature and the nature of the adsorbate, more than one type of organic radical was formed. A phenoxyl-type radical, with g-value between 2.0029 and 2.0044, and a semiquinone-type radical, with g-value from 2.0050 to as high as 2.0081, were observed. The half-lives on Ni(II)O were long and ranged from 1.5 to 5.2 days, which were similar to what were observed on Fe(III)2O3,. The yields of the EPFRs formed on Ni(II)O was ~ 8x higher than on Cu(II)O and ~50x higher than on Fe(III)2O3. PMID:22831558

  3. The ionic liquid isopropylammonium formate as a mobile phase modifier to improve protein stability during reversed phase liquid chromatography.

    PubMed

    Zhou, Ling; Danielson, Neil D

    2013-12-01

    The room temperature ionic liquid isopropylammonium formate (IPAF) is studied as a reversed phase HPLC mobile phase modifier for separation of native proteins using a polymeric column and the protein stability is compared to that using acetonitrile (MeCN) as the standard organic mobile phase modifier. A variety of important proteins with different numbers of subunits are investigated, including non-subunit proteins: albumin, and amyloglucosidase (AMY); a two subunit protein: thyroglobulin (THY); and four subunit proteins: glutamate dehydrogenase (GDH) and lactate dehydrogenase (LDH). A significant enhancement in protein stability is observed in the chromatograms upon using IPAF as a mobile phase modifier. The first sharper peak at about 2min represented protein in primarily the native form and a second broader peak more retained at about 5-6min represented substantially denatured or possibly aggregated protein. The investigated proteins (except LDH) could maintain the native form within up to 50% IPAF, while a mobile phase, with as low as 10% MeCN, induced protein denaturation. The assay for pyruvate using LDH has further shown that enzymatic activity can be maintained up to 30% IPAF in water in contrast to no activity using 30% MeCN.

  4. Surface-Induced Phase of Tyrian Purple (6,6'-Dibromoindigo): Thin Film Formation and Stability.

    PubMed

    Truger, Magdalena; Roscioni, Otello M; Röthel, Christian; Kriegner, Dominik; Simbrunner, Clemens; Ahmed, Rizwan; Głowacki, Eric D; Simbrunner, Josef; Salzmann, Ingo; Coclite, Anna Maria; Jones, Andrew O F; Resel, Roland

    2016-07-06

    The appearance of surface-induced phases of molecular crystals is a frequently observed phenomenon in organic electronics. However, despite their fundamental importance, the origin of such phases is not yet fully resolved. The organic molecule 6,6'-dibromoindigo (Tyrian purple) forms two polymorphs within thin films. At growth temperatures of 150 °C, the well-known bulk structure forms, while at a substrate temperature of 50 °C, a surface-induced phase is observed instead. In the present work, the crystal structure of the surface-induced polymorph is solved by a combined experimental and theoretical approach using grazing incidence X-ray diffraction and molecular dynamics simulations. A comparison of both phases reveals that π-π stacking and hydrogen bonds are common motifs for the intermolecular packing. In-situ temperature studies reveal a phase transition from the surface-induced phase to the bulk phase at a temperature of 210 °C; the irreversibility of the transition indicates that the surface-induced phase is metastable. The crystallization behavior is investigated ex-situ starting from the sub-monolayer regime up to a nominal thickness of 9 nm using two different silicon oxide surfaces; island formation is observed together with a slight variation of the crystal structure. This work shows that surface-induced phases not only appear for compounds with weak, isotropic van der Waals bonds, but also for molecules exhibiting strong and highly directional hydrogen bonds.

  5. Evaluation of the geological relationships to gas hydrate formation and stability

    SciTech Connect

    Not Available

    1985-01-01

    During the reported year we have enhanced our knowledge on and gained considerable experience in assessment of the gas hydrate resources in the offshore environments. Specifically, we have learned and gained experience in the following: Efficiently locating data sources, including published literature and unpublished information. We have established personal communication extremely critical in data accessability and acquisition. We have updated information pertinent to gas hydrate knowledge, also based on thorough study and evaluation of most Russian literature and additional publications in languages other than English. Besides critical evaluation of widely spread literature, in many cases our reports include previously unpublished information (e.g. BSRs from the Gulf of Mexico). The assessment of the gas resources potential associated with the gas hydrates, although in most cases at a low level of confidence, appears also very encouraging for further, more detailed, study. We are also confident that, because of the present reports' format, new data and a concept-oriented approach, the result of our study will be of strong interest to various industries, research institutions and numerous governmental agencies.

  6. CCM2-CCM3 interaction stabilizes their protein expression and permits endothelial network formation

    SciTech Connect

    Draheim, Kyle M.; Li, Xiaofeng; Zhang, Rong; Fisher, Oriana S.; Villari, Giulia; Boggon, Titus J.; Calderwood, David A.

    2015-04-21

    Mutations in the essential adaptor proteins CCM2 or CCM3 lead to cerebral cavernous malformations (CCM), vascular lesions that most frequently occur in the brain and are strongly associated with hemorrhagic stroke, seizures, and other neurological disorders. CCM2 binds CCM3, but the molecular basis of this interaction, and its functional significance, have not been elucidated. Here, we used x-ray crystallography and structure-guided mutagenesis to show that an α-helical LD-like motif within CCM2 binds the highly conserved “HP1” pocket of the CCM3 focal adhesion targeting (FAT) homology domain. By knocking down CCM2 or CCM3 and rescuing with binding-deficient mutants, we establish that CCM2–CCM3 interactions protect CCM2 and CCM3 proteins from proteasomal degradation and show that both CCM2 and CCM3 are required for normal endothelial cell network formation. However, CCM3 expression in the absence of CCM2 is sufficient to support normal cell growth, revealing complex-independent roles for CCM3.

  7. CCM2–CCM3 interaction stabilizes their protein expression and permits endothelial network formation

    PubMed Central

    Draheim, Kyle M.; Li, Xiaofeng; Zhang, Rong; Fisher, Oriana S.; Villari, Giulia

    2015-01-01

    Mutations in the essential adaptor proteins CCM2 or CCM3 lead to cerebral cavernous malformations (CCM), vascular lesions that most frequently occur in the brain and are strongly associated with hemorrhagic stroke, seizures, and other neurological disorders. CCM2 binds CCM3, but the molecular basis of this interaction, and its functional significance, have not been elucidated. Here, we used x-ray crystallography and structure-guided mutagenesis to show that an α-helical LD-like motif within CCM2 binds the highly conserved “HP1” pocket of the CCM3 focal adhesion targeting (FAT) homology domain. By knocking down CCM2 or CCM3 and rescuing with binding-deficient mutants, we establish that CCM2–CCM3 interactions protect CCM2 and CCM3 proteins from proteasomal degradation and show that both CCM2 and CCM3 are required for normal endothelial cell network formation. However, CCM3 expression in the absence of CCM2 is sufficient to support normal cell growth, revealing complex-independent roles for CCM3. PMID:25825518

  8. Self-assembling SAS-6 multimer is a core centriole building block.

    PubMed

    Gopalakrishnan, Jayachandran; Guichard, Paul; Smith, Andrew H; Schwarz, Heinz; Agard, David A; Marco, Sergio; Avidor-Reiss, Tomer

    2010-03-19

    Centrioles are conserved microtubule-based organelles with 9-fold symmetry that are essential for cilia and mitotic spindle formation. A conserved structure at the onset of centriole assembly is a "cartwheel" with 9-fold radial symmetry and a central tubule in its core. It remains unclear how the cartwheel is formed. The conserved centriole protein, SAS-6, is a cartwheel component that functions early in centriole formation. Here, combining biochemistry and electron microscopy, we characterize SAS-6 and show that it self-assembles into stable tetramers, which serve as building blocks for the central tubule. These results suggest that SAS-6 self-assembly may be an initial step in the formation of the cartwheel that provides the 9-fold symmetry. Electron microscopy of centrosomes identified 25-nm central tubules with repeating subunits and show that SAS-6 concentrates at the core of the cartwheel. Recombinant and native SAS-6 self-oligomerizes into tetramers with approximately 6-nm subunits, and these tetramers are components of the centrosome, suggesting that tetramers are the building blocks of the central tubule. This is further supported by the observation that elevated levels of SAS-6 in Drosophila cells resulted in higher order structures resembling central tubule morphology. Finally, in the presence of embryonic extract, SAS-6 tetramers assembled into high density complexes, providing a starting point for the eventual in vitro reconstruction of centrioles.

  9. Formation of diffusion barrier coating on superalloy 690 substrate and its stability in borosilicate melt at elevated temperature

    NASA Astrophysics Data System (ADS)

    Dutta, R. S.; Yusufali, C.; Paul, B.; Majumdar, S.; Sengupta, P.; Mishra, R. K.; Kaushik, C. P.; Kshirsagar, R. J.; Kulkarni, U. D.; Dey, G. K.

    2013-01-01

    Aluminized and thermally oxidized superalloy 690 substrates forming Al2O3 layer on (NiCr)Al + Cr5Al8 types aluminides and bare substrates were exposed in sodium borosilicate melt at 1248 K for 192 h. SEM-EDXS analysis along the cross-section of bare substrate with adhered glass revealed formation of a continuous, thick Cr2O3 layer at the substrate/glass interface due to its low solubility in borosilicate melt. XRD on aluminide coated and thermally oxidized specimen revealed existence of Al2O3 along with NiAl and Cr5Al8 type phases after the exposure in borosilicate melt. SEM-EDXS analysis along the cross-section of aluminide coated and thermally oxidized sample with adhered glass indicated good stability of coating in borosilicate melt without any phase formation at the coating/glass interface. However, some Al enrichment in glass phase adjacent to interface was noticed without any significant Ni or Cr enrichment.

  10. Sol-gel reaction stability studied: Influence in the formation temperature and properties of ferroelectric thin films

    SciTech Connect

    Perez, J. Vilarinho, P.M.; Kholkin, A.L.; Almeida, A.

    2009-03-05

    Lead zirconium titanate (PZT) sol-gel solutions were prepared based on distilled lead acetate precursor solutions. A detailed analysis of the distillation effect on the lead precursor and the final PZT solution were carried out by Infrared and Raman techniques. It was found that the increase in the number of distillation steps experienced by the lead precursor solutions removes the constitutional water and increases the lead acetate-2-methoxyethanol interconnectivity; thus improving stability and avoiding the aging effect of the resulting PZT solutions. The thermal decomposition process of the PZT solutions was analyzed based on the thermogravimetric (TG) and differential thermogravimetric analysis (DTA) measurements. It was found that as the number of distillation steps in the lead precursor solutions increases, the decomposition rate increases and the formation temperature of pure perovskite PZT films decreases. X-ray diffraction (XRD) technique was used to study the film phase formation. A pure perovskite phase at 500 deg. C was found by the XRD analysis after the second distillation step. Scanning electron microscope technique was used to carry out the microstructural analysis. Dense microstructure was found in all analyzed films and an incipient columnar grain growth was revealed in PZT films prepared based on lead precursor solution with more than three distillation steps. The dependence of the dielectric, ferroelectric and piezoelectric properties on the number of distillation steps was revealed and a correlation between the distillation process, film microstructure properties and electrical performance was established.

  11. On the formation and stability of long-lived impurity-ion snakes in Alcator C-Mod

    NASA Astrophysics Data System (ADS)

    Delgado-Aparicio, L.; Sugiyama, L.; Granetz, R.; Gates, D.; Rice, J.; Reinke, M. L.; Bergerson, W.; Bitter, M.; Brower, D. L.; Fredrickson, E.; Gao, C.; Greenwald, M.; Hill, K.; Hubbard, A.; Irby, J.; Hughes, J. W.; Marmar, E.; Pablant, N.; Scott, S.; Wilson, R.; Wolfe, S.; Wukitch, S.

    2013-04-01

    Long-lived (1, 1) ‘snake’ modes were discovered nearly three decades ago, but basic questions regarding their formation, stability, and superb particle confinement—shown by surviving tens to hundreds of sawtooth cycles—have remained unanswered. High-resolution spectroscopic imaging diagnostics permit studies of heavy-impurity-ion snakes with unprecedented temporal and spatial resolution, making it possible to positively identify the SXR signals with specific ion charge states and to infer, for the first time, the perturbed impurity density, Zeff, and resistivity at the centre of these long-lived helical modes. The results show a new scenario for the formation of heavy-impurity-ion snakes, which can begin as a broad 1/1 kink asymmetry of the central impurity-ion density, that grows and undergoes a seamless transition to a large crescent-shaped helical island-like structure inside q < 1, with a regularly sawtoothing core. This type of formation departs strongly from the nonlinear island model based on a modified Rutherford equation proposed originally to describe the pellet-induced snakes and expanded further to account for the impurity effects (e.g. \\tilde{P}_rad and \\tilde{Z}_eff ). These new high-resolution observations show details of their evolution and the accompanying sawtooth oscillations that suggest important differences between the density and temperature dynamics, ruling out a purely pressure-driven process. Instead, many features arise naturally from nonlinear interactions in a 3D MHD model that separately evolves the plasma density and temperature.

  12. Formation and Fragmentation of Unsaturated Fatty Acid [M - 2H + Na]- Ions: Stabilized Carbanions for Charge-Directed Fragmentation

    NASA Astrophysics Data System (ADS)

    Thomas, Michael C.; Kirk, Benjamin B.; Altvater, Jens; Blanksby, Stephen J.; Nette, Geoffrey W.

    2013-12-01

    Fatty acids are long-chain carboxylic acids that readily produce [M - H]- ions upon negative ion electrospray ionization (ESI) and cationic complexes with alkali, alkaline earth, and transition metals in positive ion ESI. In contrast, only one anionic monomeric fatty acid-metal ion complex has been reported in the literature, namely [M - 2H + FeIICl]-. In this manuscript, we present two methods to form anionic unsaturated fatty acid-sodium ion complexes (i.e., [M - 2H + Na]-). We find that these ions may be generated efficiently by two distinct methods: (1) negative ion ESI of a methanolic solution containing the fatty acid and sodium fluoride forming an [M - H + NaF]- ion. Subsequent collision-induced dissociation (CID) results in the desired [M - 2H + Na]- ion via the neutral loss of HF. (2) Direct formation of the [M - 2H + Na]- ion by negative ion ESI of a methanolic solution containing the fatty acid and sodium hydroxide or bicarbonate. In addition to deprotonation of the carboxylic acid moiety, formation of [M - 2H + Na]- ions requires the removal of a proton from the fatty acid acyl chain. We propose that this deprotonation occurs at the bis-allylic position(s) of polyunsaturated fatty acids resulting in the formation of a resonance-stabilized carbanion. This proposal is supported by ab initio calculations, which reveal that removal of a proton from the bis-allylic position, followed by neutral loss of HX (where X = F- and -OH), is the lowest energy dissociation pathway.

  13. Formation of supramolecular hydrogels with controlled microstructures and stability via molecular assembling in a two-component system.

    PubMed

    Wu, Jiwei; Tang, Liming; Chen, Kai; Yan, Liang; Li, Fei; Wang, Yujiang

    2007-03-01

    Two isomeric building units, 4-oxo-4-(2-pyridinylamino) butanoic acid (defined as G1) and 4-oxo-4-(3-pyridinylamino) butanoic acid (defined as G2) formed fiber- and tree-like crystals in aqueous solutions, respectively. The crystal formation process of G1 was suggested based on the layered cross section of an individual crystal and the single crystal structure. Through cooling the aqueous solutions of their mixtures under G1/G2 molar ratios ranged from 7/1 to 1/3, a series of supramolecular hydrogels were formed based on hydrogen bonds as the main driving force. As decreasing G1/G2 ratios, the first observed aggregates in solution changed from fiber to particle form, while the gelating time became longer and longer. At the collapsing temperature, the gels formed at G1/G2 ratio 3/1 kept the original gel shape but released water, while at G1/G2 ratio 2/1 they broke into pieces without releasing water. The "dropping ball" experiment indicated that the highest gel-to-sol dissociation temperature (T(gel)) is obtained at G1/G2 ratio of 2/1. As measured by UV-vis spectroscopy, the two building units distributed uniformly within the gel formed at G1/G2 ratio of 1/1, indicating they assembled together in forming hydrogel. The scanning electron microscope (SEM) and infrared spectrometer (FT-IR) analysis of the dried samples indicated that the backbone shape changed from fiber to sheet and the content of free carboxyl groups increased with decreasing G1/G2 ratios, therefore resulting in hydrogels with different stability. The simple gelator structures and the possibility in controlling gel structure and stability make the hydrogels suitable for various uses.

  14. Copper stabilization via spinel formation during the sintering of simulated copper-laden sludge with aluminum-rich ceramic precursors.

    PubMed

    Tang, Yuanyuan; Chui, Stephen Sin-Yin; Shih, Kaimin; Zhang, Lingru

    2011-04-15

    The feasibility of incorporating copper-laden sludge into low-cost ceramic products, such as construction ceramics, was investigated by sintering simulated copper-laden sludge with four aluminum-rich ceramic precursors. The results indicated that all of these precursors (γ-Al(2)O(3), corundum, kaolinite, mullite) could crystallochemically stabilize the hazardous copper in the more durable copper aluminate spinel (CuAl(2)O(4)) structure. To simulate the process of copper transformation into a spinel structure, CuO was mixed with the four aluminum-rich precursors, and fired at 650-1150 °C for 3 h. The products were examined using powder X-ray diffraction (XRD) and scanning electron microscopic techniques. The efficiency of copper transformation among crystalline phases was quantitatively determined through Rietveld refinement analysis of the XRD data. The sintering experiment revealed that the optimal sintering temperature for CuAl(2)O(4) formation was around 1000 °C and that the efficiency of copper incorporation into the crystalline CuAl(2)O(4) structure after 3 h of sintering ranged from 40 to 95%, depending on the type of aluminum precursor used. Prolonged leaching tests were carried out by using acetic acid with an initial pH value of 2.9 to leach CuO and CuAl(2)O(4) samples for 22 d. The sample leachability analysis revealed that the CuAl(2)O(4) spinel structure was more superior to stabilize copper, and suggested a promising and reliable technique for incorporating copper-laden sludge or its incineration ash into usable ceramic products. Such results also demonstrated the potential of a waste-to-resource strategy by using waste materials as part of the raw materials with the attainable temperature range used in the production of ceramics.

  15. Folding Landscape of Mutant Huntingtin Exon1: Diffusible Multimers, Oligomers and Fibrils, and No Detectable Monomer

    PubMed Central

    Sahoo, Bankanidhi; Arduini, Irene; Drombosky, Kenneth W.; Kodali, Ravindra; Sanders, Laurie H.; Greenamyre, J. Timothy; Wetzel, Ronald

    2016-01-01

    Expansion of the polyglutamine (polyQ) track of the Huntingtin (HTT) protein above 36 is associated with a sharply enhanced risk of Huntington’s disease (HD). Although there is general agreement that HTT toxicity resides primarily in N-terminal fragments such as the HTT exon1 protein, there is no consensus on the nature of the physical states of HTT exon1 that are induced by polyQ expansion, nor on which of these states might be responsible for toxicity. One hypothesis is that polyQ expansion induces an alternative, toxic conformation in the HTT exon1 monomer. Alternative hypotheses posit that the toxic species is one of several possible aggregated states. Defining the nature of the toxic species is particularly challenging because of facile interconversion between physical states as well as challenges to identifying these states, especially in vivo. Here we describe the use of fluorescence correlation spectroscopy (FCS) to characterize the detailed time and repeat length dependent self-association of HTT exon1-like fragments both with chemically synthesized peptides in vitro and with cell-produced proteins in extracts and in living cells. We find that, in vitro, mutant HTT exon1 peptides engage in polyQ repeat length dependent dimer and tetramer formation, followed by time dependent formation of diffusible spherical and fibrillar oligomers and finally by larger, sedimentable amyloid fibrils. For expanded polyQ HTT exon1 expressed in PC12 cells, monomers are absent, with tetramers being the smallest molecular form detected, followed in the incubation time course by small, diffusible aggregates at 6–9 hours and larger, sedimentable aggregates that begin to build up at 12 hrs. In these cell cultures, significant nuclear DNA damage appears by 6 hours, followed at later times by caspase 3 induction, mitochondrial dysfunction, and cell death. Our data thus defines limits on the sizes and concentrations of different physical states of HTT exon1 along the reaction

  16. Formation of H2-He substellar bodies in cold conditions. Gravitational stability of binary mixtures in a phase transition

    NASA Astrophysics Data System (ADS)

    Füglistaler, A.; Pfenniger, D.

    2016-06-01

    Context. Molecular clouds typically consist of 3/4 H2, 1/4 He and traces of heavier elements. In an earlier work we showed that at very low temperatures and high densities, H2 can be in a phase transition leading to the formation of ice clumps as large as comets or even planets. However, He has very different chemical properties and no phase transition is expected before H2 in dense interstellar medium conditions. The gravitational stability of fluid mixtures has been studied before, but these studies did not include a phase transition. Aims: We study the gravitational stability of binary fluid mixtures with special emphasis on when one component is in a phase transition. The numerical results are aimed at applications in molecular cloud conditions, but the theoretical results are more general. Methods: First, we study the gravitational stability of van der Waals fluid mixtures using linearized analysis and examine virial equilibrium conditions using the Lennard-Jones intermolecular potential. Then, combining the Lennard-Jones and gravitational potentials, the non-linear dynamics of fluid mixtures are studied via computer simulations using the molecular dynamics code LAMMPS. Results: Along with the classical, ideal-gas Jeans instability criterion, a fluid mixture is always gravitationally unstable if it is in a phase transition because compression does not increase pressure. However, the condensed phase fraction increases. In unstable situations the species can separate: in some conditions He precipitates faster than H2, while in other conditions the converse occurs. Also, for an initial gas phase collapse the geometry is essential. Contrary to spherical or filamentary collapses, sheet-like collapses starting below 15 K easily reach H2 condensation conditions because then they are fastest and both the increase of heating and opacity are limited. Conclusions: Depending on density, temperature and mass, either rocky H2 planetoids, or gaseous He planetoids form. H2

  17. Formation of a Stabilized Cysteine Sulfinic Acid Is Critical for the Mitochondrial Function of the Parkinsonism Protein DJ-1*

    PubMed Central

    Blackinton, Jeff; Lakshminarasimhan, Mahadevan; Thomas, Kelly J.; Ahmad, Rili; Greggio, Elisa; Raza, Ashraf S.; Cookson, Mark R.; Wilson, Mark A.

    2009-01-01

    The formation of cysteine-sulfinic acid has recently become appreciated as a modification that links protein function to cellular oxidative status. Human DJ-1, a protein associated with inherited parkinsonism, readily forms cysteine-sulfinic acid at a conserved cysteine residue (Cys106 in human DJ-1). Mutation of Cys106 causes the protein to lose its normal protective function in cell culture and model organisms. However, it is unknown whether the loss of DJ-1 protective function in these mutants is due to the absence of Cys106 oxidation or the absence of the cysteine residue itself. To address this question, we designed a series of substitutions at a proximal glutamic acid residue (Glu18) in human DJ-1 that alter the oxidative propensity of Cys106 through changes in hydrogen bonding. We show that two mutations, E18N and E18Q, allow Cys106 to be oxidized to Cys106-sulfinic acid under mild conditions. In contrast, the E18D mutation stabilizes a cysteine-sulfenic acid that is readily reduced to the thiol in solution and in vivo. We show that E18N and E18Q can both partially substitute for wild-type DJ-1 using mitochondrial fission and cell viability assays. In contrast, the oxidatively impaired E18D mutant behaves as an inactive C106A mutant and fails to protect cells. We therefore conclude that formation of Cys106-sulfinic acid is a key modification that regulates the protective function of DJ-1. PMID:19124468

  18. Foam-stabilizing effects and cling formation patterns of iso-alpha-acids and reduced iso-alpha-acids in lager beer.

    PubMed

    Kunimune, Takeshi; Shellhammer, Thomas H

    2008-09-24

    Foam-stabilizing properties and cling formation patterns of iso-alpha-acids and reduced iso-alpha-acids were investigated using an unhopped lager beer. Unhopped beer was dosed with iso-alpha-acid (Iso), rho-iso-alpha-acid (Rho), tetrahydro-iso-alpha-acid (Tetra), and hexahydro-iso-alpha-acid (Hexa), separately, over a range of concentrations from 2 to 10 ppm. A uniform foam was created by Inpack 2000 Flasher Head and was measured by a NIBEM Foam Stability Tester (NIBEM-TPH) followed by a NIBEM Cling Meter (NIBEM-CLM) to determine the relationship between the concentration and NIBEM-30 and the cling formation ability of each compound. The foam-stabilizing power was determined to be Tetra, Hexa, Iso, and Rho from the strongest to weakest. Linear regression models were created using the NIBEM-TPH data set, and on the basis of 95% confidence intervals, the foam stability of Tetra or Hexa became significantly larger than that of Iso when 2.4 or 4.2 ppm of Tetra or Hexa was used as a replacement for Iso, respectively. Cling formation patterns could be categorized into three groups: "ring", "mesh", and "powdery". The control beer had the lowest foam stability and did not yield any foam cling.

  19. Effects of biodegradable plastics on the predominant culturable bacteria associated with soil aggregate formation and stability after 9 months of incubation in natural soil

    Technology Transfer Automated Retrieval System (TEKTRAN)

    An in vitro study of the effects of biodegradable plastics on the predominant soil aggregating bacteria associated to soil aggregate formation and stability after 9 months of incubation in soil. Caesar-TonThat TC, Fukui R*, Caesar AJ., Lartey, RT, and Gaskin, JF. USDA-Agricultural Research Service, ...

  20. The identification of goat peroxiredoxin-5 and the evaluation and enhancement of its stability by nanoparticle formation

    NASA Astrophysics Data System (ADS)

    Feng, Xiaozhou; Liu, Juanjuan; Fan, Shuai; Liu, Fan; Li, Yadong; Jin, Yuanyuan; Bai, Liping; Yang, Zhaoyong

    2016-04-01

    An anticancer bioactive peptide (ACBP), goat peroxiredoxin-5 (gPRDX5), was identified from goat-spleen extract after immunizing the goat with gastric cancer-cell lysate. Its amino acid sequence was determined by employing 2D nano-LC-ESI-LTQ-Orbitrap MS/MS combined with Mascot database search in the goat subset of the Uniprot database. The recombinant gPRDX5 protein was acquired by heterogeneous expression in Escherichia coli. Subsequently, the anti-cancer bioactivity of the peptide was measured by several kinds of tumor cells. The results indicated that the gPRDX5 was a good anti-cancer candidate, especially for killing B16 cells. However, the peptide was found to be unstable without modification with pharmaceutical excipients, which would be a hurdle for future medicinal application. In order to overcome this problem and find an effective way to evaluate the gPRDX5, nanoparticle formation, which has been widely used in drug delivery because of its steadiness in application, less side-effects and enhancement of drug accumulation in target issues, was used here to address the issues. In this work, the gPRDX5 was dispersed into nanoparticles before delivered to B16 cells. By the nanotechnological method, the gPRDX5 was stabilized by a fast and accurate procedure, which suggests a promising way for screening the peptide for further possible medicinal applications.

  1. The heat of formation of chlorine-isocyanate and the relative stability of isoelectronic molecules: an experimental and theoretical study.

    PubMed

    Ji, Yuanyuan; Bobadova-Parvanova, Petia; Larson, Chris; Samartzis, Peter C; Morokuma, Keiji; Lin, Jim Jr-Min; Ching, Tao-Tsung; Chaudhuri, Chanchal; Lee, Shih-Huang; Wodtke, Alec M

    2006-06-28

    Accurate thermochemical data of small molecules are invaluable to the progress of every aspect of chemistry, especially in the atmosphere, combustion and industry. In this work, photofragmentation translational spectroscopy and 1st principles electronic structure theory reveal the literature value of the heat of formation of chlorine-isocyanate to be in error by more than 40 kcalmol. We report a revised experimental value for D0(Cl-NCO) = 51+/-3 kcal/mol which leads to a Delta Hf (ClNCO) = 8.5+/-3 kcal/mol. High level ab initio (CCSD(T)) electronic structure calculations extrapolated to the complete basis set limit give D0(Cl-NCO) = 6.3 kcal/mol, in good agreement with experiment. In light of the present results, the destabilization of azides relative to isoelectronic isocyanates has been evaluated empirically for three pairs of related molecules. It is found to be 90-110 kcal/mol, and has been attributed mainly to the weakening of the N-NN bond relative to the N-CO bond. Electronic structure calculations employing decomposition analysis suggest that, compared to homopolar N2, the (+delta)CO(-delta) pi polarity provides better orbital interaction (charge transfer) and electrostatic attraction and results in a closer encounter and larger stabilization between the fragments and that this is the origin of isoelectronic destabilization of azides relative to the isocyanates.

  2. Label-free fluorescent sensor for lead ion detection based on lead(II)-stabilized G-quadruplex formation.

    PubMed

    Zhan, Shenshan; Wu, Yuangen; Luo, Yanfang; Liu, Le; He, Lan; Xing, Haibo; Zhou, Pei

    2014-10-01

    A label-free fluorescent DNA sensor for the detection of lead ions (Pb(2+)) based on lead(II)-stabilized G-quadruplex formation is proposed in this article. A guanine (G)-rich oligonucleotide, T30695, was used as a recognition probe, and a DNA intercalator, SYBR Green I (SG), was used as a signal reporter. In the absence of Pb(2+), the SG intercalated with the single-stranded random-coil T30695 and emitted strong fluorescence. While in the presence of Pb(2+), the random-coil T30695 would fold into a G-quadruplex structure and the SG could barely show weak fluorescence, and the fluorescence intensity was inversely proportional to the involving amount of Pb(2+). Based on this, a selective lead ion sensor with a limit of detection of 3.79 ppb (parts per billion) and a detection range from 0 to 600 ppb was constructed. Because detection for real samples was also demonstrated to be reliable, this simple, low-cost, sensitive, and selective sensor holds good potential for Pb(2+) detection in real environmental samples.

  3. The identification of goat peroxiredoxin-5 and the evaluation and enhancement of its stability by nanoparticle formation

    PubMed Central

    Feng, Xiaozhou; Liu, Juanjuan; Fan, Shuai; Liu, Fan; Li, Yadong; Jin, Yuanyuan; Bai, Liping; Yang, Zhaoyong

    2016-01-01

    An anticancer bioactive peptide (ACBP), goat peroxiredoxin-5 (gPRDX5), was identified from goat-spleen extract after immunizing the goat with gastric cancer-cell lysate. Its amino acid sequence was determined by employing 2D nano-LC-ESI-LTQ-Orbitrap MS/MS combined with Mascot database search in the goat subset of the Uniprot database. The recombinant gPRDX5 protein was acquired by heterogeneous expression in Escherichia coli. Subsequently, the anti-cancer bioactivity of the peptide was measured by several kinds of tumor cells. The results indicated that the gPRDX5 was a good anti-cancer candidate, especially for killing B16 cells. However, the peptide was found to be unstable without modification with pharmaceutical excipients, which would be a hurdle for future medicinal application. In order to overcome this problem and find an effective way to evaluate the gPRDX5, nanoparticle formation, which has been widely used in drug delivery because of its steadiness in application, less side-effects and enhancement of drug accumulation in target issues, was used here to address the issues. In this work, the gPRDX5 was dispersed into nanoparticles before delivered to B16 cells. By the nanotechnological method, the gPRDX5 was stabilized by a fast and accurate procedure, which suggests a promising way for screening the peptide for further possible medicinal applications. PMID:27074889

  4. Influence of calcium, magnesium, or potassium ions on the formation and stability of emulsions prepared using highly hydrolyzed whey proteins.

    PubMed

    Ramkumar, C; Singh, H; Munro, P A; Singh, A M

    2000-05-01

    Oil-in-water emulsions (4 wt % soy oil) containing 4 wt % whey protein hydrolysate (WPH) (27% degree of hydrolysis) and different levels of calcium, magnesium, or potassium chloride were prepared in a two-stage homogenizer. Other emulsions containing 4 wt % WPH but including 0.35 wt % hydroxylated lecithin and different levels of the above minerals were similarly prepared. The formation and stability of these emulsions were determined by measuring oil droplet size distributions using laser light scattering and by confocal scanning laser microscopy and a gravity creaming test. Both lecithin-free and lecithin-containing emulsions showed no change in droplet size distributions with increasing concentration of potassium in the range 0-37.5 mM. In contrast, the diameter of emulsion droplets increased with increasing calcium or magnesium concentration >12.5 mM. Emulsions containing hydroxylated lecithin were more sensitive to the addition of calcium or magnesium than the lecithin-free emulsions. Storage of emulsions at 20 degrees C for 24 h further increased the diameter of droplets and resulted in extensive creaming in emulsions containing >25 mM calcium or magnesium. It appears that both flocculation and coalescence processes were involved in the destabilization of emulsions induced by the addition of divalent cations.

  5. Chitosan-mediated formation of biomimetic silica nanoparticles: an effective method for manganese peroxidase immobilization and stabilization.

    PubMed

    Luan, Pan-Pan; Jiang, Yan-Jun; Zhang, Song-Ping; Gao, Jing; Su, Zhi-Guo; Ma, Guang-Hui; Zhang, Yu-Fei

    2014-11-01

    Our work here, for the first time, reported the use of chitosan-mediated biomimetic silica nanoparticles in enzyme immobilization. In order to make clear the relationship among silicification process, silica nanoparticle structure and immobilized enzyme activity, a mechanism of chitosan-mediated silicification using sodium silicate as the silica source was primarily evaluated. Chitosan was demonstrated effectively to promote the silicification not only in accelerating the aggregation rate of sodium silicate, but also in templating the formation of silica nanoparticles. Although the whole biomimetic silicification process contained polycondensation-aggregation-precipitation three stages, the elemental unit in precipitated silica was confirmed to be nanoparticles with 100 nm diameter regardless of the chitosan and silicate concentration used. Furthermore, the effect of enzyme on silicification process was also investigated. The introducing of manganese peroxidase (MnP) to silica precursor solution had no obvious effect on the silicification rate and nanoparticle morphology. The residual activity and embedding rate of immobilized MnP were 64.2% and 36.4% respectively under the optimum conditions. In addition, compared to native MnP, the MnP embedded in chitosan/silica nanoparticles exhibited improved stability against organic solvent and ultrasonic wave. After ultrasonic treatment for 20 min, 77% of the initial activity was remained due to the protective effect of chitosan/silica nanoparticles, while native MnP lost almost all of its original activity.

  6. Imagens do céu ontem e hoje - um multimídia interativo de astronomia e uma nova exposição no MAST

    NASA Astrophysics Data System (ADS)

    Caretta, C. A.; Lima, F. P.; Requeijo, F.; Vieira, G. G.; Alves, F.; Valente, M. E. A.; de Almeida, R.; de Garcia, G. C.; Quixadá, A. C.

    2003-08-01

    "Imagens do Céu Ontem e Hoje" é o título de uma nova exposição que está sendo inaugurada no Museu de Astronomia e Ciências Afins (MCT), que inclui experimentos interativos, maquetes, réplicas e 8 terminais de computador com um multimídia interativo sobre Astronomia para consulta dos visitantes. O multimídia apresenta um conteúdo bastante extenso, que engloba quase todos os temas em Astronomia, consistindo numa fonte de divulgação e pesquisa para um público que vai das crianças até estudantes universitários. O conteúdo está distribuído em mais de 500 páginas de texto divididas em 4 módulos: "O Universo", "Espectroscopia", "Telescópios" e "Observando o Céu". Cada módulo é subdividido em 5 seções, em média, cada uma iniciada por uma animação que ilustra os temas a serem abordados na seção. Ao final da animação, uma lista de temas é apresentada sob o título "Saiba Mais". Para exemplificar, o módulo "O Universo" contém as seguintes seções: "O Universo visto pelo homem", "Conhecendo o Sistema Solar", "Indo além do Sistema Solar", "Nossa Galáxia, a Via-Láctea" e "Indo mais além, a imensidão do Universo". A seção "Conhecendo o Sistema Solar", por sua vez, tem os seguintes temas: "A origem do Sistema Solar", "O Sol", "Os planetas", "Satélites, asteróides, cometas e outros bichos..." e "O Sistema Solar em números". Cada texto é repleto de imagens, quadros, desenhos, esquemas, etc, além de passatempos ao final de cada seção, incluindo jogos interativos, quadrinhos e curiosidades, que auxiliam o aprendizado de forma divertida. Apresentamos neste trabalho as idéias gerais que permearam a produção da exposição, e uma viagem pelo multimídia para exemplificar sua estrutura e conteúdo. O multimídia será posteriormente disponibilizado para o público externo pela página eletrônica do MAst e/ou por intermédio de uma publicação comercial.

  7. Effect of 5-methylcytosine on the structure and stability of DNA. Formation of triple-stranded concatenamers by overlapping oligonucleotides.

    PubMed

    Xodo, L E; Alunni-Fabbroni, M; Manzini, G

    1994-02-01

    A triple helix can be formed upon binding of a pyrimidine oligonucleotide to the major groove of a homopurine-homopyrimidine (R.Y) double-stranded DNA target site. Here, we report that this reaction can be influenced by base methylation. The pyrimidine strand 5'-TmCTmCTmCTmCTTmCT (mY12), whose cytosine residues are methylated at C5, does not bind the duplex 5'-AGAGAGAGAAGA.3'-TCTCTCTCTTCT (R12.Y12) to yield a 12-triad triplex, as would be expected from these DNA sequences. Rather, a complex of overlapping oligonucleotides, which we define concatenamer, is formed. The concatenamer is clearly evidenced by polyacrylamide gel electrophoresis (PAGE) since it migrates with a smeared band of very low mobility. The stoichiometry of the concatenamer, determined by both UV mixing curves and electrophoresis, is surprisingly found to be (R12.2mY12)n, thus showing that the unmethylated Y12 strand is excluded from the complex. Denaturation experiments performed by ultraviolet absorbance (UV) and differential scanning calorimetry (DSC) show that the concatenamers melt with a single and highly cooperative transition whose Tm strongly depends on pH. Overall, the data point to the conclusion that the concatenamers are in triple helix, where the methylated mY12 strand is engaged in both Watson-Crick and Hoogsteen base pairings, thus displacing the Y12 strand from the R12.Y12 duplex. A possible mechanism of concatenamer formation is proposed. The results presented in this paper show that 5-methylcytosine brings about a strong stabilizing effect on both double and triple DNA helices, and that pyrimidine oligonucleotides containing 5-methylcytosine can displace from R.Y duplexes the analogous non-methylated strand. The advantage of using methylated oligonucleotides in antisense technology is discussed.

  8. Evaluation of the geological relationships to gas hydrate formation and stability. Second annual technical progress report, October 1, 1985--September 30, 1986

    SciTech Connect

    Not Available

    1986-12-31

    Although there are many publications pertaining to gas hydrates, their formation and stability in various geological conditions are poorly known. Therefore, for the same reasons and because of the very broad scope of our research, limited amount and extremely dispersed information, the study regions are very large. Moreover, almost without exception the geological environments controlling gas hydrates formation and stability of the studied regions are very complex. The regions studied (completed and partially completed - total 17 locations) during the reporting period, particularly the Gulf of Mexico and the Middle America Trench, are the most important in this entire research project. In the past, both of these regions have been extensively studied, the presence of gas hydrates confirmed and samples recovered. In our investigation it was necessary not only to review all previous data and interpretations, but to do a thorough analysis of the basins, and a critical evaluation of an previously reported and publicly available but not published information.

  9. Inhibition of Tongue Coat and Dental Plaque Formation by Stabilized Chlorine Dioxide Vs Chlorhexidine Mouthrinse: A Randomized, Triple Blinded Study

    PubMed Central

    Kini, Vineet Vaman; Padhye, Ashvini

    2015-01-01

    Background Chlorine dioxide (ClO2) is an oxidizing agent with known bactericidal, viricidal and fungicidal properties. Its efficacy in reducing the halitosis has been established by previous literature. However, data evaluating its antiplaque property is scarce. Chlorhexidine (CHX) is considered as the gold standard and an effective adjunctive to mechanical plaque removal. However, it is associated with few reversible side effects. Therefore a study was conducted to assess the antiplaque property of ClO2 containing mouthrinse against CHX mouthrinse. Aims and Objectives To evaluate the efficacy of stabilized chlorine dioxide containing mouthrinse and CHX containing mouthrinse in inhibition of tongue coat accumulation and dental plaque formation using a four day plaque regrowth model clinically and microbiologically in a healthy dental cohort. Materials and Methods A Single Center, Randomized, Triple blinded, Microbiological clinical trial was conducted involving 25 healthy dental students volunteers (11 males, 14 females). Two commercially available mouthrinse: Mouthrinse A – Aqueous based ClO2 mouthrinse Freshchlor® and Mouthrinse B - Aqueous based 0.2% CHX mouthrinse Hexidine® were selected as the test products. Subjects were asked to rinse and gargle for 1 minute with the allocated mouthrinse under supervision after supragingival scaling, polishing and tongue coat removal. After four hours, smears were taken from the buccal mucosa and tooth surface. On the fifth day from baseline of four day non brushing plaque regrowth model the samples were again taken from buccal mucosa and tooth surface followed by recording of plaque scores by Rastogi Modification of Navy Plaque index, extent of tongue coat by Winkel’s tongue coating index and measuring tongue coat wet weight in grams. The samples collected were subjected to microbial analysis and the results were expressed as colony forming units (CFUs) per sample. Statistical Analysis The Data was analysed using SPSS

  10. Formation of Pickering emulsions stabilized via interaction between nanoparticles dispersed in aqueous phase and polymer end groups dissolved in oil phase.

    PubMed

    Okada, Masahiro; Maeda, Hayata; Fujii, Syuji; Nakamura, Yoshinobu; Furuzono, Tsutomu

    2012-06-26

    The influence of end groups of a polymer dissolved in an oil phase on the formation of a Pickering-type hydroxyapatite (HAp) nanoparticle-stabilized emulsion and on the morphology of HAp nanoparticle-coated microspheres prepared by evaporating solvent from the emulsion was investigated. Polystyrene (PS) molecules with varying end groups and molecular weights were used as model polymers. Although HAp nanoparticles alone could not function as a particulate emulsifier for stabilizing dichloromethane (oil) droplets, oil droplets could be stabilized with the aid of carboxyl end groups of the polymers dissolved in the oil phase. Lower-molecular-weight PS molecules containing carboxyl end groups formed small droplets and deflated microspheres, due to the higher concentration of carboxyl groups on the droplet/microsphere surface and hence stronger adsorption of the nanoparticles at the water/oil interface. In addition, Pickering-type suspension polymerization of styrene droplets stabilized by PS molecules containing carboxyl end groups successfully led to the formation of spherical HAp-coated microspheres.

  11. Evaluation of three different formats of a neutralizing single chain human antibody against toxin Cn2: neutralization capacity versus thermodynamic stability.

    PubMed

    Quintero-Hernández, Veronica; Del Pozo-Yauner, Luis; Pedraza-Escalona, Martha; Juárez-González, Victor R; Alcántara-Recillas, Israel; Possani, Lourival D; Becerril, Baltazar

    2012-04-30

    The single-chain antibody fragment (scFv) 6009F, obtained by directed evolution, neutralizes the effects of the Cn2 toxin, which is the major toxic component of Centruroides noxius scorpion venom. In this work we compared the neutralization capacity and the thermodynamic stability of scFv 6009F with those of two other derived formats: Fab 6009F and diabody 6009F. Additionally, the affinity constants to Cn2 toxin of the three recombinant antibody fragments were determined by means of BIAcore. We found a correlation between the thermodynamic stability of these antibody fragments with their neutralization capacity. The order of thermodynamic stability determined was Fab≫scFv>diabody. The Fab and scFv were capable of neutralizing the toxic effects of Cn2 and whole venom but the diabody was unable to fully neutralize intoxication. In silico analysis of the diabody format indicates that the reduction of stability and neutralization capacity could be explained by a less cooperative interface between the heavy and the light variable domains.

  12. Presentation of the Multimédia Game "Geolover" Concept, to Educational Enchancement of the Geolocical Heritage of the Following Regions: "Ilha do Fogo" (Cabo-Verde), Seridó (Brasil), Sabugal (Portugal) and Açores (Portugal)

    NASA Astrophysics Data System (ADS)

    Cabral, João; Gomes, Ana; Alfama, Vera; Oliveira, Sirlene; Pinharandas, Carlos; Fonseca, Pedro; Campos, José; Nobre, José

    2013-04-01

    "Geolover" - Presentation of the multimédia game concept, to educational enchancement of the geolocical heritage of the following regions: : "Ilha do Fogo" (Cabo-Verde), Seridó (Brasil), Sabugal and Açores (Portugal). "Geolover" is a multitouch game, played by four players simultaneously, identified by 4 mascots and using as sceneries, the four regions landscapes, aimed to the young people with ages between 8 and 12 years old. The main objective is value the geological heritage of the Ilha do Fogo (Cabo Verde), Seridó in State of Rio Grande do Norte (Brasil) , Sabugal in Beira Alta province (Portugal) and Arquipélago dos Açores (Portuguese autonomous region). These regions have a great geological heritage like volcanology, plutonic rocks, sedimentar formations, metamorphic, paleontologic, mineralogic, geomorphologic, hydric and mining resources. Such heritage is being used in the different regions has base of studies to senior scientists and were used to great scientific researches. The diversified and distinguished cultural heritage of these four regions is referenced and it's a value to the union of the students from these three continents, with the Portuguese language as communication tool. The variety of the geological wealth and cultural of these regions, results in the common objective of their valuing like Geoparks. His creation on these three regions is a strategy with a great relevance to the socio-economic development. With the creation of this game, we promote the union of these 3 countries from these three continents, the universal values of the heritage richness that are offered by our planet.

  13. H-treatment impact on conductive-filament formation and stability in Ta{sub 2}O{sub 5}-based resistive-switching memory cells

    SciTech Connect

    Goux, L. Redolfi, A.; Jurczak, M.; Kim, J. Y.; Magyari-Kope, B.; Nishi, Y.

    2015-03-28

    In this article, we evidence the lower formation energy and improved stability of the conductive filament (CF) formed in TiN\\Ta{sub 2}O{sub 5}\\Ta resistive-switching memory cells treated in NH{sub 3} atmosphere at 400 °C. This annealing treatment results in (i) lower forming voltage, (ii) lower CF resistance, and (iii) longer retention lifetime of the oxygen-vacancy (V{sub o}) chain constituting the CF. Atomistic insights into these processes are provided by ab initio calculations performed for hydrogen (H) species incorporated in non-stoichiometric Ta{sub 2}O{sub 5} supercells: (i) V{sub o} formation energy is reduced by the presence of H, (ii) V{sub o}-chain CF conductivity is increased by V{sub o} + OH complex formation, and (iii) V{sub o}-chain retention is strengthened by the stable V{sub o} + OH complex. As a result, efficient CF formation and excellent state stability are obtained after 15 days at 250 °C.

  14. Synthesis, properties and formation of (RCp)Co- and (RCp)Rh-stabilized[4.8]3cyclacene derivatives.

    PubMed

    Kornmayer, Stefan C; Hellbach, Björn; Rominger, Frank; Gleiter, Rolf

    2009-01-01

    Metal-stabilized belts: A torus, 3, consisting of three four- and three eight-membered conjugated rings and stabilized by (RCp)Co- and (RCp)Rh- units, was generated by irradiation of [(RCp)Co(CO)(2)] and [(RCp)Rh(C(2)H(4))(2)], respectively, and 1.Eleven metal stabilized [4.8](3)cyclacene derivatives were synthesized. The substances were prepared in one-pot reactions by irradiation of a solution of 5,6,11,12-tetradehydro-dibenzo[a,e]cyclooctatetraene and the corresponding cobalt reagents or rhodium compounds. The resulting cyclacene derivatives reveal D(3h) symmetry in solution. In the solid state the hoop shaped systems crystallize in layers, which are intercalated with solvent layers. To unravel the mechanism of the one-pot reaction we isolated an intermediate, which shows almost planar cyclooctatetraene rings.

  15. Formation and stabilization of the telomeric antiparallel G-quadruplex and inhibition of telomerase by novel benzothioxanthene derivatives with anti-tumor activity

    NASA Astrophysics Data System (ADS)

    Zhang, Wen; Chen, Min; Ling Wu, Yan; Tanaka, Yoshimasa; Juan Ji, Yan; Lin Zhang, Su; He Wei, Chuan; Xu, Yan

    2015-09-01

    G-quadruplexes formed in telomeric DNA sequences at human chromosome ends can be a novel target for the development of therapeutics for the treatment of cancer patients. Herein, we examined the ability of six novel benzothioxanthene derivatives S1-S6 to induce the formation of and stabilize an antiparallel G-quadruplex by EMSA, UV-melting and CD techniques and the influence of S1-S6 on A549 and SGC7901 cells through real-time cell analysis, wound healing, trap assay methods. Results show that six compounds could differentially induce 26 nt G-rich oligonucleotides to form the G-quadruplex with high selectivity vs C-rich DNA, mutated DNA and double-stranded DNA, stabilize it with high affinity, promote apoptosis and inhibit mobility and telomerase activity of A549 cells and SGC7901 cells. Especially, S1, S3, S4 displayed stronger abilities, of which S3 was the most optimal with the maximum ΔTm value being up to 29.8 °C for G-quadruplex, the minimum IC50 value being 0.53 μM and the maximum cell inhibitory rate being up to 97.2%. This study suggests that this type of compounds that induce the formation of and stabilize the telomeric antiparallel G-quadruplex, and consequently inhibit telomerase activity, leading to cell apoptosis, can be screened for the discovery of novel antitumor therapeutics.

  16. The coupling between stability and ion pair formation in magnesium electrolytes from first-principles quantum mechanics and classical molecular dynamics.

    PubMed

    Rajput, Nav Nidhi; Qu, Xiaohui; Sa, Niya; Burrell, Anthony K; Persson, Kristin A

    2015-03-11

    In this work we uncover a novel effect between concentration dependent ion pair formation and anion stability at reducing potentials, e.g., at the metal anode. Through comprehensive calculations using both first-principles as well as well-benchmarked classical molecular dynamics over a matrix of electrolytes, covering solvents and salt anions with a broad range in chemistry, we elucidate systematic correlations between molecular level interactions and composite electrolyte properties, such as electrochemical stability, solvation structure, and dynamics. We find that Mg electrolytes are highly prone to ion pair formation, even at modest concentrations, for a wide range of solvents with different dielectric constants, which have implications for dynamics as well as charge transfer. Specifically, we observe that, at Mg metal potentials, the ion pair undergoes partial reduction at the Mg cation center (Mg(2+) → Mg(+)), which competes with the charge transfer mechanism and can activate the anion to render it susceptible to decomposition. Specifically, TFSI(-) exhibits a significant bond weakening while paired with the transient, partially reduced Mg(+). In contrast, BH4(-) and BF4(-) are shown to be chemically stable in a reduced ion pair configuration. Furthermore, we observe that higher order glymes as well as DMSO improve the solubility of Mg salts, but only the longer glyme chains reduce the dynamics of the ions in solution. This information provides critical design metrics for future electrolytes as it elucidates a close connection between bulk solvation and cathodic stability as well as the dynamics of the salt.

  17. Data analysis as a source of variability of the HLA-peptide multimer assay: from manual gating to automated recognition of cell clusters.

    PubMed

    Gouttefangeas, Cécile; Chan, Cliburn; Attig, Sebastian; Køllgaard, Tania T; Rammensee, Hans-Georg; Stevanović, Stefan; Wernet, Dorothee; thor Straten, Per; Welters, Marij J P; Ottensmeier, Christian; van der Burg, Sjoerd H; Britten, Cedrik M

    2015-05-01

    Multiparameter flow cytometry is an indispensable method for assessing antigen-specific T cells in basic research and cancer immunotherapy. Proficiency panels have shown that cell sample processing, test protocols and data analysis may all contribute to the variability of the results obtained by laboratories performing ex vivo T cell immune monitoring. In particular, analysis currently relies on a manual, step-by-step strategy employing serial gating decisions based on visual inspection of one- or two-dimensional plots. It is therefore operator dependent and subjective. In the context of continuing efforts to support inter-laboratory T cell assay harmonization, the CIMT Immunoguiding Program organized its third proficiency panel dedicated to the detection of antigen-specific CD8(+) T cells by HLA-peptide multimer staining. We first assessed the contribution of manual data analysis to the variability of reported T cell frequencies within a group of laboratories staining and analyzing the same cell samples with their own reagents and protocols. The results show that data analysis is a source of variation in the multimer assay outcome. To evaluate whether an automated analysis approach can reduce variability of proficiency panel data, we used a hierarchical statistical mixture model to identify cell clusters. Challenges for automated analysis were the need to process non-standardized data sets from multiple centers, and the fact that the antigen-specific cell frequencies were very low in most samples. We show that this automated method can circumvent difficulties inherent to manual gating strategies and is broadly applicable for experiments performed with heterogeneous protocols and reagents.

  18. Thermal analysis and FTIR spectral curve-fitting investigation of formation mechanism and stability of indomethacin-saccharin cocrystals via solid-state grinding process.

    PubMed

    Zhang, Gang-Chun; Lin, Hong-Liang; Lin, Shan-Yang

    2012-07-01

    The cocrystal formation of indomethacin (IMC) and saccharin (SAC) by mechanical cogrinding or thermal treatment was investigated. The formation mechanism and stability of IMC-SAC cocrystal prepared by cogrinding process were explored. Typical IMC-SAC cocrystal was also prepared by solvent evaporation method. All the samples were identified and characterized by using differential scanning calorimetry (DSC) and Fourier transform infrared (FTIR) microspectroscopy with curve-fitting analysis. The physical stability of different IMC-SAC ground mixtures before and after storage for 7 months was examined. The results demonstrate that the stepwise measurements were carried out at specific intervals over a continuous cogrinding process showing a continuous growth in the cocrystal formation between IMC and SAC. The main IR spectral shifts from 3371 to 3,347 cm(-1) and 1693 to 1682 cm(-1) for IMC, as well as from 3094 to 3136 cm(-1) and 1718 to 1735 cm(-1) for SAC suggested that the OH and NH groups in both chemical structures were taken part in a hydrogen bonding, leading to the formation of IMC-SAC cocrystal. A melting at 184 °C for the 30-min IMC-SAC ground mixture was almost the same as the melting at 184 °C for the solvent-evaporated IMC-SAC cocrystal. The 30-min IMC-SAC ground mixture was also confirmed to have similar components and contents to that of the solvent-evaporated IMC-SAC cocrystal by using a curve-fitting analysis from IR spectra. The thermal-induced IMC-SAC cocrystal formation was also found to be dependent on the temperature treated. Different IMC-SAC ground mixtures after storage at 25 °C/40% RH condition for 7 months had an improved tendency of IMC-SAC cocrystallization.

  19. Molecular dynamics simulation to investigate the impact of disulfide bond formation on conformational stability of chicken cystatin I66Q mutant.

    PubMed

    He, Jianwei; Xu, Linan; Zou, Zhiyuan; Ueyama, Nobuhiro; Li, Hui; Kato, Akio; Jones, Gary W; Song, Youtao

    2013-10-01

    Chicken cystatin (cC) mutant I66Q is located in the hydrophobic core of the protein and increases the propensity for amyloid formation. Here, we demonstrate that under physiological conditions, the replacement of Ile with the Gln in the I66Q mutant increases the susceptibility for the disulfide bond Cys71-Cys81 to be reduced when compared to the wild type (WT) cC. Molecular dynamics (MD) simulations under conditions favoring cC amyloid fibril formation are in agreement with the experimental results. MD simulations were also performed to investigate the impact of disrupting the Cys71-Cys81 disulfide bond on the conformational stability of cC at the atomic level, and highlighted major disruption to the cC appendant structure. Domain swapping and extensive unfolding has been proposed as one of the possible mechanisms initiating amyloid fibril formation by cystatin. Our in silico studies suggest that disulfide bond formation between residues Cys95 and Cys115 is necessary to maintain conformational stability of the I66Q mutant following breakage of the Cys71-Cys81 disulfide bridge. Subsequent breakage of disulfide bond Cys95-Cys115 resulted in large structural destabilization of the I66Q mutant, which increased the α-β interface distance and expanded the hydrophobic core. These experimental and computational studies provide molecular-level insight into the relationship between disulfide bond formation and progressive unfolding of amyloidogenic cC mutant I66Q. An animated Interactive 3D Complement (I3DC) is available in Proteopedia at http://proteopedia.org/w/Journal:JBSD:23.

  20. Formation and stabilization of nanoemulsion-based vitamin E delivery systems using natural biopolymers: Whey protein isolate and gum arabic.

    PubMed

    Ozturk, Bengu; Argin, Sanem; Ozilgen, Mustafa; McClements, David Julian

    2015-12-01

    Natural biopolymers, whey protein isolate (WPI) and gum arabic (GA), were used to fabricate emulsion-based delivery systems for vitamin E-acetate. Stable delivery systems could be formed when vitamin E-acetate was mixed with sufficient orange oil prior to high pressure homogenization. WPI (d32=0.11 μm, 1% emulsifier) was better than GA (d32=0.38 μm, 10% emulsifier) at producing small droplets at low emulsifier concentrations. However, WPI-stabilized nanoemulsions were unstable to flocculation near the protein isoelectric point (pH 5.0), at high ionic strength (>100mM), and at elevated temperatures (>60 °C), whereas GA-stabilized emulsions were stable. This difference was attributed to differences in emulsifier stabilization mechanisms: WPI by electrostatic repulsion; GA by steric repulsion. These results provide useful information about the emulsifying and stabilizing capacities of natural biopolymers for forming food-grade vitamin-enriched delivery systems.

  1. Electronic structure, stability, and formation dynamics of hypervalent molecular clusters: CH 3NH 3(CH 3NH 2) n

    NASA Astrophysics Data System (ADS)

    Okai, Nobuhiro; Takahata, Akihiro; Fuke, Kiyokazu

    2004-03-01

    The formation and decay processes of CH 3NH 3(CH 3NH 2) n produced by the photolysis of (CH 3NH 2) n are studied by a pump-probe technique with femtosecond laser. The dissociation time of CH 3NH 2 in clusters is estimated to be less than 500 fs, while the formation time of CH 3NH 3(CH 3NH 2) n is less than 2 ps in the photolysis at 200 nm. The lifetime of free CH 3NH 3 is determined to be 30 ps and is elongated by 10 5 times in clusters. The ionization potentials and the binding energies of these clusters are determined by photoionization threshold measurements. On the basis of these results, the formation and decay processes for these clusters are discussed.

  2. The methane hydrate formation and the resource estimate resulting from free gas migration in seeping seafloor hydrate stability zone

    NASA Astrophysics Data System (ADS)

    Guan, Jinan; Liang, Deqing; Wu, Nengyou; Fan, Shuanshi

    2009-10-01

    It is a typical multiphase flow process for hydrate formation in seeping seafloor sediments. Free gas can not only be present but also take part in formation of hydrate. The volume fraction of free gas in local pore of hydrate stable zone (HSZ) influences the formation of hydrate in seeping seafloor area, and methane flux determines the abundance and resource of hydrate-bearing reservoirs. In this paper, a multiphase flow model including water (dissolved methane and salt)-free gas hydrate has been established to describe this kind of flow-transfer-reaction process where there exists a large scale of free gas migration and transform in seafloor pore. In the order of three different scenarios, the conversions among permeability, capillary pressure, phase saturations and salinity along with the formation of hydrate have been deducted. Furthermore, the influence of four sorts of free gas saturations and three classes of methane fluxes on hydrate formation and the resource has also been analyzed and compared. Based on the rules drawn from the simulation, and combined information gotten from drills in field, the methane hydrate(MH) formation in Shenhu area of South China Sea has been forecasted. It has been speculated that there may breed a moderate methane flux below this seafloor HSZ. If the flux is about 0.5 kg m -2 a -1, then it will go on to evolve about 2700 ka until the hydrate saturation in pore will arrive its peak (about 75%). Approximately 1.47 × 10 9 m 3 MH has been reckoned in this marine basin finally, is about 13 times over preliminary estimate.

  3. IL1RAPL1 associated with mental retardation and autism regulates the formation and stabilization of glutamatergic synapses of cortical neurons through RhoA signaling pathway.

    PubMed

    Hayashi, Takashi; Yoshida, Tomoyuki; Ra, Moonjin; Taguchi, Ryo; Mishina, Masayoshi

    2013-01-01

    Interleukin-1 receptor accessory protein-like 1 (IL1RAPL1) is associated with X-linked mental retardation and autism spectrum disorder. We found that IL1RAPL1 regulates synapse formation of cortical neurons. To investigate how IL1RAPL1 controls synapse formation, we here screened IL1RAPL1-interacting proteins by affinity chromatography and mass spectroscopy. IL1RAPL1 interacted with Mcf2-like (Mcf2l), a Rho guanine nucleotide exchange factor, through the cytoplasmic Toll/IL-1 receptor domain. Knockdown of endogenous Mcf2l and treatment with an inhibitor of Rho-associated protein kinase (ROCK), the downstream kinase of RhoA, suppressed IL1RAPL1-induced excitatory synapse formation of cortical neurons. Furthermore, we found that the expression of IL1RAPL1 affected the turnover of AMPA receptor subunits. Insertion of GluA1-containing AMPA receptors to the cell surface was decreased, whereas that of AMPA receptors composed of GluA2/3 was enhanced. Mcf2l knockdown and ROCK inhibitor treatment diminished the IL1RAPL1-induced changes of AMPA receptor subunit insertions. Our results suggest that Mcf2l-RhoA-ROCK signaling pathway mediates IL1RAPL1-dependent formation and stabilization of glutamatergic synapses of cortical neurons.

  4. Experimental Constraints on the Stability of Clinopyroxene (+) Magnesite in Iron Bearing Planetary Mantles: Implications for Nakhlite Formation

    NASA Technical Reports Server (NTRS)

    Martin, Audrey M.; Righter, Kevin

    2010-01-01

    Carbon is present in various forms in the Earth s upper mantle (carbonate- or diamond-bearing mantle xenoliths, carbonatite magmas, CO2 emissions from volcanoes...). Moreover, there is enough carbon in chondritic material to stabilize carbonates into the mantles of Mars or Venus as well as in the Earth. However, the interactions with iron have to be constrained, because Fe is commonly thought to buffer oxygen fugacity into planetary mantles. [1] and [2] show evidences of the stability of clinopyroxene Ca(Mg,Fe)Si2O6 + magnesite (Mg,Fe)CO3 in the Earth s mantle around 6GPa (about 180km). The stability of oxidized forms of carbon (like magnesite) depends on the oxygen fugacity of the system. In the Earth s mantle, the maximum carbon content is 10000 ppm [3]. The fO2 parameter varies vertically as a function of pressure, but also laterally because of geodynamic processes like subduction. Thus, carbonates, graphite, diamond, C-rich gases and melts are all stable forms of carbon in the Earth s mantle. [4] show that the fO2 variations observed in SNC meteorites can be explained by polybaric graphite-CO-CO2 equilibria in the Martian mantle. [5] inferred from thermodynamic calculations that the stable form of carbon in the source regions of the Martian basalts should be graphite (and/or diamond). After [6], a metasomatizing agent like a CO2-rich melt may infiltrate the mantle source of nakhlites. However, according to [7] and [8], the FeO wt% value in the Martian bulk mantle is more than twice that of the Earth s mantle (KLB-1 composition by [9]). As iron and carbon are two elements with various oxidation states, Fe/C interaction mechanisms must be considered.

  5. The formation and physical stability of two-phase solid dispersion systems of indomethacin in supercooled molten mixtures with different matrix formers.

    PubMed

    Semjonov, Kristian; Kogermann, Karin; Laidmäe, Ivo; Antikainen, Osmo; Strachan, Clare J; Ehlers, Henrik; Yliruusi, Jouko; Heinämäki, Jyrki

    2017-01-15

    Amorphous solid dispersions (SDs) are a promising approach to improve the dissolution rate of and oral bioavailability of poorly water-soluble drugs. In some cases multi-phase, instead of single-phase, SD systems with amorphous drug are obtained. While it is widely assumed that one-phase amorphous systems are desirable, two-phase systems may still potentially exhibit enhanced stability and dissolution advantages over undispersed systems. The objective of the present study was to understand the solid-state properties of two-phase SDs with amorphous drug and their relation to physical stability. Two different types of excipients for SD formation were used, one being a polymer and the other a small molecule excipient. The supercooled molten SDs of a poorly water-soluble indomethacin (IND) with a graft copolymer, Soluplus® (SOL) and sugar alcohol, xylitol (XYL) were prepared. Supercooled molten SDs of IND with SOL were two-phase glassy suspension in which the amorphous drug was dispersed in an amorphous polymer matrix. A short-term aging of the SDs led to the formation of glassy suspensions where the crystalline drug was dispersed in an amorphous polymer matrix. These were physically stable at room temperature for the time period studied (RT, 23±2°C), but aging at high-humidity conditions (75% RH) recrystallization to metastable α-IND occurred. Interestingly, the SDs with XYL were two-phase amorphous precipitation systems in which the drug was in an amorphous form in the crystalline sugar alcohol matrix. The SDs of IND and XYL exhibited fast drug recrystallization. In conclusion, the preparation method of two-phase systems via co-melting in association with the rapid quench cooling is a feasible method for the formulation of poorly water-soluble drugs. The physical stability of these two-phase systems, however, is dependent on the carrier material and storage conditions.

  6. The coupling between stability and ion pair formation in magnesium electrolytes from first-principles quantum mechanics and classical molecular dynamics

    DOE PAGES

    Rajput, Nav Nidhi; Qu, Xiaohuui; Sa, Niya; ...

    2015-02-10

    Here in this work we uncover a novel effect between concentration dependent ion pair formation and anion stability at reducing potentials, e.g., at the metal anode. Through comprehensive calculations using both first-principles as well as well-benchmarked classical molecular dynamics over a matrix of electrolytes, covering solvents and salt anions with a broad range in chemistry, we elucidate systematic correlations between molecular level interactions and composite electrolyte properties, such as electrochemical stability, solvation structure, and dynamics. We find that Mg electrolytes are highly prone to ion pair formation, even at modest concentrations, for a wide range of solvents with different dielectricmore » constants, which have implications for dynamics as well as charge transfer. Specifically, we observe that, at Mg metal potentials, the ion pair undergoes partial reduction at the Mg cation center (Mg2+ -> Mg+), which competes with the charge transfer mechanism and can activate the anion to render it susceptible to decomposition. Specifically, TFSI exhibits a significant bond weakening while paired with the transient, partially reduced Mg+. In contrast, BH4$-$ and BF4$-$ are shown to be chemically stable in a reduced ion pair configuration. Furthermore, we observe that higher order glymes as well as DMSO improve the solubility of Mg salts, but only the longer glyme chains reduce the dynamics of the ions in solution. This information provides critical design metrics for future electrolytes as it elucidates a close connection between bulk solvation and cathodic stability as well as the dynamics of the salt.« less

  7. Long-term Formation of Aggressive Bony Lesions in Dogs with Mid-Diaphyseal Fractures Stabilized with Metallic Plates: Incidence in a Tertiary Referral Hospital Population

    PubMed Central

    Gilley, Robert S.; Hiebert, Elizabeth; Clapp, Kemba; Bartl-Wilson, Lara; Nappier, Michael; Werre, Stephen; Barnes, Katherine

    2017-01-01

    The incidence of complications secondary to fracture stabilization, particularly osteolytic lesions and bony tumor formation, has long been difficult to evaluate. The objective of this study was to describe the long-term incidence of aggressive bony changes developing in dogs with long bone diaphyseal fractures stabilized by metallic bone plates compared to a breed-, sex-, and age-matched control group. The medical records of a tertiary referral center were retrospectively reviewed for dogs that matched each respective criterion. Signalment, history, cause of death (if applicable), and aggressive bony changes at previous fracture sites were recorded. Ninety dogs met the criteria for inclusion in the fracture group and were matched with appropriate control dogs. Four of the dogs in the fracture group developed aggressive bony changes at the site of previous fracture repairs most consistent with osseous neoplasia. One lesion was confirmed with cytology as neoplastic. The population of dogs was mixed with regard to breed and body weight, but all dogs with aggressive bony lesions were male. Incidence of aggressive bony lesion formation in the fracture group was 4 (4.4%) and was 0 (0%) in the control group; three (75%) of the affected dogs in the fracture group included cerclage as a component of their primary fracture stabilizations. Incidence of aggressive bony lesions in the fracture group compared to the control group was determined to be statistically significant (p = 0.0455), as was the incidence of cerclage among dogs affected by aggressive bony lesions compared to the rest of the fracture group (p = 0.0499). Development of aggressive bony lesions is an uncommon complication of fracture fixation. Additional research is needed to further identify and elucidate the long-term effects of metallic implants in dogs. PMID:28197406

  8. The coupling between stability and ion pair formation in magnesium electrolytes from first-principles quantum mechanics and classical molecular dynamics

    SciTech Connect

    Rajput, Nav Nidhi; Qu, Xiaohuui; Sa, Niya; Burrell, Anthony K.; Persson, Kristin A.

    2015-02-10

    Here in this work we uncover a novel effect between concentration dependent ion pair formation and anion stability at reducing potentials, e.g., at the metal anode. Through comprehensive calculations using both first-principles as well as well-benchmarked classical molecular dynamics over a matrix of electrolytes, covering solvents and salt anions with a broad range in chemistry, we elucidate systematic correlations between molecular level interactions and composite electrolyte properties, such as electrochemical stability, solvation structure, and dynamics. We find that Mg electrolytes are highly prone to ion pair formation, even at modest concentrations, for a wide range of solvents with different dielectric constants, which have implications for dynamics as well as charge transfer. Specifically, we observe that, at Mg metal potentials, the ion pair undergoes partial reduction at the Mg cation center (Mg2+ -> Mg+), which competes with the charge transfer mechanism and can activate the anion to render it susceptible to decomposition. Specifically, TFSI exhibits a significant bond weakening while paired with the transient, partially reduced Mg+. In contrast, BH4$-$ and BF4$-$ are shown to be chemically stable in a reduced ion pair configuration. Furthermore, we observe that higher order glymes as well as DMSO improve the solubility of Mg salts, but only the longer glyme chains reduce the dynamics of the ions in solution. This information provides critical design metrics for future electrolytes as it elucidates a close connection between bulk solvation and cathodic stability as well as the dynamics of the salt.

  9. Long-term Formation of Aggressive Bony Lesions in Dogs with Mid-Diaphyseal Fractures Stabilized with Metallic Plates: Incidence in a Tertiary Referral Hospital Population.

    PubMed

    Gilley, Robert S; Hiebert, Elizabeth; Clapp, Kemba; Bartl-Wilson, Lara; Nappier, Michael; Werre, Stephen; Barnes, Katherine

    2017-01-01

    The incidence of complications secondary to fracture stabilization, particularly osteolytic lesions and bony tumor formation, has long been difficult to evaluate. The objective of this study was to describe the long-term incidence of aggressive bony changes developing in dogs with long bone diaphyseal fractures stabilized by metallic bone plates compared to a breed-, sex-, and age-matched control group. The medical records of a tertiary referral center were retrospectively reviewed for dogs that matched each respective criterion. Signalment, history, cause of death (if applicable), and aggressive bony changes at previous fracture sites were recorded. Ninety dogs met the criteria for inclusion in the fracture group and were matched with appropriate control dogs. Four of the dogs in the fracture group developed aggressive bony changes at the site of previous fracture repairs most consistent with osseous neoplasia. One lesion was confirmed with cytology as neoplastic. The population of dogs was mixed with regard to breed and body weight, but all dogs with aggressive bony lesions were male. Incidence of aggressive bony lesion formation in the fracture group was 4 (4.4%) and was 0 (0%) in the control group; three (75%) of the affected dogs in the fracture group included cerclage as a component of their primary fracture stabilizations. Incidence of aggressive bony lesions in the fracture group compared to the control group was determined to be statistically significant (p = 0.0455), as was the incidence of cerclage among dogs affected by aggressive bony lesions compared to the rest of the fracture group (p = 0.0499). Development of aggressive bony lesions is an uncommon complication of fracture fixation. Additional research is needed to further identify and elucidate the long-term effects of metallic implants in dogs.

  10. Thermal stability of plant sterols and formation of their oxidation products in vegetable oils and margarines upon controlled heating.

    PubMed

    Lin, Yuguang; Knol, Diny; Valk, Iris; van Andel, Vincent; Friedrichs, Silvia; Lütjohann, Dieter; Hrncirik, Karel; Trautwein, Elke A

    2017-02-02

    Fat-based products like vegetable oils and margarines are commonly used for cooking, which may enhance oxidation of plant sterols (PS) present therein, leading to the formation of PS oxidation products (POP). The present study aims to assess the kinetics of POP formation in six different fat-based products. Vegetable oils and margarines without and with added PS (7.5-7.6% w/w) in esterified form were heated in a Petri-dish at temperatures of 150, 180 and 210°C for 8, 12 and 16min. PS and POP were analysed using GC-FID and GC-MS-SIM, respectively. Increasing PS content, temperature and heating time led to higher POP formation in all tested fat-based products. PS (either naturally occurring or added) in margarines were less susceptible to oxidation as compared to PS in vegetable oils. The susceptibility of sitosterol to oxidation was about 20% lower than that of campesterol under all the applied experimental conditions. During heating, the relative abundance of 7-keto-PS (expressed as% of total POP) decreased in all the fat-based products regardless of their PS contents, which was accompanied by an increase in the relative abundance of 7-OH-PS and 5,6-epoxy-PS, while PS-triols were fairly unchanged. In conclusion, heating time, temperature, initial PS content and the matrix of the fat-based products (vegetable oil vs. margarine) showed distinct effects on POP formation and composition of individual POP formed.

  11. Formation of natural gas hydrates in marine sediments. Gas hydrate growth and stability conditioned by host sediment properties

    USGS Publications Warehouse

    Clennell, M.B.; Henry, P.; Hovland, M.; Booth, J.S.; Winters, W.J.; Thomas, M.

    2000-01-01

    The stability conditions of submarine gas hydrates (methane clathrates) are largely dictated by pressure, temperature, gas composition, and pore water salinity. However, the physical properties and surface chemistry of the host sediments also affect the thermodynamic state, growth kinetics, spatial distributions, and growth forms of clathrates. Our model presumes that gas hydrate behaves in a way analogous to ice in the pores of a freezing soil, where capillary forces influence the energy balance. Hydrate growth is inhibited within fine-grained sediments because of the excess internal phase pressure of small crystals with high surface curvature that coexist with liquid water in small pores. Therefore, the base of gas hydrate stability in a sequence of fine sediments is predicted by our model to occur at a lower temperature, and so nearer to the seabed than would be calculated from bulk thermodynamic equilibrium. The growth forms commonly observed in hydrate samples recovered from marine sediments (nodules, sheets, and lenses in muds; cements in sand and ash layers) can be explained by a requirement to minimize the excess of mechanical and surface energy in the system.

  12. Bacterial adhesion and biofilm formation on yttria-stabilized, tetragonal zirconia and titanium oral implant materials with low surface roughness - an in situ study.

    PubMed

    Al-Ahmad, Ali; Karygianni, Lamprini; Schulze Wartenhorst, Max; Bächle, Maria; Hellwig, Elmar; Follo, Marie; Vach, Kirstin; Han, Jung-Suk

    2016-04-19

    Bacterially-driven mucosal inflammation and the development of periimplantitis can lead to oral implant failure. In this study, initial bacterial adhesion after 2 h and biofilm formation after 1 day and 3 days were analyzed in situ on novel 3 mol% yttria-stabilized tetragonal zirconia polycrystal samples (Zr; 3Y-TZP), as well as on alumina and niobium co-doped yttria-stabilized tetragonal zirconia samples (Al-Zr; Al2O3/Y(Nb)-TZP). Pure titanium implant material (Ti) and bovine enamel slabs (BES) served as controls. The initially adherent oral bacteria were determined by DAPI-staining. Biofilm thickness, surface covering grade and content of oral streptococci within the biofilm were measured by fluorescence in situ hybridization. No significant differences between the ceramic and titanium surfaces were detectable for either initial bacterial adhesion or the oral streptococci content of the in situ biofilm. The values of oral biofilm thickness on the implant surfaces were almost doubled after three days compared to the first day of oral exposure. Nevertheless, the biofilm thickness values among the different implant surfaces and controls did not differ significantly for any time point of measurement after 1 day or 3 days of biofilm formation. Significant differences in the covering grade were only detected between day 1 and day 3 for each tested implant material group. The content of oral streptococci increased significantly in parallel with the increase of biofilm age from day 1 to day 3. In conclusion, oral implant zirconia surfaces with low surface roughness are comparable to titanium surfaces with regard to initial bacterial adhesion and biofilm formation.

  13. Nonstandard cages in the formation process of methane clathrate: stability, structure, and spectroscopic implications from first-principles.

    PubMed

    Tang, Lingli; Su, Yan; Liu, Yuan; Zhao, Jijun; Qiu, Ruifeng

    2012-06-14

    Endohedral CH(4)@(H(2)O)(n) (n = 16, 18, 20, 22, 24) clusters with standard and nonstandard cage configurations containing four-, five-, six-, seven-membered rings were generated by spiral algorithm and were systematically explored using DFT-D methods. The geometries of all isomers were optimized in vacuum and aqueous solution. In vacuum, encapsulation of methane molecules can stabilize the hollow (H(2)O)(n) cage by 2.31~5.44 kcal/mol; but the endohedral CH(4)@(H(2)O)(n) cages are still less stable than the pure (H(2)O)(n) clusters. Aqueous environment could promote the stabilities of the hollow (H(2)O)(n) cages as well as the CH(4)@(H(2)O)(n) clusters, and the CH(4)@(H(2)O)(n) clusters possess larger stabilization energies with regard to the pure (H(2)O)(n) clusters except for n = 24. The lowest energy structures of the CH(4)@(H(2)O)(20) and CH(4)@(H(2)O)(24) cages are identical to the building units in the crystalline sI clathrate hydrate. All of the low-energy cages (including both regular and irregular ones) have large structural similarity and can be connected by "dimer-insertion" operation and Stone-Wales transformation. Our calculation also showed that in the range of cluster size n = 16-24, the relative energies of cage isomers tend to decrease with increasing number of the adjacent pentagons in the oxygen skeleton structures. In addition to the regular endohedral CH(4)@(H(2)O)(20) and CH(4)@(H(2)O)(24) cage structures, some nonstandard CH(4)@(H(2)O)(n) (n = 18, 20, 22, 24) cages have lower energies and might appear during nucleation process of methane hydrate. For the methane molecules in these low-energy cage isomers, we found that the C-H symmetric stretching frequencies show a red-shift trend and the (13)C NMR chemical shifts generally move toward negative values as the cavity size increases. These theoretical results are comparable to the available experimental data and might help experimental identification of the endohedral water cages during

  14. Quantum many-body intermetallics: Phase stability of Fe3Al and small-gap formation in Fe2VAl

    NASA Astrophysics Data System (ADS)

    Kristanovski, Oleg; Richter, Raphael; Krivenko, Igor; Lichtenstein, Alexander I.; Lechermann, Frank

    2017-01-01

    Various intermetallic compounds harbor subtle electronic correlation effects. To elucidate this fact for the Fe-Al system, we perform a realistic many-body investigation based on a combination of density functional theory with dynamical mean-field theory in a charge self-consistent manner. A better characterization and understanding of the phase stability of bcc-based D 03-Fe3Al through an improved description of the correlated charge density and the magnetic energy is achieved. Upon replacement of one Fe sublattice with V, the Heusler compound Fe2VAl is realized, known to display bad-metal behavior and increased specific heat. Here we document a charge-gap opening at low temperatures in line with previous experimental work. The gap structure does not match conventional band theory and is reminiscent of (pseudo)gap characteristics in correlated oxides.

  15. Facile formation of dendrimer-stabilized gold nanoparticles modified with diatrizoic acid for enhanced computed tomography imaging applications

    NASA Astrophysics Data System (ADS)

    Peng, Chen; Li, Kangan; Cao, Xueyan; Xiao, Tingting; Hou, Wenxiu; Zheng, Linfeng; Guo, Rui; Shen, Mingwu; Zhang, Guixiang; Shi, Xiangyang

    2012-10-01

    We report a facile approach to forming dendrimer-stabilized gold nanoparticles (Au DSNPs) through the use of amine-terminated fifth-generation poly(amidoamine) (PAMAM) dendrimers modified by diatrizoic acid (G5.NH2-DTA) as stabilizers for enhanced computed tomography (CT) imaging applications. In this study, by simply mixing G5.NH2-DTA dendrimers with gold salt in aqueous solution at room temperature, dendrimer-entrapped gold nanoparticles (Au DENPs) with a mean core size of 2.5 nm were able to be spontaneously formed. Followed by an acetylation reaction to neutralize the dendrimer remaining terminal amines, Au DSNPs with a mean size of 6 nm were formed. The formed DTA-containing [(Au0)50-G5.NHAc-DTA] DSNPs were characterized via different techniques. We show that the Au DSNPs are colloid stable in aqueous solution under different pH and temperature conditions. In vitro hemolytic assay, cytotoxicity assay, flow cytometry analysis, and cell morphology observation reveal that the formed Au DSNPs have good hemocompatibility and are non-cytotoxic at a concentration up to 3.0 μM. X-ray absorption coefficient measurements show that the DTA-containing Au DSNPs have enhanced attenuation intensity, much higher than that of [(Au0)50-G5.NHAc] DENPs without DTA or Omnipaque at the same molar concentration of the active element (Au or iodine). The formed DTA-containing Au DSNPs can be used for CT imaging of cancer cells in vitro as well as for blood pool CT imaging of mice in vivo with significantly improved signal enhancement. With the two radiodense elements of Au and iodine incorporated within one particle, the formed DTA-containing Au DSNPs may be applicable for CT imaging of various biological systems with enhanced X-ray attenuation property and detection sensitivity.We report a facile approach to forming dendrimer-stabilized gold nanoparticles (Au DSNPs) through the use of amine-terminated fifth-generation poly(amidoamine) (PAMAM) dendrimers modified by diatrizoic acid

  16. Intrinsic karyotype stability and gene copy number variations may have laid the foundation for tetraploid wheat formation

    PubMed Central

    Zhang, Huakun; Bian, Yao; Gou, Xiaowan; Dong, Yuzhu; Rustgi, Sachin; Zhang, Bangjiao; Xu, Chunming; Li, Ning; Qi, Bao; Han, Fangpu; von Wettstein, Diter; Liu, Bao

    2013-01-01

    Polyploidy or whole-genome duplication is recurrent in plant evolution, yet only a small fraction of whole-genome duplications has led to successful speciation. A major challenge in the establishment of nascent polyploids is sustained karyotype instability, which compromises fitness. The three putative diploid progenitors of bread wheat, with AA, SS (S ∼ B), and DD genomes occurred sympatrically, and their cross-fertilization in different combinations may have resulted in fertile allotetraploids with various genomic constitutions. However, only SSAA or closely related genome combinations have led to the speciation of tetraploid wheats like Triticum turgidum and Triticum timopheevii. We analyzed early generations of four newly synthesized allotetraploid wheats with genome compositions SshSshAmAm, SlSlAA, SbSbDD, and AADD by combined fluorescence and genomic in situ hybridization-based karyotyping. Results of karyotype analyses showed that although SshSshAmAm and SlSlAA are characterized by immediate and persistent karyotype stability, massive aneuploidy and extensive chromosome restructuring are associated with SbSbDD and AADD in which parental subgenomes showed markedly different propensities for chromosome gain/loss and rearrangements. Although compensating aneuploidy and reciprocal translocation between homeologs prevailed, reproductive fitness was substantially compromised due to chromosome instability. Strikingly, localized genomic changes in repetitive DNA and copy-number variations in gene homologs occurred in both chromosome stable lines, SshSshAmAm and SlSlAA. Our data demonstrated that immediate and persistent karyotype stability is intrinsic to newly formed allotetraploid wheat with genome combinations analogous to natural tetraploid wheats. This property, coupled with rapid gene copy-number variations, may have laid the foundation of tetraploid wheat establishment. PMID:24218593

  17. Effects of Size and Stability of Native Fat Globules on the Formation of Milk Gel Induced by Rennet.

    PubMed

    Luo, Jie; Wang, Yuhan; Guo, Huiyuan; Ren, Fazheng

    2017-03-01

    Rennet-induced gelation crucially impacts cheese structure. In this study, effects of the size and stability of native fat globules on the kinetics of rennet-induced coagulation were revealed by determining the caseinomacropeptide release rate and rheological properties of milk. Moreover, the mobility and stability of fat globules during renneting was revealed using diffusing wave spectroscopy and confocal laser scanning microscopy. By use of a 2-stage gravity separation combined centrifugation scheme, native fat globules were selectively separated into small (SFG, D4,3 = 1.87 ± 0.02 μm) and large fat globules (LFG, D4,3 = 5.65 ± 0.03 μm). The protein and fat content of SFG and LFG milk were then standardized to 3.2 g/100 mL and 1.2 g/100 mL, respectively. The milk containing different sized globules were then subjected to renneting experiments in the laboratory. Reduction of globule size accelerated the aggregation of casein micelles during renneting, giving a shorter gelation time and earlier 1/l(*) change. The gel produced from LFG milk was broken due to coalescent fat globules and generated coarser gel strands compared to the finer strands formed with SFG milk. Structural differences were also confirmed with a higher final storage modulus of the curd made from SFG milk than that from the LFG. In conclusion, the size of fat globules affects the aggregation of casein micelles. Moreover, fat globule coalescence and creaming during renneting, also affects the structure of the rennet gel. A better understanding of the size of globules effect on milk gelation could lead to the development of cheese with specific properties.

  18. Intrinsic karyotype stability and gene copy number variations may have laid the foundation for tetraploid wheat formation.

    PubMed

    Zhang, Huakun; Bian, Yao; Gou, Xiaowan; Dong, Yuzhu; Rustgi, Sachin; Zhang, Bangjiao; Xu, Chunming; Li, Ning; Qi, Bao; Han, Fangpu; von Wettstein, Diter; Liu, Bao

    2013-11-26

    Polyploidy or whole-genome duplication is recurrent in plant evolution, yet only a small fraction of whole-genome duplications has led to successful speciation. A major challenge in the establishment of nascent polyploids is sustained karyotype instability, which compromises fitness. The three putative diploid progenitors of bread wheat, with AA, SS (S ∼ B), and DD genomes occurred sympatrically, and their cross-fertilization in different combinations may have resulted in fertile allotetraploids with various genomic constitutions. However, only SSAA or closely related genome combinations have led to the speciation of tetraploid wheats like Triticum turgidum and Triticum timopheevii. We analyzed early generations of four newly synthesized allotetraploid wheats with genome compositions S(sh)S(sh)A(m)A(m), S(l)S(l)AA, S(b)S(b)DD, and AADD by combined fluorescence and genomic in situ hybridization-based karyotyping. Results of karyotype analyses showed that although S(sh)S(sh)A(m)A(m) and S(l)S(l)AA are characterized by immediate and persistent karyotype stability, massive aneuploidy and extensive chromosome restructuring are associated with S(b)S(b)DD and AADD in which parental subgenomes showed markedly different propensities for chromosome gain/loss and rearrangements. Although compensating aneuploidy and reciprocal translocation between homeologs prevailed, reproductive fitness was substantially compromised due to chromosome instability. Strikingly, localized genomic changes in repetitive DNA and copy-number variations in gene homologs occurred in both chromosome stable lines, S(sh)S(sh)A(m)A(m) and S(l)S(l)AA. Our data demonstrated that immediate and persistent karyotype stability is intrinsic to newly formed allotetraploid wheat with genome combinations analogous to natural tetraploid wheats. This property, coupled with rapid gene copy-number variations, may have laid the foundation of tetraploid wheat establishment.

  19. Aspartase/fumarase superfamily: a common catalytic strategy involving general base-catalyzed formation of a highly stabilized aci-carboxylate intermediate.

    PubMed

    Puthan Veetil, Vinod; Fibriansah, Guntur; Raj, Hans; Thunnissen, Andy-Mark W H; Poelarends, Gerrit J

    2012-05-29

    Members of the aspartase/fumarase superfamily share a common tertiary and quaternary fold, as well as a similar active site architecture; the superfamily includes aspartase, fumarase, argininosuccinate lyase, adenylosuccinate lyase, δ-crystallin, and 3-carboxy-cis,cis-muconate lactonizing enzyme (CMLE). These enzymes all process succinyl-containing substrates, leading to the formation of fumarate as the common product (except for the CMLE-catalyzed reaction, which results in the formation of a lactone). In the past few years, X-ray crystallographic analysis of several superfamily members in complex with substrate, product, or substrate analogues has provided detailed insights into their substrate binding modes and catalytic mechanisms. This structural work, combined with earlier mechanistic studies, revealed that members of the aspartase/fumarase superfamily use a common catalytic strategy, which involves general base-catalyzed formation of a stabilized aci-carboxylate (or enediolate) intermediate and the participation of a highly flexible loop, containing the signature sequence GSSxxPxKxN (named the SS loop), in substrate binding and catalysis.

  20. Fibril stability in solutions of twisted Format="TEX"/>-sheet peptides: a new kind of micellization in chiral systems

    NASA Astrophysics Data System (ADS)

    Nyrkova, I. A.; Semenov, A. N.; Aggeli, A.; Boden, N.

    2000-10-01

    The problem of fibril (fibre) formation in chiral systems is explored theoretically being supported by experiments on synthetic de novo 11-mer peptide forming self-assembled -sheet tapes. Experimental data unambiguously indicate that the tapes form fibrils of nearly monodisperse thickness ca. 8-10 nm. Fibril formation and stabilisation are attributed to inter-tape face-to-face attraction and their intrinsic twist, correspondingly. The proposed theory is capable of predicting the fibril aggregation number and its equilibrium twist in terms of molecular parameters of the primary tapes. The suggested novel mechanism of twist stabilisation of finite aggregates (fibrils) is different to the well-known stabilisation of micelles in amphiphilic systems, and it is likely to explain the formation and stability of fibrils in a wide variety of systems including proteinaceous amyloid fibres, sickle-cell hemoglobin fibres responsible for HbS anemia, corkscrew threads found in chromonics in the presence of chiral additives and native cellulose microfibrillar crystallites. The theory also makes it possible to extract the basic molecular parameters of primary tapes (inter-tape attraction energy, helical twist step, elastic moduli) from the experimental data.

  1. Formation of 3-MCPD Fatty Acid Esters from Monostearoyl Glycerol and the Thermal Stability of 3-MCPD Monoesters.

    PubMed

    Zhao, Yue; Zhang, Yaqiong; Zhang, Zhongfei; Liu, Jie; Wang, Yi-Lin; Gao, Boyan; Niu, Yuge; Sun, Xiangjun; Yu, Liangli

    2016-11-23

    Formation of 3-monochloropropanediol (3-MCPD) esters from monostearoyl glycerol (MSG) was investigated under high temperature and low moisture conditions. Different organic and inorganic chlorides, including lindane, KCl, CaCl2, NaCl, MgCl2, AlCl3, CuCl2, MnCl2, SnCl2, ZnCl2, and FeCl3, were evaluated for their potential to react with MSG to form 3-MCPD and glycidyl esters at 120 and 240 °C using a UPLC-Q-TOF MS analysis. The results indicated that different chlorine compounds differed in their capacity to react with MSG and formed different products including 3-MCPD mono- and diesters, distearoylglycerol, and glycidyl esters. According to electron spin resonance (ESR) and Fourier transform infrared (FT-IR) spectroscopies, free radical mediated formation mechanisms involving either five-membered or six-membered cyclic acyloxonium free radicals (CAFR) from monoacylglycerol (MAG) were proposed. Tandem quadrupole-time-of-flight (Q-TOF) MS and MS/MS analyses confirmed the free radical mechanisms. In addition, the results from the present study showed that 3-MCPD monoester could be degraded upon thermal treatment and suggested a possible catalytic role of Fe(3+) under the experimental conditions.

  2. Layered double hydroxide stability. 2. Formation of Cr(III)-containing layered double hydroxides directly from solution

    NASA Technical Reports Server (NTRS)

    Boclair, J. W.; Braterman, P. S.; Jiang, J.; Lou, S.; Yarberry, F.

    1999-01-01

    Solutions containing divalent metal [M(II) = Mg2+, Zn2+, Co2+, Ni2+, Mn2+] chlorides and CrCl3 6H2O were titrated with NaOH to yield, for M(II) = Zn, Co, and Ni, hydrotalcite-like layered double hydroxides (LDHs), [[M(II)]1-z[Cr(III)]z(OH)2][Cl]z yH2O, in a single step, without intermediate formation of chromium hydroxide. Analysis of the resultant titration curves yields solubility constants for these compounds. These are in the order Zn < Ni approximately Co, with a clear preference for formation of the phase with z = 1/3. With Mg2+ as chloride, titration gives a mixture of Cr(OH)3 and Mg(OH)2, but the metal sulfates give Mg2Cr(OH)6 1/2(SO4) by a two-step process. Titrimetric and spectroscopic evidence suggests short-range cation order in the one-step LDH systems.

  3. On the formation of phases and their influence on the thermal stability and thermoelectric properties of nanostructured zinc antimonide

    NASA Astrophysics Data System (ADS)

    Balasubramanian, Priyadarshini; Battabyal, Manjusha; Sivaprahasam, Duraiswamy; Gopalan, Raghavan

    2017-01-01

    To investigate the thermal reliability of the structure and thermoelectric properties of the zinc antimony compounds, undoped (Zn4Sb3) and doped (Zn4Sb2.95Sn0.05 and Co0.05Zn3.95Sb3) zinc antimonide samples were processed using the powder metallurgy route. It was observed that the as-prepared undoped sample contains a pure β-Zn4Sb3 phase, whereas the doped samples consist of Ω-ZnSb as the major phase and β-Zn4Sb3 as the minor phase. Differential scanning calorimetry analysis confirms the stability of the β-Zn4Sb3 phase up to 600 K. X-ray diffraction data of the undoped and doped samples show that the nanocrystallinity of the as-prepared samples is retained after one thermal cycle. The thermal bandgap, thermopower and thermal conductivity are not affected by the thermal cycle for the doped samples. A maximum power factor of 0.6 mW m-1 K-2 was achieved in the Sn-doped sample (Zn4Sb2.95Sn0.05). This is enhanced to 0.72 mW m-1 K-2 after one thermal cycle at 650 K under Ar atmosphere and slightly decreases after the third thermal cycle. In the case of the Co-doped sample (Co0.05Zn3.95Sb3), the power factor increases from 0.4 mW m-1 K-2 to 0.7 mW m-1 K-2 after the third thermal cycle. A figure of merit of ~0.3 is achieved at 573 K in the Zn4Sb2.95Sn0.05 sample. The results from the nanoindentation experiment show that Young’s modulus of the Sn-doped sample (Zn4Sb2.95Sn0.05) after the thermal cycle is enhanced (96 GPa) compared to the as-prepared sample (~76 GPa). These important findings on the thermal stability of the thermoelectric and mechanical properties of Sn-doped samples (Zn4Sb2.95Sn0.05) confirm that Sn-doped zinc antimonide samples can be used as efficient thermoelectric materials for device applications.

  4. Structure, stability, and formation pathways of colloidal gels in systems with short-range attraction and long-range repulsion.

    PubMed

    van Schooneveld, Matti M; de Villeneuve, Volkert W A; Dullens, Roel P A; Aarts, Dirk G A L; Leunissen, Mirjam E; Kegel, Willem K

    2009-04-09

    We study colloidal gels formed upon centrifugation of dilute suspensions of spherical colloids (radius 446 nm) that interact through a long-range electrostatic repulsion (Debye length approximately 850 nm) and a short-range depletion attraction (approximately 12.5 nm), by means of confocal scanning laser microscopy (CSLM). In these systems, at low colloid densities, colloidal clusters are stable. Upon increasing the density by centrifugation, at different stages of cluster formation, we show that colloidal gels are formed that significantly differ in structure. While significant single-particle displacements do not occur on the hour time scale, the different gels slowly evolve within several weeks to a similar structure that is at least stable for over a year. Furthermore, while reference systems without long-range repulsion collapse into dense glassy states, the repulsive colloidal gels are able to support external stress in the form of a centrifugal field of at least 9g.

  5. Formation and stability of oil-in-water nanoemulsions containing rice bran oil: in vitro and in vivo assessments

    PubMed Central

    2011-01-01

    Background Nanoemulsions have practical application in a multitude of commercial areas, such as the chemical, pharmaceutical and cosmetic industries. Cosmetic industries use rice bran oil in sunscreen formulations, anti ageing products and in treatments for skin diseases. The aim of this study was to create rice bran oil nanoemulsions using low energy emulsification methods and to evaluate their physical stability, irritation potential and moisturising activity on volunteers with normal and diseased skin types. Results The nanoemulsion developed by this phase diagram method was composed of 10% rice bran oil, 10% surfactants sorbitan oleate/PEG-30 castor oil, 0.05% antioxidant and 0.50% preservatives formulated in distilled water. The nanoemulsion was stable over the time course of this study. In vitro assays showed that this formulation has a low irritation potential, and when applied to human skin during in vivo studies, the nanoemulsion improved the skin's moisture and maintained normal skin pH values. Conclusion The results of irritation potential studies and in vivo assessments indicate that this nanoemulsion has potential to be a useful tool to treat skin diseases, such as atopic dermatitis and psoriasis. PMID:21952107

  6. The study of polyplex formation and stability by time-resolved fluorescence spectroscopy of SYBR Green I-stained DNA.

    PubMed

    D'Andrea, Cosimo; Pezzoli, Daniele; Malloggi, Chiara; Candeo, Alessia; Capelli, Giulio; Bassi, Andrea; Volonterio, Alessandro; Taroni, Paola; Candiani, Gabriele

    2014-12-01

    Polyplexes are nanoparticles formed by the self-assembly of DNA/RNA and cationic polymers specifically designed to deliver exogenous genetic material to cells by a process called transfection. There is a general consensus that a subtle balance between sufficient extracellular protection and intracellular release of nucleic acids is a key factor for successful gene delivery. Therefore, there is a strong need to develop suitable tools and techniques for enabling the monitoring of the stability of polyplexes in the biological environment they face during transfection. In this work we propose time-resolved fluorescence spectroscopy in combination with SYBR Green I-DNA dye as a reliable tool for the in-depth characterization of the DNA/vector complexation state. As a proof of concept, we provide essential information on the assembly and disassembly of complexes formed between DNA and each of three cationic polymers, namely a novel promising chitosan-graft-branched polyethylenimine copolymer (Chi-g-bPEI), one of its building block 2 kDa bPEI and the gold standard transfectant 25 kDa bPEI. Our results highlight the higher information content provided by the time-resolved studies of SYBR Green I/DNA, as compared to conventional steady state measurements of ethidium bromide/DNA that enabled us to draw relationships among fluorescence lifetime, polyplex structural changes and transfection efficiency.

  7. Formation of the -N(NO)N(NO)- polymer at high pressure and stabilization at ambient conditions.

    PubMed

    Xiao, Hai; An, Qi; Goddard, William A; Liu, Wei-Guang; Zybin, Sergey V

    2013-04-02

    A number of exotic structures have been formed through high-pressure chemistry, but applications have been hindered by difficulties in recovering the high-pressure phase to ambient conditions (i.e., one atmosphere and 300 K). Here we use dispersion-corrected density functional theory [PBE-ulg (Perdew-Burke-Ernzerhof flavor of DFT with the universal low gradient correction for long range London dispersion)] to predict that above 60 gigapascal (GPa) the most stable form of N2O (the laughing gas in its molecular form) is a one-dimensional polymer with an all-nitrogen backbone analogous to cis-polyacetylene in which alternate N are bonded (ionic covalent) to O. The analogous trans-polymer is only 0.03∼0.10 eV/molecular unit less stable. Upon relaxation to ambient conditions, both polymers relax below 14 GPa to the same stable nonplanar trans-polymer. The predicted phonon spectrum and dissociation kinetics validates the stability of this trans-poly-NNO at ambient conditions, which has potential applications as a type of conducting nonlinear optical polymer with all-nitrogen chains and as a high-energy oxidizer for rocket propulsion. This work illustrates in silico materials discovery particularly in the realm of extreme conditions (very high pressure or temperature).

  8. Formation of the –N(NO)N(NO)– polymer at high pressure and stabilization at ambient conditions

    PubMed Central

    Xiao, Hai; An, Qi; Goddard, William A.; Liu, Wei-Guang; Zybin, Sergey V.

    2013-01-01

    A number of exotic structures have been formed through high-pressure chemistry, but applications have been hindered by difficulties in recovering the high-pressure phase to ambient conditions (i.e., one atmosphere and 300 K). Here we use dispersion-corrected density functional theory [PBE-ulg (Perdew-Burke-Ernzerhof flavor of DFT with the universal low gradient correction for long range London dispersion)] to predict that above 60 gigapascal (GPa) the most stable form of N2O (the laughing gas in its molecular form) is a one-dimensional polymer with an all-nitrogen backbone analogous to cis-polyacetylene in which alternate N are bonded (ionic covalent) to O. The analogous trans-polymer is only 0.03∼0.10 eV/molecular unit less stable. Upon relaxation to ambient conditions, both polymers relax below 14 GPa to the same stable nonplanar trans-polymer. The predicted phonon spectrum and dissociation kinetics validates the stability of this trans-poly-NNO at ambient conditions, which has potential applications as a type of conducting nonlinear optical polymer with all-nitrogen chains and as a high-energy oxidizer for rocket propulsion. This work illustrates in silico materials discovery particularly in the realm of extreme conditions (very high pressure or temperature). PMID:23503849

  9. Factors that influence the formation and stability of hydrated ferrous sulfate in coal dusts. Possible relation to the emphysema of coal miners

    SciTech Connect

    Huang, Xi; Zalma, R.; Pezerat, H.

    1994-05-01

    Epidemiological studies have shown that a causal relationship may exist between coal dust exposure and emphysema in coal miners. Emphysema can be considered as one of the human pathologies associated with oxidative stress, resulting from oxidant-induced {alpha}{sub 1}-antitrypsin ({alpha}{sub 1}-AT) inactivation and uncontrolled proteolysis of lung tissue. We have previously reported that certain coal dusts contained hydrated ferrous sulfate (FeSO{sub 4}) that inactivated {alpha}{sub 1}-AT. In the present study, we have shown that the FeSO{sub 4} originated from oxidation of pyrite (FeS{sub 2}), which is a typical contaminant of coal dusts. The relative humidity and microenvironmental around individual pyrite particles influence the formation of FeSO{sub 4} in the coal. However, the subsequent human exposure to coal dust containing FeSO{sub 4} depends on the stability of the formed FeSO{sub 4}. We found that pH played the most important role in stabilizing the FeSO{sub 4}, such that a final pH < 4.5 after oxidation of pyrite stabilized FeSO{sub 4}, whereas at high pH the conversion of reactive Fe{sup 2+} to Fe{sup 3+} was immediate. Sulfuric acid (H{sub 2}SO{sub 4}), which is also produced by the oxidation of pyrite, can lower the pH, but it can also be neutralized by other minerals in coal dusts, such as calcite (CaCO{sub 3}). The stability of FeSO{sub 4} in coal dust can also be influenced by the length of exposure to air. Our studies demonstrated that coal samples differed in their capacity to stabilize FeSO{sub 4}. This current study strengthens our previous reported hypothesis that emphysema, which occurs irregularly in coal miners, could be directly related to exposure to coal dust containing FeSO{sub 4}. 35 refs., 3 figs., 4 tabs.

  10. A Benchmarking Analysis for Five Radionuclide Vadose Zone Models (Chain, Multimed{_}DP, Fectuz, Hydrus, and Chain 2D) in Soil Screening Level Calculations

    SciTech Connect

    Chen, J-S.; Drake, R.; Lin, Z.; Jewett, D. G.

    2002-02-26

    Five vadose zone models with different degrees of complexity (CHAIN, MULTIMED{_}DP, FECTUZ, HYDRUS, and CHAIN 2D) were selected for use in radionuclide soil screening level (SSL) calculations. A benchmarking analysis between the models was conducted for a radionuclide ({sup 99}Tc) release scenario at the Las Cruces Trench Site in New Mexico. Sensitivity of three model outputs to the input parameters were evaluated and compared among the models. The three outputs were peak contaminant concentrations, time to peak concentrations at the water table, and time to exceed the contaminants maximum critical level at a representative receptor well. Model parameters investigated include soil properties such as bulk density, water content, soil water retention parameters and hydraulic conductivity. Chemical properties examined include distribution coefficient, radionuclide half-life, dispersion coefficient, and molecular diffusion. Other soil characteristics, such as recharge rate, also were examined. Model sensitivity was quantified in the form of sensitivity and relative sensitivity coefficients. Relative sensitivities were used to compare the sensitivities of different parameters. The analysis indicates that soil water content, recharge rate, saturated soil water content, and soil retention parameter, {beta}, have a great influence on model outputs. In general, the results of sensitivities and relative sensitivities using five models are similar for a specific scenario. Slight differences were observed in predicted peak contaminant concentrations due to different mathematical treatment among models. The results of benchmarking and sensitivity analysis would facilitate the model selection and application of the model in SSL calculations.

  11. Facile Formation of Redox-Active Totally Organic Nanoparticles in Water by In Situ Reduction of Organic Precursors Stabilized through Aromatic-Aromatic Interactions by Aromatic Polyelectrolytes.

    PubMed

    Flores, Mario E; Garcés-Jerez, Pablo; Fernández, Daniel; Aros-Perez, Gustavo; González-Cabrera, Diego; Álvarez, Eduardo; Cañas, Ignacio; Oyarzun-Ampuero, Felipe; Moreno-Villoslada, Ignacio

    2016-11-01

    The formation of redox-active, totally organic nanoparticles in water is achieved following a strategy similar to that used to form metal nanoparticles. It is based on two fundamental concepts: i) complexation through aromatic-aromatic interactions of a water-soluble precursor aromatic molecule with polyelectrolytes bearing complementary charged aromatic rings, and ii) reduction of the precursor molecule to achieve stabilized nanoparticles. Thus, formazan nanoparticles are synthesized by reduction of a tetrazolium salt with ascorbic acid using polyelectrolytes bearing benzene sulfonate residues of high linear aromatic density, but cannot be formed in the presence of nonaromatic polyelectrolytes. The red colored nanoparticles are efficiently encapsulated in calcium alginate beads, showing macroscopic homogeneity. Bleaching kinetics with chlorine show linear rates on the order of tenths of milli-meters per minute. A linear behavior of the dependence of the rate of bleaching on the chlorine concentration is found, showing the potential of the nanoparticles for chlorine sensing.

  12. Stability of Microturbulent Drift Modes during Internal Transport Barrier Formation in the Alcator C-Mod Radio Frequency Heated H-mode

    SciTech Connect

    M.H. Redi; C.L. Fiore; W. Dorland; D.R. Mikkelsen; G. Rewoldt; P.T. Bonoli; D.R. Ernst; J.E. Rice; S.J. Wukitch

    2003-11-20

    Recent H-mode experiments on Alcator C-Mod [I.H. Hutchinson, et al., Phys. Plasmas 1 (1994) 1511] which exhibit an internal transport barrier (ITB), have been examined with flux tube geometry gyrokinetic simulations, using the massively parallel code GS2 [M. Kotschenreuther, G. Rewoldt, and W.M. Tang, Comput. Phys. Commun. 88 (1995) 128]. The simulations support the picture of ion/electron temperature gradient (ITG/ETG) microturbulence driving high xi/ xe and that suppressed ITG causes reduced particle transport and improved ci on C-Mod. Nonlinear calculations for C-Mod confirm initial linear simulations, which predicted ITG stability in the barrier region just before ITB formation, without invoking E x B shear suppression of turbulence. Nonlinear fluxes are compared to experiment, which both show low heat transport in the ITB and higher transport within and outside of the barrier region.

  13. ATF7IP-Mediated Stabilization of the Histone Methyltransferase SETDB1 Is Essential for Heterochromatin Formation by the HUSH Complex.

    PubMed

    Timms, Richard T; Tchasovnikarova, Iva A; Antrobus, Robin; Dougan, Gordon; Lehner, Paul J

    2016-10-11

    The histone methyltransferase SETDB1 plays a central role in repressive chromatin processes, but the functional requirement for its binding partner ATF7IP has remained enigmatic. Here, we show that ATF7IP is essential for SETDB1 stability: nuclear SETDB1 protein is degraded by the proteasome upon ablation of ATF7IP. As a result, ATF7IP is critical for repression that requires H3K9 trimethylation by SETDB1, including transgene silencing by the HUSH complex. Furthermore, we show that loss of ATF7IP phenocopies loss of SETDB1 in genome-wide assays. ATF7IP and SETDB1 knockout cells exhibit near-identical defects in the global deposition of H3K9me3, which results in similar dysregulation of the transcriptome. Overall, these data identify a critical functional role for ATF7IP in heterochromatin formation by regulating SETDB1 abundance in the nucleus.

  14. Understanding the Mechanism of the Divergent Reactivity of Non-Heteroatom-Stabilized Chromium Carbene Complexes with Furfural Imines: Formation of Benzofurans and Azetines.

    PubMed

    Funes-Ardoiz, Ignacio; González, Jairo; Santamaría, Javier; Sampedro, Diego

    2016-02-19

    The mechanisms of the reaction between non-heteroatom-stabilized alkynyl chromium carbene complexes prepared in situ and furfural imines to yield benzofurans and/or azetines have been explored by means of density functional theory method calculations. The reaction proceeds through a complex cascade of steps triggered by a nucleophilic addition of the imine nitrogen atom. The formation of two benzofuran regioisomers has been explained in terms of competitive nucleophilic attacks to different positions of the carbene complex. Each of these regioisomers can be obtained as the major product depending on the starting materials. The overall sequence could be controlled to yield benzofurans or azetines by adjusting the substituents present in the initial carbene complex. This mechanistic information allowed for the preparation of new benzofurans and azetinylcarbenes in good yields.

  15. Influence of Water Content on the β-Sheet Formation, Thermal Stability, Water Removal, and Mechanical Properties of Silk Materials.

    PubMed

    Yazawa, Kenjiro; Ishida, Kana; Masunaga, Hiroyasu; Hikima, Takaaki; Numata, Keiji

    2016-03-14

    Silk, which has excellent mechanical toughness and is lightweight, is used as a structural material in nature, for example, in silkworm cocoons and spider draglines. However, the industrial use of silk as a structural material has garnered little attention. For silk to be used as a structural material, its thermal processability and associated properties must be well understood. Although water molecules influence the glass transition of silk, the effects of water content on the other thermal properties of silks are not well understood. In this study, we prepared Bombyx mori cocoon raw fibers, degummed fibers, and films with different water contents and then investigated the effects of water content on crystallization, degradation, and water removal during thermal processing. Thermal gravimetric analyses of the silk materials showed that water content did not affect the thermal degradation temperature but did influence the water removal behavior. By increasing the water content of silk, the water molecules were removed at lower temperatures, indicating that the amount of free water in silk materials increased; additionally, the glass transition temperature decreased with increasing water plasticization. Differential scanning calorimetry and wide-angle X-ray scattering of the silk films also suggested that the water molecules in the amorphous regions of the silk films acted as a plasticizer and induced β-sheet crystallization. The plasticizing effect of water was not detected in silk fibers, owing to their lower amorphous content and mobility. The structural and mechanical characterizations of the silk films demonstrated the silk film prepared at RH 97% realized both crystallinity and ductility simultaneously. Thus, the thermal stability, mechanical, and other properties of silk materials are regulated by their water content and crystallinity.

  16. Interface stability of a TiO₂/3-methoxypropionitrile-based electrolyte: first evidence for solid electrolyte interphase formation and implications.

    PubMed

    Flasque, Miguel; Van Nhien, Albert Nguyen; Swiatowska, Jolanta; Seyeux, Antoine; Davoisne, Carine; Sauvage, Frédéric

    2014-04-14

    We report an in-depth study focusing on the stability of a benchmark electrolyte composition based on a low-volatile 3-methoxypropionitrile (MPN) solvent employed in dye-sensitized solar cells. In the presence of TiO2, the semi-conductor surface plays a catalytic role in the thermal degradation of the electrolyte, which induces, among other effects, the nucleation and growth of a uniform solid electrolyte interphase (SEI) layer that wraps TiO2. On the basis of our actual understanding, we argue that SEI formation is responsible for triiodide depletion in the electrolyte during ageing and also has a simultaneous impact on TiO2 optoelectronic properties through the onset of a visible-light absorption tail, energy modification of intraband trap states, and the induction of an increase in both electron lifetime and transport time in TiO2. In-depth characterization of this layer by using XPS and ToF-SIMS indicates that the chemical composition of this SEI results from solvent and additive degradation, that is, iodide, sulfur, cyano, nitrogen, carbon, and imidazolium rings. The SEI thickness, its content, and the concentration profile strongly vary depending on the ageing conditions. The outcome of this new finding is discussed in comparison with literature observations and stresses the difficulties in reaching long-term stability at 85 °C by using MPN-based electrolytes unless new interfacial engineering is accomplished to impede pinholes between dye molecules on TiO2.

  17. Chemical stabilization and improved thermal resilience of molecular arrangements: possible formation of a surface network of bonds by multiple pulse atomic layer deposition.

    PubMed

    de Pauli, Muriel; Matos, Matheus J S; Siles, Pablo F; Prado, Mariana C; Neves, Bernardo R A; Ferreira, Sukarno O; Mazzoni, Mário S C; Malachias, Angelo

    2014-08-14

    In this work, we make use of an atomic layer deposition (ALD) surface reaction based on trimethyl-aluminum (TMA) and water to modify O-H terminated self-assembled layers of octadecylphosphonic acid (OPA). The structural modifications were investigated by X-ray reflectivity, X-ray diffraction, and atomic force microscopy. We observed a significant improvement in the thermal stability of ALD-modified molecules, with the existence of a supramolecular packing structure up to 500 °C. Following the experimental observations, density functional theory (DFT) calculations indicate the possibility of formation of a covalent network with aluminum atoms connecting OPA molecules at terrace surfaces. Chemical stability is also achieved on top of such a composite surface, inhibiting further ALD oxide deposition. On the other hand, in the terrace edges, where the covalent array is discontinued, the chemical conditions allow for oxide growth. Analysis of the DFT results on band structure and density of states of modified OPA molecules suggests that besides the observed thermal resilience, the dielectric character of OPA layers is preserved. This new ALD-modified OPA composite is potentially suitable for applications such as dielectric layers in organic devices, where better thermal performance is required.

  18. Mechanical shear contributes to granule formation resulting in quick start-up and stability of a hybrid anammox reactor.

    PubMed

    Gao, Yanning; Liu, Zhijun; Liu, Fengxia; Furukawa, Kenji

    2012-06-01

    It appears that if suspended biomass washout can be reduced effectively, granule formation will be fastened in fluidized bed. Quicker reactor start-up can be anticipated especially for those system keeping slow growth bacteria such as anammox. A hybrid reactor combined fixed-bed with nonwoven fabrics as biomass carrier and fluidized bed with slow speed mechanical stirring was therefore developed, and its nitrogen removal performances was evaluated experimentally. Only in 38 days, the total nitrogen removal rate (NRR) reached to 1.9 kg(N) m(-3) day (-1) and then doubled within 17 days, with total nitrogen removal efficiency kept above 70%. After 180 days reactor operating, the NRR reached a maximum value of 6.6 kg(N) m(-3) day(-1) and the specific anammox activity was gradually constant in 0.32 kg(N) kg(VSS)(-1) day(-1). Biomass attached on nonwoven fabrics could additionally improve reactor nitrogen removal by 8%. The dominant size of granular sludge reached to 0.78 mm with stirring speed adjusted from 30 to 80 rpm and the hydraulic retention time (HRT) from 8 to 1.5 h during the whole operating time. Scanning electron microscope observation showed especially compact structure of granular sludge. A 70% of anammox bacteria percentage was identified by fluorescence in situ hybridization analysis.

  19. Surface-Induced Phase of Tyrian Purple (6,6′-Dibromoindigo): Thin Film Formation and Stability

    PubMed Central

    2016-01-01

    The appearance of surface-induced phases of molecular crystals is a frequently observed phenomenon in organic electronics. However, despite their fundamental importance, the origin of such phases is not yet fully resolved. The organic molecule 6,6′-dibromoindigo (Tyrian purple) forms two polymorphs within thin films. At growth temperatures of 150 °C, the well-known bulk structure forms, while at a substrate temperature of 50 °C, a surface-induced phase is observed instead. In the present work, the crystal structure of the surface-induced polymorph is solved by a combined experimental and theoretical approach using grazing incidence X-ray diffraction and molecular dynamics simulations. A comparison of both phases reveals that π–π stacking and hydrogen bonds are common motifs for the intermolecular packing. In-situ temperature studies reveal a phase transition from the surface-induced phase to the bulk phase at a temperature of 210 °C; the irreversibility of the transition indicates that the surface-induced phase is metastable. The crystallization behavior is investigated ex-situ starting from the sub-monolayer regime up to a nominal thickness of 9 nm using two different silicon oxide surfaces; island formation is observed together with a slight variation of the crystal structure. This work shows that surface-induced phases not only appear for compounds with weak, isotropic van der Waals bonds, but also for molecules exhibiting strong and highly directional hydrogen bonds. PMID:27418882

  20. On the crucial importance of the pH for the formation and self-stabilization of protein microgels and strands.

    PubMed

    Phan-Xuan, Tuan; Durand, Dominique; Nicolai, Taco; Donato, Laurence; Schmitt, Christophe; Bovetto, Lionel

    2011-12-20

    Stable suspensions of protein microgels are formed by heating salt-free β-lactoglobulin solutions at concentrations up to about C = 50 g·L(-1) if the pH is set within a narrow range between 5.75 and 6.1. The internal protein concentration of these spherical particles is about 150 g·L(-1) and the average hydrodynamic radius decreases with increasing pH from 200 to 75 nm. The formation of the microgels leads to an increase of the pH, which is a necessary condition to obtain stable suspensions. The spontaneous increase of the pH during microgel formation leads to an increase of their surface charge density and inhibits secondary aggregation. This self-stabilization mechanism is not sufficient if the initial pH is below 5.75 in which case secondary aggregation leads to precipitation. Microgels are no longer formed above a critical initial pH, but instead short, curved protein strands are obtained with a hydrodynamic radius of about 15-20 nm.

  1. Molybdenum-containing membrane-bound formate dehydrogenase isolated from Citrobacter sp. S-77 having high stability against oxygen, pH, and temperature.

    PubMed

    Nguyen, Nga T; Yatabe, Takeshi; Yoon, Ki-Seok; Ogo, Seiji

    2014-10-01

    Membrane-bound formate dehydrogenase (FDH) was purified to homogeneity from a facultative anaerobic bacterium Citrobacter sp. S-77. The FDH from Citrobacter sp. S-77 (FDHS77) was a monomer with molecular mass of approximately 150 kDa. On SDS-PAGE, the purified FDHS77 showed as three different protein bands with molecular mass of approximately 95, 87, and 32 kDa, respectively. Based on the N-terminal amino acid sequence analysis, the sequence alignments observed for the 87 kDa protein band were identical to that of the large subunit of 95 kDa, indicating that the purified FDHS77 consisted of two subunits; a 95 kDa large subunit and a 32 kDa small subunit. The purified FDHS77 in this purification did not contain a heme b subunit, but the FDHS77 showed significant activity for formate oxidation, determined by the Vmax of 30.4 U/mg using benzyl viologen as an electron acceptor. The EPR and ICP-MS spectra indicate that the FDHS77 is a molybdenum-containing enzyme, displaying a remarkable O2-stability along with thermostability and pH resistance. This is the first report of the purification and characterization of a FDH from Citrobacter species.

  2. Formation and Stability of Equiatomic and Nonequiatomic Nanocrystalline CuNiCoZnAlTi High-Entropy Alloys by Mechanical Alloying

    NASA Astrophysics Data System (ADS)

    Varalakshmi, S.; Kamaraj, M.; Murty, B. S.

    2010-10-01

    Nanocrystalline equiatomic high-entropy alloys (HEAs) have been synthesized by mechanical alloying in the Cu-Ni-Co-Zn-Al-Ti system from the binary CuNi alloy to the hexanary CuNiCoZnAlTi alloy. An attempt also has been made to find the influence of nonequiatomic compositions on the HEA formation by varying the Cu content up to 50 at. pct (Cu x NiCoZnAlTi; x = 0, 8.33, 33.33, 49.98 at. pct). The phase formation and stability of mechanically alloyed powder at an elevated temperature (1073 K [800 °C] for 1 hour) were studied. The nanocrystalline equiatomic Cu-Ni-Co-Zn-Al-Ti alloys have a face-centered cubic (fcc) structure up to quinary compositions and have a body-centered cubic (bcc) structure in a hexanary alloy. In nonequiatomic alloys, bcc is the dominating phase in the alloys containing 0 and 8.33 at. pct of Cu, and the fcc phase was observed in alloys with 33.33 and 49.98 at. pct of Cu. The Vicker’s bulk hardness and compressive strength of the equiatomic nanocrystalline hexanary CuNiCoZnAlTi HEA after hot isostatic pressing is 8.79 GPa, and the compressive strength is 2.76 GPa. The hardness of these HEAs is higher than most commercial hard facing alloys ( e.g., Stellite, which is 4.94 GPa).

  3. Geotechnical Characterization and Stability of a Slope in the Marnoso-Arenacea Formation for the Realization of an Underground Car Park in Urbino (Italy)

    NASA Astrophysics Data System (ADS)

    Gori, Umberto; Polidori, Ennio; Tonelli, Gianluigi; Veneri, Francesco

    The plan of an underground car park located near the historical centre of Urbino town, has required characterizing the Marnoso-Arenacea Formation (Tortonian), from a geomechanical point of view. The project implies that the intervention will be insert inside the flank of the hill, in order to mitigate the effect of the environmental impact. It also involves an excavation front 42 m high and 100 m large. To analyze the mechanical behaviour of the soils, many samples both from the Marnoso-Arenacea Formation and from the cover, have been tested in laboratory. The anisotropy index evaluated by point load test in natural water conditions shows a higher value of the arenitic levels in comparison with the marls. On the contrary, the marls level tested in dry condition provides greater anisotropy index data. In the mono-axial compression test the arenaceous sediments show higher results. The stability analysis carried out with distinct element method shows the opportunity to retain the upper part of the cut with anchored bulkhead.

  4. A new look at the statistical assessment of approximate and rigorous methods for the estimation of stabilized formation temperatures in geothermal and petroleum wells

    NASA Astrophysics Data System (ADS)

    Espinoza-Ojeda, O. M.; Santoyo, E.; Andaverde, J.

    2011-06-01

    Approximate and rigorous solutions of seven heat transfer models were statistically examined, for the first time, to estimate stabilized formation temperatures (SFT) of geothermal and petroleum boreholes. Constant linear and cylindrical heat source models were used to describe the heat flow (either conductive or conductive/convective) involved during a borehole drilling. A comprehensive statistical assessment of the major error sources associated with the use of these models was carried out. The mathematical methods (based on approximate and rigorous solutions of heat transfer models) were thoroughly examined by using four statistical analyses: (i) the use of linear and quadratic regression models to infer the SFT; (ii) the application of statistical tests of linearity to evaluate the actual relationship between bottom-hole temperatures and time function data for each selected method; (iii) the comparative analysis of SFT estimates between the approximate and rigorous predictions of each analytical method using a β ratio parameter to evaluate the similarity of both solutions, and (iv) the evaluation of accuracy in each method using statistical tests of significance, and deviation percentages between 'true' formation temperatures and SFT estimates (predicted from approximate and rigorous solutions). The present study also enabled us to determine the sensitivity parameters that should be considered for a reliable calculation of SFT, as well as to define the main physical and mathematical constraints where the approximate and rigorous methods could provide consistent SFT estimates.

  5. The Combined Effect of High Hydrostatic Pressure and Calcium Salts on the Stability, Solubility and Gel Formation of β-Lactoglobulin

    PubMed Central

    Saalfeld, Daniel; Riegel, Ina; Kulozik, Ulrich; Gebhardt, Ronald

    2015-01-01

    Stability, aggregation and gelation of β-Lactoglobulin are affected by high pressure and salts of the Hofmeister series. Little is known about their combined effects on structure formation processes of β-Lactoglobulin, mainly because many salts of the series are not suitable for use in food. Here, we investigate the effect of calcium salts on the strength of pressure-induced gels, inspired by the fact that high pressure and salts change the water structure in a similar way. We find that the larger the applied pressures, the higher the strength of the gels. In addition to pressure, there is a significant influence by the type of anions and the amount of added calcium salts. Gel strength increases in the order CaCl2 < Ca (NO3)2 < CaI2. This trend correlates with the position of the salts in the Hofmeister series. The results are explained by analogy with the thermal aggregate formation by taking reaction rates for unfolding and aggregation, as well as specific/non-specific salts effect into consideration. PMID:28231200

  6. The formation of a hydroxyl bond and the effects thereof on bone-like apatite formation on a magnesia partially stabilized zirconia (MgO-PSZ) bioceramic following CO2 laser irradiation.

    PubMed

    Hao, L; Lawrence, J; Chian, K S; Low, D K Y; Lim, G C; Zheng, H Y

    2004-09-01

    For the purpose of improving the bioactivity of a magnesia partially stabilized zirconia (MgO-PSZ) and to explore a new technique for inducing OH group and apatite formation, a CO(2) laser has been used to modified the surface properties. The bioactivity of the CO(2) laser modified MgO-PSZ has been investigated in stimulated human fluids (SBF) with ion concentrations almost equal to those in human blood plasma. Some hydroxyl groups were found on the MgO-PSZ following CO(2) laser treatment with selected power densities. The surface melting on the MgO-PSZ induced by CO(2) laser processing provides the Zr(4+) ion and OH(-) ion, in turn, the incorporation of the Zr(4+) ion and the OH(-) ion creates the Zr-OH group on the surface. After 14 days of SBF soaking, the apatites formed on the MgO-PSZ with relatively high amount of hydroxyl groups generated by the CO(2) laser treatment, while no apatite was observed on the untreated with few hydroxyl groups. It exhibits that the Zr-OH groups on the MgO-PSZ surface is the functional groups to facilitate the apatite formation. The increased surface roughness provides more active sites, meantime, increased surface energy benefits to the adsorption and reaction on the surface.

  7. Cysteine residues in the major capsid protein, Vp1, of the JC virus are important for protein stability and oligomer formation.

    PubMed

    Kobayashi, Shintaro; Suzuki, Tadaki; Igarashi, Manabu; Orba, Yasuko; Ohtake, Noriko; Nagakawa, Keita; Niikura, Kenichi; Kimura, Takashi; Kasamatsu, Harumi; Sawa, Hirofumi

    2013-01-01

    The capsid of the human polyomavirus JC virus (JCV) consists of 72 pentameric capsomeres of a major structural protein, Vp1. The cysteine residues of the related Vp1 of SV40 are known to contribute to Vp1 folding, pentamer formation, pentamer-pentamer contacts, and capsid stabilization. In light of the presence of a slight structural difference between JCV Vp1 and SV40 counterpart, the way the former folds could be either different from or similar to the latter. We found a difference: an important contribution of Vp1 cysteines to the formation of infectious virions, unique in JCV and absent in SV40. Having introduced amino acid substitution at each of six cysteines (C42, C80, C97, C200, C247, and C260) in JCV Vp1, we found that, when expressed in HeLa cells, the Vp1 level was decreased in C80A and C247A mutants, and remained normal in the other mutants. Additionally, the C80A and C247A Vp1-expressing cell extracts did not show the hemagglutination activity characteristic of JCV particles. The C80A and C247A mutant Vp1s were found to be less stable than the wild-type Vp1 in HeLa cells. When produced in a reconstituted in vitro protein translation system, these two mutant proteins were stable, suggesting that some cellular factors were responsible for their degradation. As determined by their sucrose gradient sedimentation profiles, in vitro translated C247A Vp1 formed pentamers, but in vitro translated C80A Vp1 was entirely monomeric. When individually incorporated into the JCV genome, the C80A and C247A mutants, but not the other Vp1 cysteine residues mutants, interfered with JCV infectivity. Furthermore, the C80A, but not the C247A, mutation prevented the nuclear localization of Vp1 in JCV genome transfected cells. These findings suggest that C80 of JCV Vp1 is required for Vp1 stability and pentamer formation, and C247 is involved in capsid assembly in the nucleus.

  8. A UV-vis study of the effects of alcohols on formation and stability of Mn(por)(O)(OAc) complexes.

    PubMed

    Mohajer, Daryoush; Jahanbani, Maryam

    2012-06-01

    Interactions of three different (acetato) (tetraarylporphyrinato) manganese (III) Mn(III)(por) with tetra-n-butylammonium hydrogen monopersulfate (n-Bu(4)NHSO(5)), in the presence of excess tetra-n-butylammonium acetate (n-Bu(4)NOAc) and in the absence or presence of various alcohols (alcohols=CH(3)OH, C(2)H(5)OH, i-C(3)H(7)OH, t-C(4)H(9)OH) in CH(2)Cl(2), were monitored by their UV-vis spectral changes, under identical conditions, at room temperature. (Acetato) (tetrakispentafluorophenylporphyrinato) manganese (III) Mn(III)(tpfpp)(OAc) and (acetato) (tetramesitylporphyrinato) manganese (III) Mn(III)(tmp)(OAc) produced their corresponding high valent Mn(tpfpp)(O)(OAc) and Mn(tmp)(O)(OAc) both in the absence or presence of alcohols. Whereas, (acetato) (tetraphenylporphyrinato) manganese (III) Mn(III)(tpp)(OAc) only generated Mn(tpp)(O)(OAc) in the presence of less bulky alcohols. In the absence of alcohols or in the presence of t-C(4)H(9)OH, the UV-vis spectra displayed a very weak sign of formation of Mn(tpp)(O)(OAc) complex. It was observed that alcohols generally increased the rate of formation of Mn-oxo species in accordance with their acidity or hydrogen bonding strength, and enhanced the stability of Mn-oxo complexes, as their size increases. Attempts are made to explain these effects. A mechanistic scheme is also suggested for the decomposition of HSO(5)(-) to O(2) and HSO(4)(-), through the formation and dimerization of Mn-oxo species.

  9. A UV-vis study of the effects of alcohols on formation and stability of Mn(por)(O)(OAc) complexes

    NASA Astrophysics Data System (ADS)

    Mohajer, Daryoush; Jahanbani, Maryam

    2012-06-01

    Interactions of three different (acetato) (tetraarylporphyrinato) manganese (III) MnIII(por) with tetra-n-butylammonium hydrogen monopersulfate (n-Bu4NHSO5), in the presence of excess tetra-n-butylammonium acetate (n-Bu4NOAc) and in the absence or presence of various alcohols (alcohols = CH3OH, C2H5OH, i-C3H7OH, t-C4H9OH) in CH2Cl2, were monitored by their UV-vis spectral changes, under identical conditions, at room temperature. (Acetato) (tetrakispentafluorophenylporphyrinato) manganese (III) MnIII(tpfpp)(OAc) and (acetato) (tetramesitylporphyrinato) manganese (III) MnIII(tmp)(OAc) produced their corresponding high valent Mn(tpfpp)(O)(OAc) and Mn(tmp)(O)(OAc) both in the absence or presence of alcohols. Whereas, (acetato) (tetraphenylporphyrinato) manganese (III) MnIII(tpp)(OAc) only generated Mn(tpp)(O)(OAc) in the presence of less bulky alcohols. In the absence of alcohols or in the presence of t-C4H9OH, the UV-vis spectra displayed a very weak sign of formation of Mn(tpp)(O)(OAc) complex. It was observed that alcohols generally increased the rate of formation of Mn-oxo species in accordance with their acidity or hydrogen bonding strength, and enhanced the stability of Mn-oxo complexes, as their size increases. Attempts are made to explain these effects. A mechanistic scheme is also suggested for the decomposition of HSO5- to O2 and HSO4-, through the formation and dimerization of Mn-oxo species.

  10. DNA-based nanostructures: The effect of the base sequence on octamer formation from d(XGGYGGT) tetramolecular G-quadruplexes.

    PubMed

    D'Atri, Valentina; Borbone, Nicola; Amato, Jussara; Gabelica, Valérie; D'Errico, Stefano; Piccialli, Gennaro; Mayol, Luciano; Oliviero, Giorgia

    2014-04-01

    In a previous work we have demonstrated that the DNA sequence CGGTGGT folds into a higher order G-quadruplex structure (2Q), obtained by the 5'-5' stacking of two unusual G(:C):G(:C):G(:C):G(:C) planar octads belonging to two identical tetra-stranded parallel quadruplexes, when annealed in the presence of ammonium or potassium ions. In the present paper, we discuss the role played by the title nucleosides X and Y (where X and Y stand for A, C, G, or T) on the formation and stability of 2Q structures formed by the XGGYGGT oligodeoxynucleotides. We found that the above mentioned dimerization pathway is not peculiar to the CGGTGGT sequence, but is possible for all the remaining CGGYGGT sequences (with Y = A, C, or G). Furthermore, we have found that the TGGAGGT sequence, despite the absence of the 5'-ending C, is also capable of forming a 2Q-like higher order quadruplex by using a slightly different dimerization interface, as characterized by NMR spectroscopy. To the best of our knowledge, this is the first characterization of a quadruplex multimer formed by an oligodeoxynucleotide presenting a thymine at its 5'-end. Examples of such structures were observed previously only in crystals and in the presence of non-physiological cations. Our results expand the repertoire of DNA quadruplex nanostructures of chosen length and add further complexity to the structural polymorphism of G-rich DNA sequences.

  11. Effect of hygroscopicity of the metal salt on the formation and air stability of lyotropic liquid crystalline mesophases in hydrated salt-surfactant systems.

    PubMed

    Albayrak, Cemal; Barım, Gözde; Dag, Ömer

    2014-11-01

    It is known that alkali, transition metal and lanthanide salts can form lyotropic liquid crystalline (LLC) mesophases with non-ionic surfactants (such as CiH2i+1(OCH2CH2)jOH, denoted as CiEj). Here we combine several salt systems and show that the percent deliquescence relative humidity (%DRH) value of a salt is the determining parameter in the formation and stability of the mesophases and that the other parameters are secondary and less significant. Accordingly, salts can be divided into 3 categories: Type I salts (such as LiCl, LiBr, LiI, LiNO3, LiClO4, CaCl2, Ca(NO3)2, MgCl2, and some transition metal nitrates) have low %DRH and form stable salt-surfactant LLC mesophases in the presence of a small amount of water, type II salts (such as some sodium and potassium salts) that are moderately hygroscopic form disordered stable mesophases, and type III salts that have high %DRH values, do not form stable LLC mesophases and leach out salt crystals. To illustrate this effect, a large group of salts from alkali and alkaline earth metals were investigated using XRD, POM, FTIR, and Raman techniques. Among the different salts investigated in this study, the LiX (where X is Cl(-), Br(-), I(-), NO3(-), and ClO4(-)) and CaX2 (X is Cl(-), and NO3(-)) salts were more prone to establish LLC mesophases because of their lower %DRH values. The phase behavior with respect to concentration, stability, and thermal behavior of Li(I) systems were investigated further. It is seen that the phase transitions among different anions in the Li(I) systems follow the Hofmeister series.

  12. Proton-coupled electron transfer and adduct configuration are important for C4a-hydroperoxyflavin formation and stabilization in a flavoenzyme.

    PubMed

    Wongnate, Thanyaporn; Surawatanawong, Panida; Visitsatthawong, Surawit; Sucharitakul, Jeerus; Scrutton, Nigel S; Chaiyen, Pimchai

    2014-01-08

    Determination of the mechanism of dioxygen activation by flavoenzymes remains one of the most challenging problems in flavoenzymology for which the underlying theoretical basis is not well understood. Here, the reaction of reduced flavin and dioxygen catalyzed by pyranose 2-oxidase (P2O), a flavoenzyme oxidase that is unique in its formation of C4a-hydroperoxyflavin, was investigated by density functional calculations, transient kinetics, and site-directed mutagenesis. Based on work from the 1970s-1980s, the current understanding of the dioxygen activation process in flavoenzymes is believed to involve electron transfer from flavin to dioxygen and subsequent proton transfer to form C4a-hydroperoxyflavin. Our findings suggest that the first step of the P2O reaction is a single electron transfer coupled with a proton transfer from the conserved residue, His548. In fact, proton transfer enhances the electron acceptor ability of dioxygen. The resulting ·OOH of the open-shell diradical pair is placed in an optimal position for the formation of C4a-hydroperoxyflavin. Furthermore, the C4a-hydroperoxyflavin is stabilized by the side chains of Thr169, His548, and Asn593 in a "face-on" configuration where it can undergo a unimolecular reaction to generate H2O2 and oxidized flavin. The computational results are consistent with kinetic studies of variant forms of P2O altered at residues Thr169, His548, and Asn593, and kinetic isotope effects and pH-dependence studies of the wild-type enzyme. In addition, the calculated energy barrier is in agreement with the experimental enthalpy barrier obtained from Eyring plots. This work revealed new insights into the reaction of reduced flavin with dioxygen, demonstrating that the positively charged residue (His548) plays a significant role in catalysis by providing a proton for a proton-coupled electron transfer in dioxygen activation. The interaction around the N5-position of the C4a-hydroperoxyflavin is important for dictating the

  13. Elimination of a Free Cysteine by Creation of a Disulfide Bond Increases the Activity and Stability of Candida boidinii Formate Dehydrogenase

    PubMed Central

    Zheng, Junxian; Yang, Taowei; Zhou, Junping; Xu, Meijuan; Zhang, Xian

    2016-01-01

    ABSTRACT NAD+-dependent formate dehydrogenase (FDH; EC 1.2.1.2) is an industrial enzyme widely used for NADH regeneration. However, enzyme inactivation caused by the oxidation of cysteine residues is a flaw of native FDH. In this study, we relieved the oxidation of the free cysteine of FDH from Candida boidinii (CboFDH) through the construction of disulfide bonds between A10 and C23 as well as I239 and C262. Variants A10C, I239C, and A10C/I239C were obtained by the site-directed mutagenesis and their properties were studied. Results showed that there were no significant changes in the optimum temperature and pH between variants and wild-type CboFDH. However, the stabilities of all variant enzymes were improved. Specifically, the CboFDH variant A10C (A10Cfdh) showed a significant increase in copper ion resistance and acid resistance, a 6.7-fold increase in half-life at 60°C, and a 1.4-fold increase in catalytic efficiency compared with the wild type. Asymmetric synthesis of l-tert-leucine indicated that the process time was reduced by 40% with variant A10Cfdh, which benefited from the increase in catalytic efficiency. Circular dichroism analysis and molecular dynamics simulation indicated that variants that contained disulfide bonds lowered the overall root mean square deviation (RMSD) and consequently increased the protein rigidity without affecting the secondary structure of enzyme. This work is expected to provide a viable strategy to avoid the microbial enzyme inactivation caused by the oxidation of the free cysteine residues and improving their performances. IMPORTANCE FDH is widely used for NADH regeneration in dehydrogenase-based synthesis of optically active compounds to decrease the cost of production. This study highlighted a viable strategy that was used to eliminate the oxidation of free cysteine residues of FDH from Candida boidinii by the introduction of disulfide bonds. Using this strategy, we obtained a variant FDH with improved activity and

  14. Synthesis of Cu-rich, Al2O3-stabilized oxygen carriers using a coprecipitation technique: redox and carbon formation characteristics.

    PubMed

    Imtiaz, Qasim; Kierzkowska, Agnieszka M; Broda, Marcin; Müller, Christoph R

    2012-03-20

    Chemical looping combustion (CLC) is an emerging, new technology for carbon capture and storage (CCS). Copper-based oxygen carriers are of particular interest due to their high oxygen carrying capacity and reactivity, low tendency for carbon deposition, and exothermic reduction reactions. In this work, CuO-based and Al(2)O(3)-stabilized oxygen carriers with high CuO loadings were developed using a coprecipitation technique. The cyclic redox performance of the synthesized oxygen carriers was evaluated at 800 °C in a laboratory-scale fluidized bed reactor using a reducing atmosphere comprising 10 vol. % CH(4) and 90 vol. % N(2). The CuO content in the oxygen carrier was found to increase with the pH value at which the coprecipitation was performed. The oxygen carrying capacity of the oxygen carrier containing 87.8 wt % CuO was found to be high (5.5 mmol O(2)/g oxygen carrier) and stable over 25 redox cycles. Increasing the CuO content further, i.e. > 90 wt %, resulted in materials which showed a decreasing oxygen carrying capacity with cycle number. It was also shown that the incorporation of K(+) ions in the oxygen carrier can avoid the formation of the spinel CuAl(2)O(4) and significantly reduce carbon deposition.

  15. H2SO4 formation from the gas-phase reaction of stabilized Criegee Intermediates with SO2: Influence of water vapour content and temperature

    NASA Astrophysics Data System (ADS)

    Berndt, Torsten; Jokinen, Tuija; Sipilä, Mikko; Mauldin, Roy L.; Herrmann, Hartmut; Stratmann, Frank; Junninen, Heikki; Kulmala, Markku

    2014-06-01

    The importance of gas-phase products from alkene ozonolysis other than OH radicals, most likely stabilized Criegee Intermediates (sCI), for the process of atmospheric SO2 oxidation to H2SO4 has been recently discovered. Subjects of this work are investigations on H2SO4 formation as a function of water vapour content (RH = 2-65%) and temperature (278-343 K) starting from the ozonolysis of trans-2-butene and 2,3-dimethyl-2-butene (TME). H2SO4 production other than via the OH radical reaction was attributed to the reaction of SO2 with sCI, i.e. acetaldehyde oxide arising from trans-2-butene ozonolysis and acetone oxide from TME. Measurements have been conducted in an atmospheric pressure flow tube using NO3--CI-APi-TOF mass spectrometry for H2SO4 detection. The sCI yields derived from H2SO4 measurements at 293 K were 0.49 ± 0.22 for acetaldehyde oxide and 0.45 ± 0.20 for acetone oxide. Our findings indicate a H2SO4 yield from sCI + SO2 of unity or close to unity. The deduced rate coefficient ratio for the reaction of sCI with H2O and SO2, k(sCI + H2O)/k(sCI + SO2), was found to be strongly dependent on the structure of the Criegee Intermediate, for acetaldehyde oxide at 293 K: (8.8 ± 0.4)·10-5 (syn- and anti-conformer in total) and for acetone oxide: <4·10-6. H2SO4 formation from sCI was pushed back with rising temperature in both reaction systems most probably due to an enhancement of sCI decomposition. The ratio k(dec)/k(sCI + SO2) increased by a factor of 34 (acetone oxide) increasing the temperature from 278 to 343 K. In the case of acetaldehyde oxide the temperature effect is less pronounced. The relevance of atmospheric H2SO4 formation via sCI + SO2 is discussed in view of its dependence on the structure of the Criegee Intermediate.

  16. A crossed molecular beams study on the formation and energetics of the resonantly stabilized free i-C4H3(X2A‧) radical and its isotopomers

    NASA Astrophysics Data System (ADS)

    Gu, Xibin; Guo, Ying; Zhang, Fangtong; Mebel, Alexander M.; Kaiser, Ralf I.

    2007-06-01

    The chemical dynamics of the formation of the i-C 4H 3(X 2A') radical together with its partially deuterated isotopomers were investigated in eight crossed molecular beams experiments of dicarbon molecules in their XΣg+ electronic ground and in first excited a 3Π u state with (partially deuterated) ethylene at collision energies between 12.1 and 40.9 kJ mol -1. The center-of-mass angular distributions suggest that the reaction dynamics on the singlet and triplet surfaces are indirect and involve butatriene reaction intermediates. In case of the C 2/C 2H 4 reaction, the 'symmetric' singlet butatriene intermediate would lead solely to a symmetric center-of-mass angular distribution; however, in combination with isotopically labeled reactants, we deduced that triplet butatriene intermediates excited to B/C like rotations likely account for the observed asymmetries in the center-of-mass angular distributions at higher collision energies. The translational energy distributions are also indicative of the involvement of both the triplet and singlet surfaces which lead both to the i-C 4H 3(X 2A') radicals through lose (singlet) and tight (triplet) exit transitions states. Also, our experiments helped to determine the enthalpy of formation of the i-C 4H 3(X 2A') radical to be about 504 ± 10 kJ mol -1 in good agreement with previous computational studies suggesting 498-499 kJ mol -1. The explicit identification of the resonance-stabilized i-C 4H 3(X 2A') radical proposes that the reaction of dicarbon with ethylene can lead to formation of i-C 4H 3(X 2A') in combustion flames; the n-C 4H 3(X 2A') isomer is not formed in this reaction. This conclusion correlates nicely with Hansen's et al. flame experiments at the advanced light source observing only the i-C 4H 3(X 2A') radical in hydrocarbon flames.

  17. mTFE3, an X-linked transcriptional activator containing basic helix-loop-helix and zipper domains, utilizes the zipper to stabilize both DNA binding and multimerization.

    PubMed Central

    Roman, C; Matera, A G; Cooper, C; Artandi, S; Blain, S; Ward, D C; Calame, K

    1992-01-01

    Southwestern (DNA-protein) screening of a murine L-cell cDNA library by using a probe for the microE3 site in the immunoglobulin heavy-chain enhancer yielded a clone, mTFE3, which is a member of the subset of basic helix-loop-helix (BHLH) proteins that also contain a leucine zipper (ZIP). Since the individual contribution of these domains is not well understood for proteins which contain them both, mutational analyses were performed to assess the functional roles of the HLH and ZIP regions for DNA binding and multimerization. The HLH region is stringently required for DNA binding but not for multimerization. The ZIP region is not stringently required for binding or multimerization, but stabilizes both multimer formation and DNA binding. A high degree of conservation at both the amino acid and nucleotide levels between the human transcription factor TFE3 and mTFE3 suggests that mTFE3 is the murine homolog of human TFE3. By using fluorescent in situ hybridization, mTFE3 was mapped to mouse chromosome X in band A2, which is just below the centromere. We show that in addition to the immunoglobulin heavy-chain microE3 site, mTFE3 binds to transcriptional elements important for lymphoid-specific, muscle-specific, and ubiquitously expressed genes. Binding of mTFE3 to DNA induces DNA bending. Images PMID:1732746

  18. In-line near infrared spectroscopy during freeze-drying as a tool to measure efficiency of hydrogen bond formation between protein and sugar, predictive of protein storage stability.

    PubMed

    Mensink, Maarten A; Van Bockstal, Pieter-Jan; Pieters, Sigrid; De Meyer, Laurens; Frijlink, Henderik W; van der Voort Maarschalk, Kees; Hinrichs, Wouter L J; De Beer, Thomas

    2015-12-30

    Sugars are often used as stabilizers of protein formulations during freeze-drying. However, not all sugars are equally suitable for this purpose. Using in-line near-infrared spectroscopy during freeze-drying, it is shown here that hydrogen bond formation during freeze-drying, under secondary drying conditions in particular, can be related to the preservation of the functionality and structure of proteins during storage. The disaccharide trehalose was best capable of forming hydrogen bonds with the model protein, lactate dehydrogenase, thereby stabilizing it, followed by the molecularly flexible oligosaccharide inulin 4kDa. The molecularly rigid oligo- and polysaccharides dextran 5kDa and 70kDa, respectively, formed the least amount of hydrogen bonds and provided least stabilization of the protein. It is concluded that smaller and molecularly more flexible sugars are less affected by steric hindrance, allowing them to form more hydrogen bonds with the protein, thereby stabilizing it better.

  19. Flexural Stresses and Reservoir Stability: Implications for Magma Propagation in the Lithosphere and the Formation of Giant Radial Dike Swarms on Venus

    NASA Astrophysics Data System (ADS)

    Galgana, G. A.; Grosfils, E. B.; McGovern, P. J.

    2010-12-01

    lithosphere outwards, creating stress states that favor sills and circumferential dikes in the upper lithosphere with radial dikes at the lower lithosphere. This outcome demonstrates the sensitivity of our results to uplift load geometry. With the exception of sill-producing, near-midsection rupture of magma chambers in the uppermost and lowermost lithosphere, failure generally occurs at the reservoir crest, and higher overpressures are required for failure, suggesting reservoir stability. These loads also produce surface radial and hoop strains conducive to the formation of circumferential grabens a distance (~50-180 km) from the model center. However, increasing the elastic lithosphere thickness (Te) to 40 km reduces the load shape differences, creating similar stress states for both conical and disk-shaped loads.

  20. Phase equilibria in the system K2O-FeO-MgO-Al2O3-SiO2-H2O-CO2 and the stability limit of stilpnomelane in metamorphosed Precambrian iron-formations

    NASA Astrophysics Data System (ADS)

    Miyano, Takashi; Klein, Cornelis

    1989-08-01

    The phase relations of Al- and Fe-bearing silicates in the system K2O-FeO-MgO-Al2O3-SiO2-H2O-CO2, in the presence of quartz and magnetite, are discussed on the basis of mineralogic and petrologic data from Precambrian iron-formations and blueschist facies meta-ironstone from the Franciscan Formation, California. These relations allow an estimation of the physiochemical conditions during low-grade metamorphism of iron-formations. Petrologic data together with available experimental and predicted thermodynamic data on the associated minerals place the upper stability limit of stilpnomelane in iron-formations at about 430 470° C and 5 6 kilobars. Fe-end member stilpnomelane can persist to a maximum temperature of 500° C and pressures up to 6 7 kilobars, although it is unlikely to occur in metamorphosed iron-formations. In iron-formation occurrences the stilpnomelane stability field is bordered by four equilibrium reactions with the assemblages stilpnomelane-zussmanite-chlorite-minnesotaite, stilpnomelane-zussmanite-chlorite-grunerite, stilpnomelane-biotite-chlorite-grunerite, and stilpnomelane-biotite-almandine-grunerite. The stability field is reduced by increasing X(CO2) and X {Mg/Stil}, and is also a function of a( K +)/ a( H +) in the metamorphic fluid. If the value of a( K +)/ a( H +) is smaller than that defined by the above assemblages, stilpnomelane decomposes to chlorite, but if larger, it is replaced by biotite. At pressures less than 4 kilobars, the zussmanite field is restricted to a very high value of a( K +)/a( H +) (> 5.0 in log units at 1.0 kilobar) where iron-formation assemblages are not stable.

  1. In vitro study of stability and amyloid-fibril formation of two mutants of human stefin B (cystatin B) occurring in patients with EPM1

    PubMed Central

    Rabzelj, Sabina; Turk, Vito; Žerovnik, Eva

    2005-01-01

    Myoclonus epilepsy of type 1 (EPM1) is a rare monogenic progressive and degenerative epilepsy, also known under the name Unverricht-Lundborg disease. With the aim of comparing their behavior in vitro, wild-type (wt) human stefin B (cystatin B) and the G4R and the R68X mutants observed in EPM1 were expressed and isolated from the Escherichia coli lysate. The R68X mutant (Arg68Stop) is a peptide of 67 amino acids from the N terminus of stefin B. CD spectra have shown that the R68X peptide is not folded, in contrast to the G4R mutant, which folds like wild type. The wild type and the G4R mutant were unfolded by urea and by trifluoroethanol (TFE). It has been shown that both proteins have closely similar stability and that at pH 4.8, where a native-like intermediate was demonstrated, TFE induces unfolding intermediates prior to the major transition to the all-α-helical state. Kinetics of fibril formation were followed by Thioflavin T fluorescence while the accompanying changes of morphology were followed by the transmission electron microscopy (TEM). For the two folded proteins the optimal concentration of TFE producing extensive lag phases and high fibril yields was predenaturational, 9% (v/v). The unfolded R68X peptide, which is highly prone to aggregate, formed amyloid fibrils in aqueous solution and in predenaturing 3% TFE. The G4R mutant exhibited a much longer lag phase than the wild type, with the accumulation of prefibrillar aggregates. Implications for pathology in view of the higher toxicity of prefibrillar aggregates to cells are discussed. PMID:16155205

  2. Inter-ligand azo (N=N) unit formation and stabilization of a Co(II)-diradical complex via metal-to-ligand dπ-pπ* back donation: synthesis, characterization, and theoretical study.

    PubMed

    Rakshit, Richa; Ghorai, Samir; Sarmah, Amrit; Tiwari, Archana; Roy, Ram Kinkar; Mukherjee, Chandan

    2015-02-28

    An azide (-N3) group attached at the -ortho carbon atom to the aniline moiety of 2-anilino-4,6-di-tert-butylphenol formed a diradical-containing Co(II) complex via inter-ligand azo (N=N) bond formation. Metal-to-ligand (azo), dπ-to-pπ* back donation stabilized the metal in its lower oxidation state.

  3. A Study on Formation and Thermal Stability of Nano-sized Oxide Clusters in Mechanically Alloyed Nickel Aluminum for High Temperature Applications

    NASA Astrophysics Data System (ADS)

    Kim, Yong-Deog

    the thermal stability during an extensive matrix of long-term thermal annealing. In particular, the size, number density and composition of nano-clusters were assessed. While improvements in strength were obtained in the advanced NiAl ODS alloys, and the higher strength persisted through thermal annealing for 100 hrs at 1723K, characterization revealed the presence of Al in the oxide precipitate phases. The Al incorporation is believed detrimental to the formation of a high density of thermally stable Y-Ti-O nanoscale precipitates.

  4. Fibronectin alters the rate of formation and structure of the fibrin matrix.

    PubMed

    Ramanathan, Anand; Karuri, Nancy

    2014-01-10

    Plasma fibronectin is a vital component of the fibrin clot; however its role on clot structure is not clearly understood. The goal of this study was to examine the influence of fibronectin on the kinetics of formation, structural characteristics and composition of reconstituted fibrin clots or fibrin matrices. Fibrin matrices were formed by adding thrombin to 1, 2 or 4 mg/ml fibrinogen supplemented with 0-0.4 mg/ml fibronectin. The rate of fibrin matrix formation was then monitored by measuring light absorbance properties at different time points. Confocal microscopy of fluorescein conjugated fibrinogen was used to visualize the structural characteristics of fibrin matrices. The amount of fibronectin in fibrin matrices was determined through electrophoresis and immunoblotting of solubilized matrices. Fibronectin concentration positively correlated with the initial rate of fibrin matrix formation and with steady state light absorbance values of fibrin matrices. An increase in fibronectin concentration resulted in thinner and denser fibers in the fibrin matrices. Electrophoresis and immunoblotting showed that fibronectin was covalently and non-covalently bound to fibrin matrices and in the form of high molecular weight multimers. The formation of fibronectin multimers was attributed to cross-linking of fibronectin by trace amounts Factor XIIIa. These findings are novel because they link results from light absorbance studies to microcopy analyses and demonstrate an influence of fibronectin on fibrin matrix structural characteristics. This data is important in developing therapies that destabilize fibrin clots.

  5. Influence of biopolymer emulsifier type on formation and stability of rice bran oil-in-water emulsions: whey protein, gum arabic, and modified starch.

    PubMed

    Charoen, Ratchanee; Jangchud, Anuvat; Jangchud, Kamolwan; Harnsilawat, Thepkunya; Naivikul, Onanong; McClements, David Julian

    2011-01-01

    Rice bran oil (RBO) is used in foods, cosmetics, and pharmaceuticals due to its desirable health, flavor, and functional attributes. We investigated the effects of biopolymer emulsifier type and environmental stresses on the stability of RBO emulsions. Oil-in-water emulsions (5% RBO, 10 mM citrate buffer) stabilized by whey protein isolate (WPI), gum arabic (GA), or modified starch (MS) were prepared using high-pressure homogenization. The new MS used had a higher number of octenyl succinic anhydride (OSA) groups per starch molecule than conventional MS. The droplet diameters produced by WPI and MS were considerably smaller (d < 300 nm) than those produced by GA (d > 1000 nm). The influence of pH (3 to 8), ionic strength (0 to 500 mM NaCl), and thermal treatment (30 to 90 °C) on the physical stability of the emulsions was examined. Extensive droplet aggregation occurred in WPI-stabilized emulsions around their isoelectric point (4 < pH < 6), at high salt (> 200 mM, pH 7), and at high temperatures (>70 °C, pH 7, 150 mM NaCl), which was attributed to changes in electrostatic and hydrophobic interactions between droplets. There was little effect of pH, ionic strength, and temperature on emulsions stabilized by GA or MS, which was attributed to strong steric stabilization. In summary: WPI produced small droplets at low concentrations, but they had poor stability to environmental stress; GA produced large droplets and needed high concentrations, but they had good stability to stress; new MS produced small droplets at low concentrations, with good stability to stress. Practical Application: This study showed that stable rice bran oil-in-water emulsions can be formed using biopolymer emulsifiers. These emulsions could be used to incorporate RBO into a wide range of food products. We compared the relative performance of whey protein, GA, and a new MS at forming and stabilizing the emulsions. The new OSA MS was capable of forming small stable droplets at relatively low

  6. Evaluation of nucleic acid stabilization products for ambient temperature shipping and storage of viral RNA and antibody in a dried whole blood format.

    PubMed

    Dauner, Allison L; Gilliland, Theron C; Mitra, Indrani; Pal, Subhamoy; Morrison, Amy C; Hontz, Robert D; Wu, Shuenn-Jue L

    2015-07-01

    Loss of sample integrity during specimen transport can lead to false-negative diagnostic results. In an effort to improve upon the status quo, we used dengue as a model RNA virus to evaluate the stabilization of RNA and antibodies in three commercially available sample stabilization products: Whatman FTA Micro Cards (GE Healthcare Life Sciences, Pittsburgh, PA), DNAstāble Blood tubes (Biomātrica, San Diego, CA), and ViveST tubes (ViveBio, Alpharetta, GA). Both contrived and clinical dengue-positive specimens were stored on these products at ambient temperature or 37°C for up to 1 month. Antibody and viral RNA levels were measured by enzyme-linked immunosorbent assay (ELISA) and quantitative reverse transcription polymerase chain reaction (qRT-PCR) assays, respectively, and compared with frozen unloaded controls. We observed reduced RNA and antibody levels between stabilized contrived samples and frozen controls at our earliest time point, and this was particularly pronounced for the FTA cards. However, despite some time and temperature dependent loss, a 94.6-97.3% agreement was observed between stabilized clinical specimens and their frozen controls for all products. Additional considerations such as cost, sample volume, matrix, and ease of use should inform any decision to incorporate sample stabilization products into a diagnostic testing workflow. We conclude that DNAstāble Blood and ViveST tubes are useful alternatives to traditional filter paper for ambient temperature shipment of clinical specimens for downstream molecular and serological testing.

  7. One-step formation of multiple Pickering emulsions stabilized by self-assembled poly(dodecyl acrylate-co-acrylic acid) nanoparticles.

    PubMed

    Zhu, Ye; Sun, Jianhua; Yi, Chenglin; Wei, Wei; Liu, Xiaoya

    2016-09-13

    In this study, a one-step generation of stable multiple Pickering emulsions using pH-responsive polymeric nanoparticles as the only emulsifier was reported. The polymeric nanoparticles were self-assembled from an amphiphilic random copolymer poly(dodecyl acrylate-co-acrylic acid) (PDAA), and the effect of the copolymer content on the size and morphology of PDAA nanoparticles was determined by dynamic light scattering (DLS) and transmission electron microscopy (TEM). The emulsification study of PDAA nanoparticles revealed that multiple Pickering emulsions could be generated through a one-step phase inversion process by using PDAA nanoparticles as the stabilizer. Moreover, the emulsification performance of PDAA nanoparticles at different pH values demonstrated that multiple emulsions with long-time stability could only be stabilized by PDAA nanoparticles at pH 5.5, indicating that the surface wettability of PDAA nanoparticles plays a crucial role in determining the type and stability of the prepared Pickering emulsions. Additionally, the polarity of oil does not affect the emulsification performance of PDAA nanoparticles, and a wide range of oils could be used as the oil phase to prepare multiple emulsions. These results demonstrated that multiple Pickering emulsions could be generated via the one-step emulsification process using self-assembled polymeric nanoparticles as the stabilizer, and the prepared multiple emulsions have promising potential to be applied in the cosmetic, medical, and food industries.

  8. Silicon/Organic Hybrid Solar Cells with 16.2% Efficiency and Improved Stability by Formation of Conformal Heterojunction Coating and Moisture-Resistant Capping Layer.

    PubMed

    He, Jian; Gao, Pingqi; Yang, Zhenhai; Yu, Jing; Yu, Wei; Zhang, Yu; Sheng, Jiang; Ye, Jichun; Amine, Joseph Chen; Cui, Yi

    2017-02-02

    Silicon/poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) heterojunction solar cells with 16.2% efficiency and excellent stability are fabricated on pyramid-textured silicon substrates by applying a water-insoluble ester as capping layer. It shows that conformal coating of PEDOT:PSS on textured silicon can greatly improve the junction quality with the main stability failure routes related to the moisture-induced poly(3,4-ethylenedioxythiophene) aggregations and the tunneling silicon oxide autothickening.

  9. Promotion of the halide effect in the formation of shaped metal nanocrystals via a hybrid cationic, polymeric stabilizer: Octahedra, cubes, and anisotropic growth

    NASA Astrophysics Data System (ADS)

    Sneed, Brian T.; Golden, Matthew C.; Liu, Yejing; Lee, Hiang K.; Andoni, Ilektra; Young, Allison P.; McMahon, Greg; Erdman, Natasha; Shibata, Masateru; Ling, Xing Yi; Tsung, Chia-Kuang

    2016-06-01

    To promote the effect of halide ions (Cl-, Br-, and I-) in facet-selective growth of {111} and {100} of shaped metal nanocrystals, we utilize PDADMAC, a hybrid cationic, polymeric stabilizer. SERS and synthesis experiments provide evidence supporting that the higher amount of PDADMA+ at surfaces promotes the local adsorption of halides, allowing the creation of Pd cubes, octahedra, and cuboctopods.

  10. Low-temperature formation and stabilization of rare allotropes of cyclooctasulfur (β-S8 and γ-S8) in the presence of organic carbon at a sulfur-rich glacial site in the Canadian High Arctic

    NASA Astrophysics Data System (ADS)

    Lau, Graham E.; Cosmidis, Julie; Grasby, Stephen E.; Trivedi, Christopher B.; Spear, John R.; Templeton, Alexis S.

    2017-03-01

    Large-scale deposits of elemental sulfur form annually on a glacier's surface at Borup Fiord Pass in the Canadian High Arctic. However, the mechanisms of mineralization and stabilization of elemental sulfur at this site are currently unknown. Here we show that X-ray diffraction (XRD) data for fresh sulfur precipitates collected from the surface of a melt pool over sulfide-rich ice reveal the presence of three sulfur allotropes, α-S8, β-S8, and γ-S8 (the three solid forms of cyclooctasulfur (S8)). The detection of the β-S8 allotrope of elemental sulfur is notable, since β-S8 typically only forms in high temperature environments (>96 °C). The γ-S8 allotrope is also rare in natural settings and has previously been implicated as a signature of microbial sulfur cycling. Using combustion and infrared spectroscopy approaches, organic carbon is also detected within the sample bearing the three allotropes of elemental sulfur. Electron microscopy and scanning transmission X-ray microscopy (STXM) at the C K-edge show that the sulfur precipitates are intimately associated with the organic carbon at the submicron scale. The occurrence of β-S8 and γ-S8 in this low-temperature setting indicates that there are unknown pathways for the formation and stabilization of these rare allotropes of elemental sulfur. In particular, we infer that the occurrence of these allotropes is related to their association with organic carbon. The formation of carbon-associated sulfur globules may not be a direct by-product of microbial activity; however, a potential role of direct or indirect microbial mediation in the formation and stabilization of β-S8 and γ-S8 remains to be assessed.

  11. Chaos-assisted formation of immiscible matter-wave solitons and self-stabilization in the binary discrete nonlinear Schrödinger equation

    NASA Astrophysics Data System (ADS)

    Makarov, D. V.; Uleysky, M. Yu.

    2017-02-01

    Binary discrete nonlinear Schrödinger equation is used to describe dynamics of two-species Bose-Einstein condensate loaded into an optical lattice. Linear inter-species coupling leads to Rabi transitions between the species. In the regime of strong nonlinearity, a wavepacket corresponding to condensate separates into localized and ballistic fractions. Localized fraction is predominantly formed by immiscible solitons consisted of only one species. Immiscible solitons are formed from initially non-separated states after transient chaotic regime. We calculate the finite-time Lyapunov exponent as a rate of wavepacket divergence in the Hilbert space. Appearance of immiscible solitons to spontaneous self-stabilization of the wavepacket. It is found that onset of chaos is accompanied by fast variations of interaction energy and energy of inter-site tunneling. Crossover to self-stabilization is accompanied by reduction of condensate density due to emittance of ballistically propagating waves.

  12. Formation and thermal stability of an E9{sub 3}-structured NiHf{sub 2} phase in Ni{sub 33}Hf{sub 67}

    SciTech Connect

    Liu, X.D. . E-mail: liuxd@physics.mcgill.ca; Liu, X.B.; Altounian, Z.

    2005-03-01

    The melt-spun Ni{sub 33}Hf{sub 67} glassy phase completely crystallizes into an fcc NiHf{sub 2} phase (a {approx} 12 A) upon continuous heating or isothermal annealing. Kinetics analysis shows that the NiHf{sub 2} grains are crystallized by nucleation and diffusion-controlled growth of nuclei at an average activation energy of {approx}400 kJ/mol. The resulting NiHf{sub 2} grains are extremely fine, {approx}10 nm in diameter, and exhibit excellent grain size stability upon subsequent heating over a wide temperature range. The Wigner-Seitz cell calculation results suggest that the fcc phase could be oxygen-stabilized. In the fcc lattice, the octahedral interstitial site with six nearest Hf neighbors is the most likely site for an oxygen atom to occupy. Upon further heating, part of the fcc NiHf{sub 2} crystals transform into two bct phases: the equilibrium bct NiHf{sub 2} and a metastable bct phase with a larger unit cell. Similar to the fcc phase, the metastable bct phase is most likely oxygen-stabilized. We show that the most likely oxygen site in the metastable bct lattice is the center of a tetrahedron with four nearest Hf neighbors. Upon further isothermal annealing at higher temperatures, close to the melting point of the alloy, the transformation from the metastable bct to the stable bct phase takes place.

  13. Increased stability and specificity through combined hybridization of peptide nucleic acid (PNA) and locked nucleic acid (LNA) to supercoiled plasmids for PNA-anchored "Bioplex" formation.

    PubMed

    Lundin, Karin E; Hasan, Maroof; Moreno, Pedro M; Törnquist, Elisabeth; Oprea, Iulian; Svahn, Mathias G; Simonson, E Oscar; Smith, C I Edvard

    2005-12-01

    Low cellular uptake and poor nuclear transfer hamper the use of non-viral vectors in gene therapy. Addition of functional entities to plasmids using the Bioplex technology has the potential to improve the efficiency of transfer considerably. We have investigated the possibility of stabilizing sequence-specific binding of peptide nucleic acid (PNA) anchored functional peptides to plasmid DNA by hybridizing PNA and locked nucleic acid (LNA) oligomers as "openers" to partially overlapping sites on the opposite DNA strand. The PNA "opener" stabilized the binding of "linear" PNA anchors to mixed-base supercoiled DNA in saline. For higher stability under physiological conditions, bisPNA anchors were used. To reduce nonspecific interactions when hybridizing highly cationic constructs and to accommodate the need for increased amounts of bisPNA when the molecules are uncharged, or negatively charged, we used both PNA and LNA oligomers as "openers" to increase binding kinetics. To our knowledge, this is the first time that LNA has been used together with PNA to facilitate strand invasion. This procedure allows hybridization at reduced PNA-to-plasmid ratios, allowing greater than 80% hybridization even at ratios as low as 2:1. Using significantly lower amounts of PNA-peptides combined with shorter incubation times reduces unspecific binding and facilitates purification.

  14. Water Mediated Wittig Reactions of Aldehydes in the Teaching Laboratory: Using Sodium Bicarbonate for the in Situ Formation of Stabilized Ylides

    ERIC Educational Resources Information Center

    Kelly, Michael J. B.; Fallot, Lucas B.; Gustafson, Jeffrey L.; Bergdahl, B. Mikael

    2016-01-01

    The synthesis of alkenes using the Wittig reaction is a traditional part of many undergraduate organic chemistry teaching laboratory curricula. The aqueous medium version of the Wittig reaction presented is a reliable adaptation of this alkene formation reaction as a very safe alternative in the introductory organic chemistry laboratory. The…

  15. The p in p-T is for pressure: Movement of the gas hydrate stability field during glacial sealevel lowering and its possible link to pockmark formation on the Chatham Rise, New Zealand (Invited)

    NASA Astrophysics Data System (ADS)

    Pecher, I. A.; Davy, B. W.; Wood, R.; Carter, L.; Gohl, K.

    2010-12-01

    The discussion on a possible destabilization of gas hydrates caused by climate fluctuations has in recent years focused on the role of a sub-seafloor temperature increase following bottom-water warming. We here revisit the scenario that a pressure drop during glacial sealevel lowering could lead to gas hydrate dissociation. A >20,000 km2 field of seafloor depressions that we interpret as pockmarks has been identified on the southern flanks of the Chatham Rise. Three classes of pockmarks are present in two distinct water-depth ranges. The shallowest class of pockmarks with a diameter of ~150 m are present in a water-depth range of 500-700 m, close to the current top of the gas hydrate stability field. Sub-bottom profiler data show evidence for a bottom simulating reflection making it likely that gas hydrates are present beneath the seafloor. Furthermore, buried pockmarks are identified on horizons that we correlate with sealevel lowstands suggesting that pockmark formation is linked to sealevel lowering. Assuming constant bottom-water temperatures, a glacial sealevel drop by 120 m would move much of the seafloor that is covered with these pockmarks out of the gas hydrate stability field. We therefore suggest these pockmarks were formed by gas from dissociating gas hydrate due to depressurization following sealevel lowering. Two larger classes of pockmarks with diameters of 1-5 and ~10 km, respectively, are present in water depths of 800-1100 m. Here, the seafloor has probably remained within the gas hydrate stability field during sealevel lowstands. However, the associated pressure drop has moved the base of gas hydrate stability upwards by ~30 m. It is unclear whether bottom-water temperatures have changed significantly in our study area during glacial cycles - changes of 1-3° C would be required to have a similar effect on gas hydrate stability as sealevel fluctuations. The boundary between warmer subtropical and cold subantarctic waters, the subtropical front

  16. A model for triple helix formation on human telomerase reverse transcriptase (hTERT) promoter and stabilization by specific interactions with the water soluble perylene derivative, DAPER.

    PubMed

    Rossetti, Luigi; D'Isa, Giuliana; Mauriello, Clementina; Varra, Michela; De Santis, Pasquale; Mayol, Luciano; Savino, Maria

    2007-08-01

    The promoter of human telomerase reverse transcriptase (hTERT) gene, in the region from -1000 to +1, contains two homopurine-homopyrimidine sequences (-835/-814 and -108/-90), that can be considered as potential targets to triple helix forming oligonucleotides (TFOs) for applying antigene strategy. We have chosen the sequence (-108/-90) on the basis of its unfavorable chromatin organization, evaluated by theoretical nucleosome positioning and nuclease hypersensitive sites mapping. On this sequence, anti-parallel triplex with satisfactory thermodynamic stability is formed by two TFOs, having different lengths. Triplex stability is significantly increased by specific interactions with the perylene derivative N,N'-bis[3,3'-(dimethylamino) propylamine]-3,4,9,10-perylenetetracarboxylic diimide (DAPER). Since DAPER is a symmetric molecule, the induced Circular Dichroism (CD) spectra in the range 400-600 nm allows us to obtain information on drug binding to triplex and duplex DNA. The drug-induced ellipticity is significantly higher in the case of triplex with respect to duplex and, surprisingly, it increases at decreasing of DNA. A model is proposed where self-stacked DAPER binds to triplex or to duplex narrow grooves.

  17. Mechanism of formation of the C-terminal beta-hairpin of the B3 domain of the immunoglobulin binding protein G from Streptococcus. I. Importance of hydrophobic interactions in stabilization of beta-hairpin structure.

    PubMed

    Skwierawska, Agnieszka; Makowska, Joanna; Ołdziej, Stanisław; Liwo, Adam; Scheraga, Harold A

    2009-06-01

    We previously studied a 16-amino acid-residue fragment of the C-terminal beta-hairpin of the B3 domain (residues 46-61), [IG(46-61)] of the immunoglobulin binding protein G from Streptoccocus, and found that hydrophobic interactions and the turn region play an important role in stabilizing the structure. Based on these results, we carried out systematic structural studies of peptides derived from the sequence of IG (46-61) by systematically shortening the peptide by one residue at a time from both the C- and the N-terminus. To determine the structure and stability of two resulting 12- and 14-amino acid-residue peptides, IG(48-59) and IG(47-60), respectively, we carried out circular dichroism, NMR, and calorimetric studies of these peptides in pure water. Our results show that IG(48-59) possesses organized three-dimensional structure stabilized by hydrophobic interactions (Tyr50-Phe57 and Trp48-Val59) at T = 283 and 305 K. At T = 313 K, the structure breaks down because of increased chain entropy, but the turn region is preserved in the same position observed for the structure of the whole protein. The breakdown of structure occurs near the melting temperature of this peptide (T(m) = 310 K) measured by differential scanning calorimetry (DSC). The melting temperature of IG(47-60) determined by DSC is T(m) = 330 K and its structure is similar to that of the native beta-hairpin at all (lower) temperatures examined (283-313 K). Both of these truncated sequences are conserved in all known amino acid sequences of the B domains of the immunoglobulin binding protein G from bacteria. Thus, this study contributes to an understanding of the mechanism of folding of this whole family of proteins, and provides information about the mechanism of formation and stabilization of a beta-hairpin structural element.

  18. AlFx affects the formation of focal complexes by stabilizing the Arf-GAP ASAP1 in a complex with Arf1.

    PubMed

    Klein, Stéphanie; Franco, Michel; Chardin, Pierre; Luton, Frédéric

    2005-10-24

    Aluminum fluoride (AlFx) is known to activate directly the alpha subunit of G-proteins but not the homologous small GTP-binding proteins. However, AlFx can stabilize complexes formed between Ras, RhoA or Cdc42 and their corresponding GTPase-activating proteins (GAPs). Here, we demonstrate that Arf1GDP can be converted into an active conformation by AlFx to form a complex with the Arf-GAP ASAP1 in vitro and in vivo. Within this complex ASAP1, which GAP activity is inoperative, can still alter the recruitment of paxillin to the focal complexes, thus indicating that ASAP1 interferes with focal complexes independently of its GAP activity.

  19. The influence of thermodynamic phase stabilities on the formation of nitride phases of chromium and titanium by dynamic ion beam mixing

    NASA Astrophysics Data System (ADS)

    Wolfgang, Ensinger; Masato, Kiuchi; Yuji, Horino; Akiyoshi, Chayahara; Kanenaga, Fujii; Mamoru, Satou

    1991-07-01

    Nitrogen-containing films of chromium and titanium were prepared by evaporation of the metal under simultaneous bombard- ment with highly energetic nitrogen ions. Under identical preparation conditions, i.e. ion energy, ion current density, temperature, evaporation rate, and gas pressure, titanium forms a single phase film of δ-TiN whereas chromium shows phase mixtures of Cr, Cr 2N and CrN with a lower nitrogen content than the corresponding titanium film. This different behaviour of Cr compared to Ti is attributed to the differences in chemical reactivity and in thermodynamic stability of the nitrides. The results show that chemical driving forces play a decisive role in ion-beam-assisted film synthesis.

  20. Ternary inclusion complex formation and stabilization of limaprost, a prostaglandin E1 derivative, in the presence of α- and β-cyclodextrins in the solid state.

    PubMed

    Inoue, Yasuo; Iohara, Daisuke; Sekiya, Noboru; Yamamoto, Masanobu; Ishida, Hiroyuki; Sakiyama, Yoko; Hirayama, Fumitoshi; Arima, Hidetoshi; Uekama, Kaneto

    2016-07-25

    Limaprost/α-cyclodextrin (CD)/β-CD ternary inclusion complex was prepared by freeze-drying a solution containing all three components. Under humid conditions, limaprost was more stable in the ternary α-/β-CD inclusion complex than in the binary α- or β-CD complex. Specifically, during storage at 30°C/75% relative humidity (R.H.) for 4 weeks, about 19% of limaprost degraded into 17S,20-dimethyl-trans-Δ(2)-prostaglandin A1 (referred as 11-deoxy-Δ(10)) in the β-CD complex, 8.1% degraded in the α-CD complex, and only 2.2% degraded in the α-/β-CD complex. The mechanism of limaprost stabilization in the presence of both CDs was investigated by Raman and solid-state NMR spectroscopy and powder X-ray diffractometry. The fast degradation of limaprost to 11-deoxy-Δ(10) in the β-CD complex was due to the rapid crystallization of β-CD from the complex, liberating the free amorphous drug, which is susceptible to degradation. The dissociation and crystallization of β-CD from the inclusion complex were suppressed by freeze-drying limaprost in the presence of both α- and β-CDs. In addition, the interaction between limaprost and the two CDs was reinforced by inclusion of different moieties of limaprost: α-CD predominantly included the alkyl ω-chain, whereas β-CD included the five-membered ring. Thus, a stable ternary inclusion complex was formed that included limaprost, maintaining the amorphous state of the complex and dramatically stabilizing the drug under humid conditions.

  1. Formation and characterization of an all-ferrous Rieske cluster and stabilization of the [2Fe-2S]0 core by protonation.

    PubMed

    Leggate, Ellen J; Bill, Eckhard; Essigke, Timm; Ullmann, G Matthias; Hirst, Judy

    2004-07-27

    The all-ferrous Rieske cluster, [2Fe-2S](0), has been produced in solution and characterized by protein-film voltammetry and UV-visible, EPR, and Mössbauer spectroscopies. The [2Fe-2S](0) cluster, in the overexpressed soluble domain of the Rieske protein from the bovine cytochrome bc(1) complex, is formed at -0.73 V at pH 7. Therefore, at pH 7, the [2Fe-2S](1+/0) couple is 1.0 V below the [2Fe-2S](2+/1+) couple. The two cluster-bound ferrous irons are both high spin (S = 2), and they are coupled antiferromagnetically (-J > or = 30 cm(-1), H =-2JS1.S2) to give a diamagnetic (S = 0) ground state. The ability of the Rieske cluster to exist in three oxidation states (2+, 1+, and 0) without an accompanying coupled reaction, such as a conformational change or protonation, is highly unusual. However, uncoupled reduction to the [2Fe-2S](0) state occurs at pH > 9.8 only, and at high pH the intact cluster persists in solution for <1 min. At pH < 9.8, the all-ferrous cluster is stabilized significantly by protonation. A combination of experimental data and calculations based on density functional theory suggests strongly that the proton binds to one of the cluster mu(2)-sulfides, consistent with observations that reduced [3Fe-4S] clusters are protonated also. The implications for our understanding of coupled reactions at iron-sulfur clusters and of the factors that determine the relative stabilities of their different oxidation states are discussed.

  2. Formation and stability of metastable structures and amorphous phases in PU-V, PU-TA, and PU-YB systems with positive heats of mixing

    NASA Astrophysics Data System (ADS)

    Rizzo, H. F.; Zocco, T.; Massalski, T. B.; Nastasi, M.; Echeverria, A.

    1994-08-01

    The triode sputtering technique with a “split-target” arrangement was used to obtain metastable crystalline and amorphous phases in the Pu-V, Pu-Ta, and Pu-Yb systems. The proposed phase diagrams for these systems all exhibit liquid immiscibility. The heats of mixing are estimated to be highly positive, and the atomic radii of the component atoms differ by at least 10 pct. Extended amorphous and body-centered cubic (bcc) solid-solution regions were observed in the Pu-V and Pu-Ta systems. The corresponding lattice parameters appear to follow in each case an assumed Vegard’s Law extension. In the Pu-Yb system, no amorphous phase was obtained, but an extended face-centered cubic (fcc) solid-solution region (24 to 78 at. pct Yb) was observed with a large positive deviation of the lattice parameter (˜9 pct at 40 at. pct Yb) from a linear Vegard’s Law between the pure fcc components. The observed ranges of amorphous and metastable solid-solution phases have been interpreted in terms of predicated heats of formation for these phases using Miedema’s thermodynamic approximations that include chemical, elastic, and structural contributions. The effect of the high deposition rates on the formation of amorphous and metastable phases has also been considered. Thermal annealing of Pu-Ta amorphous alloys brings about a rapid diffusion of Pu to the free surface of the amorphous phase without crystallization of the remaining Ta-rich amorphous phase. Microhardness measurements indicate that amorphous Pu-V and Pu-Ta alloys are softer than the crystalline bcc solid-solution alloys in the same composition range. Several similarities in the formation of mixed phase regions (amorphous and solid solutions), microhardness, and resistance to decomposition on heating were noted between the Pu-Ta and Pu-V systems and the Cu-W system studied previously.

  3. Critiques of the seismic hypothesis and the vegetation stabilization hypothesis for the formation of Mima mounds along the western coast of the U.S.

    NASA Astrophysics Data System (ADS)

    Gabet, Emmanuel J.; Burnham, Jennifer L. Horwath; Perron, J. Taylor

    2016-09-01

    A recent paper published in Geomorphology by Gabet et al. (2014) presents the results of a numerical model supporting the hypothesis that burrowing mammals build Mima mounds - small, densely packed hillocks found primarily in the western United States. The model is based on field observations and produces realistic-looking mounds with spatial distributions similar to real moundfields. Alternative explanations have been proposed for these Mima mounds, including formation by seismic shaking and vegetation-controlled erosion and deposition. In this short communication, we present observations from moundfields in the coastal states of the western U.S. that are incompatible with these alternative theories.

  4. SEI Formation and Interfacial Stability of a Si Electrode in a LiTDI-Salt Based Electrolyte with FEC and VC Additives for Li-Ion Batteries.

    PubMed

    Lindgren, Fredrik; Xu, Chao; Niedzicki, Leszek; Marcinek, Marek; Gustafsson, Torbjörn; Björefors, Fredrik; Edström, Kristina; Younesi, Reza

    2016-06-22

    An electrolyte based on the new salt, lithium 4,5-dicyano-2-(trifluoromethyl)imidazolide (LiTDI), is evaluated in combination with nano-Si composite electrodes for potential use in Li-ion batteries. The additives fluoroethylene carbonate (FEC) and vinylene carbonate (VC) are also added to the electrolyte to enable an efficient SEI formation. By employing hard X-ray photoelectron spectroscopy (HAXPES), the SEI formation and the development of the active material is probed during the first 100 cycles. With this electrolyte formulation, the Si electrode can cycle at 1200 mAh g(-1) for more than 100 cycles at a coulombic efficiency of 99%. With extended cycling, a decrease in Si particle size is observed as well as an increase in silicon oxide amount. As opposed to LiPF6 based electrolytes, this electrolyte or its decomposition products has no side reactions with the active Si material. The present results further acknowledge the positive effects of SEI forming additives. It is suggested that polycarbonates and a high LiF content are favorable components in the SEI over other kinds of carbonates formed by ethylene carbonate (EC) and dimethyl carbonate (DMC) decomposition. This work thus confirms that LiTDI in combination with the investigated additives is a promising salt for Si electrodes in future Li-ion batteries.

  5. Phase Shift Interferometer and Growth Set Up to Step Pattern Formation During Growth From Solutions. Influence of the Oscillatory solution Flow on Stability

    NASA Technical Reports Server (NTRS)

    Chernov, Alex A.; Booth, N. A.; Vekilov, P. G.; Murray, B. T.; McFadden, G. B.

    2000-01-01

    We have assembled an experimental setup based on Michelson interferometry with the growing crystal surface as one of the reflective surfaces. The crystallization part of the device allows optical monitoring of a face of a crystal growing at temperature stable within 0.05 C in a flow of solution of controlled direction and speed. The reference arm of the interferometer contains a liquid crystal element that allows controlled shifts of the phase of the interferograms. We employ an image-processing algorithm, which combines five images with a pi/2 phase difference between each pair of images. The images are transferred to a computer by a camera capable of capturing 60 frames per second. The device allows data collection on surface morphology and kinetics during the face layers growth over a relatively large area (approximately 4 sq. mm) in situ and in real time during growth. The estimated depth resolution of the phase shifting interferometry is approximately 50 Angstroms. The data will be analyzed in order to reveal and monitor step bunching during the growth process. The crystal chosen as a model for study in this work is KH2PO4 (KDP). This optically non-linear material is widely used in frequency doubling applications. There have been a number of studies of the kinetics of KDP crystallization that can serve as a benchmark for our investigations. However, so far, systematic quantitative characteristics of step interaction and bunching are missing. We intend to present our first quantitative results on the onset, initial stages and development of instabilities in moving step trains on vicinal crystal surfaces at varying supersaturation, flow rate, and flow direction. Behavior of a vicinal face growing from solution flowing normal to the steps and periodically changing its direction in time was considered theoretically. It was found that this oscillating flow reduces both stabilization and destabilization effects resulted from the unidirectional solution flow directed

  6. Formation of colloidal silver nanoparticles stabilized by Na+-poly(gamma-glutamic acid)-silver nitrate complex via chemical reduction process.

    PubMed

    Yu, Da-Guang

    2007-10-01

    Macromolecular and polyanionic Na(+)-poly(gamma-glutamic acid) (PGA) silver nitrate complex acted as both a metal ion provider and a particle protector to fabricate nanosized silver colloids under chemical reduction by dextrose. The formation and size of particles have been characterized from transmission electron microscopy (TEM), dynamic light scattering analysis and UV-vis spectrophotometer. The results showed that the average particle size was 17.2+/-3.4 to 37.3+/-5.5 nm, apparently depending on the complex concentration. It was found that the rate constant and conversion of silver nanoparticles were proportional to the concentration of PGA. The growth mechanism of nanosized silver colloid was fully discussed. In addition, the in vitro cytotoxicity evaluated by L929 fibroblasts proliferation and antibacterial activity against Gram-positive strain (methicillin-resistant S. aureus (MRSA)) and Gram-negative strain (P. aeruginosa) bacteria have been assessed.

  7. Formation and stability of crystalline and amorphous Al2O3 layers deposited on Ga2O3 nanowires by atomic layer epitaxy

    NASA Astrophysics Data System (ADS)

    Katz, M. B.; Twigg, M. E.; Prokes, S. M.

    2016-09-01

    Although the crystalline α and γ phases are the most stable forms of alumina, small-diameter (<6 nm) nanoparticles are known to be completely amorphous, due to the surface energy being correspondingly lower for the less stable non-crystalline phase. Al2O3 films with a thickness of 5 nm grown by low temperature (200 °C) atomic layer deposition (ALD) on small-diameter (<20 nm) Ga2O3 nanowires (NWs), however, are identified by transmission electron microscopy as belonging to the α, γ, and possibly θ crystalline phases of Al2O3, while films deposited on larger diameter (>20 nm) NWs are found to be amorphous. Indeed, until recently, all Al2O3, films deposited by low-temperature ALD using trimethylaluminum and water have been reported to be amorphous, regardless of film thickness or substrate. The formation of a crystalline ALD film can be understood in terms of the energetics of misfit dislocations that maintain the registry between the ALD film and the NW substrate, as well as the influence of strain and surface energy. The decreasing energy of co-axial misfit dislocations with NW diameter results in a corresponding decrease in the contribution of the Al2O3/Ga2O3 interface to the free energy, while the interfacial energy for an amorphous film is independent of the NW diameter. Therefore, for NW cores of sufficiently small diameter, the free energy contribution of the Al2O3/Ga2O3 interface is smaller for crystalline films than for amorphous films, thereby favoring the formation of crystalline films for small-diameter NWs. For ALD Al2O3 films of 10 nm thickness deposited on small-diameter Ga2O3 NWs, however, only the first 5 nm of the ALD film is found to be crystalline, possibly due to well-established kinetic limitations to low temperature epitaxial growth.

  8. The formation stability, hydrolytic behavior, mass spectrometry, DFT study, and luminescence properties of trivalent lanthanide complexes of H2ODO2A.

    PubMed

    Chang, C Allen; Wang, I-Fan; Lee, Hwa-Yu; Meng, Ching-Ning; Liu, Kuan-Yu; Chen, Ya-Fen; Yang, Tsai-Hua; Wang, Yun-Ming; Tsay, Yeou-Guang

    2012-12-28

    The trivalent lanthanide complex formation constants (log K(f)) of the macrocyclic ligand H(2)ODO2A (4,10-dicarboxymethyl-1-oxa-4,7,10-triazacyclododecane) have been determined by pH titration techniques to be in the range 10.84-12.62 which increase with increasing lanthanide atomic number, and are smaller than those of the corresponding H(2)DO2A (1,7-dicarboxylmethyl-1,4,7,10-tetraazacyclododecane) complexes. The equilibrium formation of the dinuclear hydrolysis species, e.g. Ln(2)(ODO2A)(2)(μ-OH)(+) and Ln(2)(ODO2A)(2)(μ-OH)(2), dominates over the mononuclear species, e.g. LnODO2A(OH) and LnODO2A(OH)(2)(-). Mass spectrometry confirmed the presence of [Eu(ODO2A)](+), [Eu(ODO2A)(OH)+H](+), [Eu(2)(ODO2A)(2)(OH(2))(2)+H](+), [Eu(ODO2A)(OH)(2)](-) and [Eu(2)(ODO2A)(2)(OH(2))(3)](-) species at pH > 7. Density function theory (DFT) calculated structures of the EuODO2A(H(2)O)(3)(+) and EuDO2A(H(2)O)(3)(+) complexes indicate that three inner-sphere coordinated water molecules are arranged in a meridional configuration, i.e. the 3 water molecules are on the same plane perpendicular to that of the basal N(3)O or N(4) atoms. However, luminescence lifetime studies reveal that the EuODO2A(+) and TbODO2A(+) complexes have 4.1 and 2.9 inner-sphere coordinated water molecules, respectively, indicating that other equilibrium species are also present for the EuODO2A(+) complex. The respective emission spectral intensities and lifetimes at 615 nm (λ(ex) = 395 nm) and 544 nm (λ(ex) = 369 nm) of the EuODO2A(+) and TbODO2A(+) complexes increase with increasing pH, consistent with the formation of μ-OH-bridged dinuclear species at higher pH. Additional DFT calculations show that each Y(iii) ion is 8-coordinated in the three possible cis-[Y(2)(ODO2A)(2)(μ-OH)(H(2)O)(2)](+), trans-[Y(2)(ODO2A)(2)(μ-OH)(H(2)O)(2)](+) and [Y(2)(ODO2A)(2)(μ-OH)(2)] dinuclear complex structures. The first and the second include 6-coordination by the ligand ODO2A(2-), one by the bridged μ-OH ion and

  9. β-Irradiation Effects on the Formation and Stability of CaMoO4 in a Soda Lime Borosilicate Glass Ceramic for Nuclear Waste Storage.

    PubMed

    Patel, Karishma B; Boizot, Bruno; Facq, Sébastien P; Lampronti, Giulio I; Peuget, Sylvain; Schuller, Sophie; Farnan, Ian

    2017-02-06

    Molybdenum solubility is a limiting factor to actinide loading in nuclear waste glasses, as it initiates the formation of water-soluble crystalline phases such as alkali molybdates. To increase waste loading efficiency, alternative glass ceramic structures are sought that prove resistant to internal radiation resulting from radioisotope decay. In this study, selective formation of water-durable CaMoO4 in a soda lime borosilicate is achieved by introducing up to 10 mol % MoO3 in a 1:1 ratio to CaO using a sintering process. The resulting homogeneously dispersed spherical CaMoO4 nanocrystallites were analyzed using electron microscopy, X-ray diffraction (XRD), Raman and electron paramagnetic resonance (EPR) spectroscopies prior to and post irradiation, which replicated internal β-irradiation damage on an accelerated scale. Following 0.77 to 1.34 GGy of 2.5 MeV electron radiation CaMoO4 does not exhibit amorphization or significant transformation. Nor does irradiation induce glass-in-glass phase separation in the surrounding amorphous matrix, or the precipitation of other molybdates, thus proving that excess molybdenum can be successfully incorporated into a structure that it is resistant to β-irradiation proportional to 1000 years of storage without water-soluble byproducts. The CaMoO4 crystallites do however exhibit a nonlinear Scherrer crystallite size pattern with dose, as determined by a Rietveld refinement of XRD patterns and an alteration in crystal quality as deduced by anisotropic peak changes in both XRD and Raman spectroscopy. Radiation-induced modifications in the CaMoO4 tetragonal unit cell occurred primarily along the c-axis indicating relaxation of stacked calcium polyhedra. Concurrently, a strong reduction of Mo(6+) to Mo(5+) during irradiation is observed by EPR, which is believed to enhance Ca mobility. These combined results are used to hypothesize a crystallite size alteration model based on a combination of relaxation and diffusion

  10. Evaluation of the geological relationships to gas hydrate formation and stability. Annual technical progress report, October 1, 1984--September 30, 1985

    SciTech Connect

    Not Available

    1985-12-31

    During the reported year we have enhanced our knowledge on and gained considerable experience in assessment of the gas hydrate resources in the offshore environments. Specifically, we have learned and gained experience in the following: Efficiently locating data sources, including published literature and unpublished information. We have established personal communication extremely critical in data accessability and acquisition. We have updated information pertinent to gas hydrate knowledge, also based on thorough study and evaluation of most Russian literature and additional publications in languages other than English. Besides critical evaluation of widely spread literature, in many cases our reports include previously unpublished information (e.g. BSRs from the Gulf of Mexico). The assessment of the gas resources potential associated with the gas hydrates, although in most cases at a low level of confidence, appears also very encouraging for further, more detailed, study. We are also confident that, because of the present reports` format, new data and a concept-oriented approach, the result of our study will be of strong interest to various industries, research institutions and numerous governmental agencies.

  11. The thermal stability and pyrolysis mechanism of boron-containing phenolic resins: The effect of phenyl borates on the char formation

    NASA Astrophysics Data System (ADS)

    Wang, Shujuan; Wang, Yong; Bian, Cheng; Zhong, Yuhu; Jing, Xinli

    2015-03-01

    Boron-containing phenolic resin (BPR) is a kind of the ablative resins with high-performance. Due to the lack of the exact knowledge concerning the pyrolysis mechanism of BPR, its development and application are greatly impeded. In the present paper, the chemical structure of the cured BPR and its structural evolution at high temperatures are investigated to clarify the reason for the high char yield of BPR. The results indicate that the high char yield of BPR is mainly attributed to the phenyl borates formed during curing, which can block parts of phenolic hydroxyl groups, and effectively inhibit their thermal decomposition reaction. Boron oxide is formed on the surface of carbonization products by the cleavage of O-C bonds from phenyl borates via pyrolysis, which avoids the release of volatile carbon dioxide and reduces the development of micro-structural defects of carbonization products. Introducing boron into PR improves the graphitization degree and graphite crystallites of carbonization products, which promotes the formation of a more ordered glassy carbon during pyrolysis. This study provides a new vision for the understanding of the high char yield of BPR, which makes it possible to develop a new ablative resin through molecular design.

  12. Thermoanalytical and Fourier transform infrared spectral curve-fitting techniques used to investigate the amorphous indomethacin formation and its physical stability in Indomethacin-Soluplus® solid dispersions.

    PubMed

    Lin, Shan-Yang; Lin, Hong-Liang; Chi, Ying-Ting; Huang, Yu-Ting; Kao, Chi-Yu; Hsieh, Wei-Hsien

    2015-12-30

    The amorphous form of a drug has higher water solubility and faster dissolution rate than its crystalline form. However, the amorphous form is less thermodynamically stable and may recrystallize during manufacturing and storage. Maintaining the amorphous state of drug in a solid dosage form is extremely important to ensure product quality. The purpose of this study was to quantitatively determine the amount of amorphous indomethacin (INDO) formed in the Soluplus® solid dispersions using thermoanalytical and Fourier transform infrared (FTIR) spectral curve-fitting techniques. The INDO/Soluplus® solid dispersions with various weight ratios of both components were prepared by air-drying and heat-drying processes. A predominate IR peak at 1683cm(-1) for amorphous INDO was selected as a marker for monitoring the solid state of INDO in the INDO/Soluplus® solid dispersions. The physical stability of amorphous INDO in the INDO/Soluplus® solid dispersions prepared by both drying processes was also studied under accelerated conditions. A typical endothermic peak at 161°C for γ-form of INDO (γ-INDO) disappeared from all the differential scanning calorimetry (DSC) curves of INDO/Soluplus® solid dispersions, suggesting the amorphization of INDO caused by Soluplus® after drying. In addition, two unique IR peaks at 1682 (1681) and 1593 (1591)cm(-1) corresponded to the amorphous form of INDO were observed in the FTIR spectra of all the INDO/Soluplus® solid dispersions. The quantitative amounts of amorphous INDO formed in all the INDO/Soluplus® solid dispersions were increased with the increase of γ-INDO loaded into the INDO/Soluplus® solid dispersions by applying curve-fitting technique. However, the intermolecular hydrogen bonding interaction between Soluplus® and INDO were only observed in the samples prepared by heat-drying process, due to a marked spectral shift from 1636 to 1628cm(-1) in the INDO/Soluplus® solid dispersions. The INDO/Soluplus® solid

  13. The formation and stability of the superoxide radical (O2-) on rock-forming minerals: Band gaps, hydroxylation state, and implications for Mars oxidant chemistry

    NASA Astrophysics Data System (ADS)

    Zent, Aaron P.; Ichimura, Andrew S.; Quinn, Richard C.; Harding, Heather K.

    2008-09-01

    We have examined the generation and stability of O2 - on TiO2 and albite, a common Na feldspar. We were not able to produce thermally stable superoxide on albite, in contrast to the results of Yen et al., who reported the generation of O2 - that was stable up to 200°C on labradorite, another common feldspar. The superoxide radical did form under UV irradiation at 77 K on albite that was not dehydrated but decayed rapidly at room temperature. On dehydrated albite, no superoxide signal was observed. We studied the kinetics of O2 - decomposition on hydrated albite and derived an activation energy, E a = 15.2 kJ/mol. Assuming pseudo first-order kinetics, a simple thermal model of Mars' regolith demonstrates that the surface O2 - population does not go to zero overnight; superoxide extinction at the surface is only complete when the seasonal CO2 cap covers the surface and surface photolysis is inhibited. Depending on the specific quantum efficiency of the e-/h+ generation process, a finite, non-equilibrium population of O2 - should be observable on Martian surface materials throughout the Martian year. However, on the basis of our inability to generate stable O2 - on hydrated albite via direct UV irradiation, we do not believe that this mechanism is capable of explaining the O2 release in the Viking Gas Exchange (GEx) results, since O2 release in that case was observed even after samples had been stored for 143 sols in the dark at 10°C, then heated to 145°C for 3 hours. At least two other potential pathways to the generation of O2 - are identified in this article. The first possibility is that metal oxides common on the Martian surface, particularly hematite, may be photoactive on Mars and play a role analogous to TiO2 in surface catalysis. Secondly, we found that superoxide that formed during the sorption or drying of a 1% H2O2 solution on TiO2, and potentially other oxides seems to be stable indefinitely.

  14. Ice Formation on Wings

    NASA Technical Reports Server (NTRS)

    Ritz, L

    1939-01-01

    This report makes use of the results obtained in the Gottingen ice tunnel in which the atmospheric conditions are simulated and the process of ice formation photographed. The effect of ice formation is threefold: 1) added weight to the airplane; 2) a change in the lift and drag forces; 3) a change in the stability characteristics.

  15. pKa values of hyodeoxycholic and cholic acids in the binary mixed micelles sodium-hyodeoxycholate-Tween 40 and sodium-cholate-Tween 40: Thermodynamic stability of the micelle and the cooperative hydrogen bond formation with the steroid skeleton.

    PubMed

    Poša, Mihalj; Pilipović, Ana; Bećarević, Mirjana; Farkaš, Zita

    2017-01-01

    Due to a relatively small size of bile acid salts, their mixed micelles with nonionic surfactants are analysed. Of the special interests are real binary mixed micelles that are thermodynamically more stable than ideal mixed micelles. Thermodynamic stability is expressed with an excess Gibbs energy (G(E)) or over an interaction parameter (βij). In this paper sodium salts of cholic (C) and hyodeoxycholic acid (HD) in their mixed micelles with Tween 40 (T40) are analysed by potentiometric titration and their pKa values are determined. Examined bile acids in mixed micelles with T40 have higher pKa values than free bile acids. The increase of ΔpKa acid constant of micellary bound C and HD is in a correlation with absolute values of an interaction parameter. According to an interaction parameter and an excess Gibbs energy, mixed micelle HD-T40 are thermodynamically more stable than mixed micelles C-T40. ΔpKa values are higher for mixed micelles with Tween 40 whose second building unit is HD, related to the building unit C. In both micellar systems, ΔpKa increases with the rise of a molar fraction of Tween 40 in binary mixtures of surfactants with sodium salts of bile acids. This suggests that, ΔpKa can be a measure of a thermodynamic stabilization of analysed binary mixed micelles as well as an interaction parameter. ΔpKa values are confirmed by determination of a distribution coefficient of HD and C in systems: water phase with Tween 40 in a micellar concentration and 1-octanol, with a change of a pH value of a water phase. Conformational analyses suggests that synergistic interactions between building units of analysed binary micelles originates from formation of hydrogen bonds between steroid OH groups and polyoxyethylene groups of the T40. Relative similarity and spatial orientation of C3 and C6 OH group allows cooperative formation of hydrogen bonds between T40 and HD - excess entropy in formation of mixed micelle. If a water solution of analysed binary

  16. Curcuma oil attenuates accelerated atherosclerosis and macrophage foam-cell formation by modulating genes involved in plaque stability, lipid homeostasis and inflammation.

    PubMed

    Singh, Vishal; Rana, Minakshi; Jain, Manish; Singh, Niharika; Naqvi, Arshi; Malasoni, Richa; Dwivedi, Anil Kumar; Dikshit, Madhu; Barthwal, Manoj Kumar

    2015-01-14

    In the present study, the anti-atherosclerotic effect and the underlying mechanism of curcuma oil (C. oil), a lipophilic fraction from turmeric (Curcuma longa L.), was evaluated in a hamster model of accelerated atherosclerosis and in THP-1 macrophages. Male golden Syrian hamsters were subjected to partial carotid ligation (PCL) or FeCl3-induced arterial oxidative injury (Ox-injury) after 1 week of treatment with a high-cholesterol (HC) diet or HC diet plus C. oil (100 and 300 mg/kg, orally). Hamsters fed with the HC diet were analysed at 1, 3 and 5 weeks following carotid injury. The HC diet plus C. oil-fed group was analysed at 5 weeks. In hyperlipidaemic hamsters with PCL or Ox-injury, C. oil (300 mg/kg) reduced elevated plasma and aortic lipid levels, arterial macrophage accumulation, and stenosis when compared with those subjected to arterial injury alone. Similarly, elevated mRNA transcripts of matrix metalloproteinase-2 (MMP-2), MMP-9, cluster of differentiation 45 (CD45), TNF-α, interferon-γ (IFN-γ), IL-1β and IL-6 were reduced in atherosclerotic arteries, while those of transforming growth factor-β (TGF-β) and IL-10 were increased after the C. oil treatment (300 mg/kg). The treatment with C. oil prevented HC diet- and oxidised LDL (OxLDL)-induced lipid accumulation, decreased the mRNA expression of CD68 and CD36, and increased the mRNA expression of PPARα, LXRα, ABCA1 and ABCG1 in both hyperlipidaemic hamster-derived peritoneal and THP-1 macrophages. The administration of C. oil suppressed the mRNA expression of TNF-α, IL-1β, IL-6 and IFN-γ and increased the expression of TGF-β in peritoneal macrophages. In THP-1 macrophages, C. oil supplementation prevented OxLDL-induced production of TNF-α and IL-1β and increased the levels of TGF-β. The present study shows that C. oil attenuates arterial injury-induced accelerated atherosclerosis, inflammation and macrophage foam-cell formation.

  17. Dimerization Mechanism of Alzheimer Aβ40 Peptides: The High Content of Intrapeptide-Stabilized Conformations in A2V and A2T Heterozygous Dimers Retards Amyloid Fibril Formation.

    PubMed

    Nguyen, Phuong H; Sterpone, Fabio; Pouplana, Ramon; Derreumaux, Philippe; Campanera, Josep M

    2016-12-01

    Amyloid beta (Aβ) oligomerization is associated with the origin and progression of Alzheimer's disease (AD). While the A2V mutation enhances aggregation kinetics and toxicity, mixtures of wild-type (WT) and A2V, and also WT and A2T, peptides retard fibril formation and protect against AD. In this study, we simulate the equilibrium ensemble of WT:A2T Aβ40 dimer by means of extensive atomistic replica exchange molecular dynamics and compare our results with previous equivalent simulations of A2V:A2V, WT:WT, and WT:A2V Aβ40 dimers for a total time scale of nearly 0.1 ms. Qualitative comparison of the resulting thermodynamic properties, such as the relative binding free energies, with the reported experimental kinetic and thermodynamic data affords us important insight into the conversion from slow-pathway to fast-pathway dimer conformations. The crucial reaction coordinate or driving force of such transformation turns out to be related to hydrophobic interpeptide interactions. Analysis of the equilibrium ensembles shows that the fast-pathway conformations contain interpeptide out-of-register antiparallel β-sheet structures at short interpeptide distances. In contrast, the slow-pathway conformations are formed by the association of peptides at large interpeptide distances and high intrapeptide compactness, such as conformations containing intramolecular three-stranded β-sheets which sharply distinguish fast (A2V:A2V and WT:WT) and slow (WT:A2T and WT:A2V) amyloid-forming sequences. Also, this analysis leads us to predict that a molecule stabilizing the intramolecular three-stranded β-sheet or inhibiting the formation of an interpeptide β-sheet spanning residues 17-20 and 31-37 would further reduce fibril formation and probably the cytotoxicity of Aβ species.

  18. Formation of oligomeric rings by XcpQ and PilQ, which are involved in protein transport across the outer membrane of Pseudomonas aeruginosa.

    PubMed

    Bitter, W; Koster, M; Latijnhouwers, M; de Cock, H; Tommassen, J

    1998-01-01

    Pseudomonas aeruginosa is able to translocate proteins across both membranes of the cell envelope. Many of these proteins are transported via the type II secretion pathway and adopt their tertiary conformation in the periplasm, which implies the presence of a large transport channel in the outer membrane. The outer membrane protein, XcpQ, which is involved in transport of folded proteins across the outer membrane of P. aeruginosa, was purified as a highly stable homomultimer. Insertion and deletion mutagenesis of xcpQ revealed that the C-terminal part of XcpQ is sufficient for the formation of the multimer. However, linker insertions in the N-terminal part can disturb complex formation completely. Furthermore, complex formation is strictly correlated with lethality, caused by overexpression of xcpQ. Electron microscopic evaluation of the XcpQ multimers revealed large, ring-shaped structures with an apparent central cavity of 95 A. Purified PilQ, a homologue of XcpQ involved in the biogenesis of type IV pili, formed similar structures. However, the apparent cavity formed by PilQ was somewhat smaller, 53 A. The size of this cavity could allow for the transport of intact type IV pili.

  19. Pore formation in lipid membranes by alamethicin.

    PubMed Central

    Fringeli, U P; Fringeli, M

    1979-01-01

    The conformation of the linear peptide antibiotic alamethicin in dipalmitoyl phosphatidylcholine multilayers was investigated in the absence of an electric field by means of infrared attenuated total reflection spectroscopy. Alamethicin was found to be incorporated into the lipid membrane not only in the dry state but also in an aqueous environment. Its molecular conformation, however, changed from a helix when dry to an extended chain when aqueous. The extended chain aggregated to di- and multimers spanning the lipid bilayer. The equilibrium concentration of alamethicin in the surrounding water was 90 nM, which is in the range of concentrations used in black film experiments. The corresponding molar ratio of lipid to peptide was 80:1. Concerning the molecular mechanism of electric field-induced pore formation, one has to conclude that the dipole model proposed by several authors is very unlikely because it is based on the assumption that the major part of alamethicin is adsorbed on the membrane surface, from which small amounts flip into the membrane under the influence of an electric field. An alternative mechanism is proposed, based on a field-induced conformational change of the peptide from the extended state to a helix. This transition is favored by the resulting dipole moment of the alamethicin helix. PMID:291045

  20. Rapid synthesis of hybrids and hollow PdO nanostructures by controlled in situ dissolution of a ZnO nanorod template: insights into the formation mechanism and thermal stability

    NASA Astrophysics Data System (ADS)

    Kundu, Subhajit; Ravishankar, N.

    2016-01-01

    Hollow nanomaterials have attracted a lot of interest by virtue of their wide range of applications that arise primarily due to their unique architecture. A common strategy to synthesize hollow nanomaterials is by nucleation of the shell material over a preformed core and subsequent dissolution of the core in the second step. Herein an ultrafast, microwave route has been demonstrated, to synthesize PdO nanotubes in a single step using ZnO as a sacrificial template. The mechanism of the nanotube formation has been investigated in detail using control experiments. By tuning the starting ratio of PdCl2 : ZnO, hollow to hybrid PdO nanostructures could be obtained using the same method. Conversion of the PdO to Pd nanotubes has been shown by simple NaBH4 treatment. The thermal stability of the PdO nanotubes has been studied. The insights presented here are general and applicable for the synthesis of hybrids/hollow structures in other systems as well.Hollow nanomaterials have attracted a lot of interest by virtue of their wide range of applications that arise primarily due to their unique architecture. A common strategy to synthesize hollow nanomaterials is by nucleation of the shell material over a preformed core and subsequent dissolution of the core in the second step. Herein an ultrafast, microwave route has been demonstrated, to synthesize PdO nanotubes in a single step using ZnO as a sacrificial template. The mechanism of the nanotube formation has been investigated in detail using control experiments. By tuning the starting ratio of PdCl2 : ZnO, hollow to hybrid PdO nanostructures could be obtained using the same method. Conversion of the PdO to Pd nanotubes has been shown by simple NaBH4 treatment. The thermal stability of the PdO nanotubes has been studied. The insights presented here are general and applicable for the synthesis of hybrids/hollow structures in other systems as well. Electronic supplementary information (ESI) available: Details of experiments

  1. Method for clay stabilization with quaternary amines

    SciTech Connect

    Himes, R.E.

    1992-03-24

    This patent describes a method of treating a subterranean formation. It comprises: contacting the formation with an aqueous treatment fluid containing a formation control additive in an amount effective to stabilize the formation; the additive comprising a quaternary ammonium compound selected from compounds.

  2. Stability and breakdown of Ca{sup 13}CO{sub 3} melt associated with formation of {sup 13}C-diamond in static high pressure experiments up to 43 GPa and 3900 K

    SciTech Connect

    Spivak, A.V.; Litvin, Yu.A.; Ovsyannikov, S.V.; Dubrovinskaia, N.A.; Dubrovinsky, L.S.

    2012-07-15

    Melting of calcium carbonate Ca{sup 13}CO{sub 3}, stability of the melt and its decomposition were studied in static high pressure experiments at pressures of 11-43 GPa and temperatures of 1600-3900 K using diamond anvil cell technique with laser heating. We observed formation of {sup 13}C-graphite (below 16 GPa) and {sup 13}C-diamond (between 16 and 43 GPa) on decomposition of the Ca{sup 13}CO{sub 3} melt at temperatures above 3400 K. At temperatures below 3400 K congruent melting of calcium carbonate was confirmed. The experimental results were applied to construction of the phase diagram of CaCO{sub 3} up to 43 GPa and 3900 K focusing at the melting curve of calcium carbonate and the decomposition phase boundary of CaCO{sub 3} melt. - Graphical abstract: Highlights: Black-Right-Pointing-Pointer Phase states of CaCO{sub 3} were studied at P=11-43 GPa and T=1600-3900 K. Black-Right-Pointing-Pointer {sup 13}C-diamond easily crystallizes in carbonate-carbon (Ca{sup 13}CO{sub 3-}{sup 13}C-graphite) melt-solutions. Black-Right-Pointing-Pointer Ca-carbonate melts congruently that was observed in experiments in DAC with laser heating. Black-Right-Pointing-Pointer Decomposition of CaCO{sub 3} melt, indicated by formation of graphite and/or diamond. Black-Right-Pointing-Pointer Decomposition of CaCO{sub 3} was observed at temperatures above 3400 K in the pressure interval studied.

  3. Membrane stabilizer

    DOEpatents

    Mingenbach, William A.

    1988-01-01

    A device is provided for stabilizing a flexible membrane secured within a frame, wherein a plurality of elongated arms are disposed radially from a central hub which penetrates the membrane, said arms imposing alternately against opposite sides of the membrane, thus warping and tensioning the membrane into a condition of improved stability. The membrane may be an opaque or translucent sheet or other material.

  4. Process Recovery after CaO Addition Due to Granule Formation in a CSTR Co-Digester-A Tool to Influence the Composition of the Microbial Community and Stabilize the Process?

    PubMed

    Liebrich, Marietta; Kleyböcker, Anne; Kasina, Monika; Miethling-Graff, Rona; Kassahun, Andrea; Würdemann, Hilke

    2016-03-17

    The composition, structure and function of granules formed during process recovery with calcium oxide in a laboratory-scale fermenter fed with sewage sludge and rapeseed oil were studied. In the course of over-acidification and successful process recovery, only minor changes were observed in the bacterial community of the digestate, while granules appeared during recovery. Fluorescence microscopic analysis of the granules showed a close spatial relationship between calcium and oil and/or long chain fatty acids. This finding further substantiated the hypothesis that calcium precipitated with carbon of organic origin and reduced the negative effects of overloading with oil. Furthermore, the enrichment of phosphate minerals in the granules was shown, and molecular biological analyses detected polyphosphate-accumulating organisms as well as methanogenic archaea in the core. Organisms related to Methanoculleus receptaculi were detected in the inner zones of a granule, whereas they were present in the digestate only after process recovery. This finding indicated more favorable microhabitats inside the granules that supported process recovery. Thus, the granule formation triggered by calcium oxide addition served as a tool to influence the composition of the microbial community and to stabilize the process after overloading with oil.

  5. Process Recovery after CaO Addition Due to Granule Formation in a CSTR Co-Digester—A Tool to Influence the Composition of the Microbial Community and Stabilize the Process?

    PubMed Central

    Liebrich, Marietta; Kleyböcker, Anne; Kasina, Monika; Miethling-Graff, Rona; Kassahun, Andrea; Würdemann, Hilke

    2016-01-01

    The composition, structure and function of granules formed during process recovery with calcium oxide in a laboratory-scale fermenter fed with sewage sludge and rapeseed oil were studied. In the course of over-acidification and successful process recovery, only minor changes were observed in the bacterial community of the digestate, while granules appeared during recovery. Fluorescence microscopic analysis of the granules showed a close spatial relationship between calcium and oil and/or long chain fatty acids. This finding further substantiated the hypothesis that calcium precipitated with carbon of organic origin and reduced the negative effects of overloading with oil. Furthermore, the enrichment of phosphate minerals in the granules was shown, and molecular biological analyses detected polyphosphate-accumulating organisms as well as methanogenic archaea in the core. Organisms related to Methanoculleus receptaculi were detected in the inner zones of a granule, whereas they were present in the digestate only after process recovery. This finding indicated more favorable microhabitats inside the granules that supported process recovery. Thus, the granule formation triggered by calcium oxide addition served as a tool to influence the composition of the microbial community and to stabilize the process after overloading with oil. PMID:27681911

  6. Rapid synthesis of hybrids and hollow PdO nanostructures by controlled in situ dissolution of a ZnO nanorod template: insights into the formation mechanism and thermal stability.

    PubMed

    Kundu, Subhajit; Ravishankar, N

    2016-01-21

    Hollow nanomaterials have attracted a lot of interest by virtue of their wide range of applications that arise primarily due to their unique architecture. A common strategy to synthesize hollow nanomaterials is by nucleation of the shell material over a preformed core and subsequent dissolution of the core in the second step. Herein an ultrafast, microwave route has been demonstrated, to synthesize PdO nanotubes in a single step using ZnO as a sacrificial template. The mechanism of the nanotube formation has been investigated in detail using control experiments. By tuning the starting ratio of PdCl2 : ZnO, hollow to hybrid PdO nanostructures could be obtained using the same method. Conversion of the PdO to Pd nanotubes has been shown by simple NaBH4 treatment. The thermal stability of the PdO nanotubes has been studied. The insights presented here are general and applicable for the synthesis of hybrids/hollow structures in other systems as well.

  7. Coupled Directional Stability of Multiple Ship Formations

    DTIC Science & Technology

    2013-06-01

    Criteria tn Hull Design using Linear Theory, • Tram;. RINA, : 993 Lyster. C. • ana l0l.1ghts. ll. L. , "Preatction Bquat1ons tor Ships• TUrning...Manoeuvring Criteria tn Hull Design using LlJlear Theory, • Trana. RINA, : 993 Lyster. C. • ana l0l.1ghts. ll. L. , "Prealction Bquatlans tor Ships• TUrning...Ship maneuvering and seakeeping,” Lecture Notes, Shanghai Jiao Tong University, 2006. [8] C. Daskam, “ DDG -2025: Combating the FIAC threat,” Project

  8. Composition Effects on Phase Formation and Stability

    NASA Technical Reports Server (NTRS)

    Kelton, Kenneth F.

    1999-01-01

    In this report, results from experimental studies of the composition dependence of nucleation are presented. A model for nucleation that takes simultaneous account of the interfacial attachment processes at the growing cluster interface and diffusion into the region surrounding the developing cluster is presented and numerical results are discussed.

  9. The formation and stability of Petschek reconnection

    SciTech Connect

    Baty, H.; Forbes, T. G.; Priest, E. R.

    2014-11-15

    A combined analytical and numerical study of magnetic reconnection in two-dimensional resistive magnetohydrodynamics is carried out by using different explicit spatial variations of the resistivity. A special emphasis on the existence of stable/unstable Petschek's solutions is taken, comparing with the recent analytical model given by Forbes et al. [Phys. Plasmas 20, 052902 (2013)]. Our results show good quantitative agreement between the analytical theory and the numerical solutions for a Petschek-type solution to within an accuracy of about 10% or better. Our simulations also show that if the resistivity profile is relatively flat near the X-point, one of two possible asymmetric solutions will occur. Which solution occurs depends on small random perturbations of the initial conditions. The existence of two possible asymmetric solutions, in a system which is otherwise symmetric, constitutes an example of spontaneous symmetry breaking.

  10. Planet Formation

    NASA Technical Reports Server (NTRS)

    Lissauer, Jack J.; Fonda, Mark (Technical Monitor)

    2002-01-01

    Modern theories of star and planet formation and of the orbital stability of planetary systems are described and used to discuss possible characteristics of undiscovered planetary systems. The most detailed models of planetary growth are based upon observations of planets and smaller bodies within our own Solar System and of young stars and their environments. Terrestrial planets are believed to grow via pairwise accretion until the spacing of planetary orbits becomes large enough that the configuration is stable for the age of the system. Giant planets begin their growth as do terrestrial planets, but they become massive enough that they are able to accumulate substantial amounts of gas before the protoplanetary disk dissipates. These models predict that rocky planets should form in orbit about most single stars. It is uncertain whether or not gas giant planet formation is common, because most protoplanetary disks may dissipate before solid planetary cores can grow large enough to gravitationally trap substantial quantities of gas. A potential hazard to planetary systems is radial decay of planetary orbits resulting from interactions with material within the disk. Planets more massive than Earth have the potential to decay the fastest, and may be able to sweep up smaller planets in their path. The implications of the giant planets found in recent radial velocity searches for the abundances of habitable planets are discussed, and the methods that are being used and planned for detecting and characterizing extrasolar planets are reviewed.

  11. Membrane stabilizer

    DOEpatents

    Mingenbach, W.A.

    1988-02-09

    A device is provided for stabilizing a flexible membrane secured within a frame, wherein a plurality of elongated arms are disposed radially from a central hub which penetrates the membrane, said arms imposing alternately against opposite sides of the membrane, thus warping and tensioning the membrane into a condition of improved stability. The membrane may be an opaque or translucent sheet or other material. 10 figs.

  12. Stabilizing population.

    PubMed

    Brown, L; Mitchell, J

    1998-04-01

    This article is a reprint of the Worldwatch Institute's "State of the World Report," Chapter 10: "Building a New Economy." 16 countries reached zero population growth by 1997. 33 countries have stabilized population, which amounts to 14% of world population. It is estimated that by 2050 population will include an additional 3.6 billion people beyond the present 6 billion. About 60% of the added population will be in Asia, an increase from 3.4 billion in 1995 to 5.4 billion in 2050. China's current population of 1.2 billion will reach 1.5 billion. India's population is expected to rapidly rise from 930 million to 1.53 billion. Populations in the Middle East and North Africa are expected to double in size. Sub-Saharan population is expected to triple in size. By 2050, Nigeria will have 339 million people, which was the entire population of Africa in 1960. There is a great need to stabilize population in a number of currently unstabilized countries. In 1971, Bangladesh and Pakistan had the same population; however, by 2050, Pakistan, without a strong commitment to reducing population growth, will have 70 million more people than Bangladesh. Population stabilization will depend on removal of physical and social barriers that prevent women from using family planning services and thereby help them control their own unwanted fertility. Stabilization will require poverty alleviation and removal of the need for large families. Family size is reduced with lower infant and child mortality risk, increased education, a higher legal age of marriage, and investment in stabilization programs. Solutions to global population growth cannot wait for health reform and budget deficit reductions.

  13. Orbit Stabilization of Nanosat

    SciTech Connect

    JOHNSON,DAVID J.

    1999-12-01

    An algorithm is developed to control a pulsed {Delta}V thruster on a small satellite to allow it to fly in formation with a host satellite undergoing time dependent atmospheric drag deceleration. The algorithm uses four short thrusts per orbit to correct for differences in the average radii of the satellites due to differences in drag and one thrust to symmetrize the orbits. The radial difference between the orbits is the only input to the algorithm. The algorithm automatically stabilizes the orbits after ejection and includes provisions to allow azimuthal positional changes by modifying the drag compensation pulses. The algorithm gives radial and azimuthal deadbands of 50 cm and 3 m for a radial measurement accuracy of {+-} 5 cm and {+-} 60% period variation in the drag coefficient of the host. Approaches to further reduce the deadbands are described. The methodology of establishing a stable orbit after ejection is illustrated in an appendix. The results show the optimum ejection angle to minimize stabilization thrust is upward at 86{sup o} from the orbital velocity. At this angle the stabilization velocity that must be supplied by the thruster is half the ejection velocity. An ejection velocity of 0.02 m/sat 86{sup o} gives an azimuthal separation after ejection and orbit stabilization of 187 m. A description of liquid based gas thrusters suitable for the satellite control is included in an appendix.

  14. Formation of multimeric antibodies for self-delivery of active monomers.

    PubMed

    Dekel, Yaron; Machluf, Yossy; Gefen, Tal; Eidelshtein, Gennady; Kotlyar, Alexander; Bram, Yaron; Shahar, Ehud; Reslane, Farah; Aizenshtein, Elina; Pitcovski, Jacob

    2017-11-01

    Proteins and peptides have been used as drugs for almost a century. Technological advances in the past 30 years have enabled the production of pure, stable proteins in vast amounts. In contrast, administration of proteins based on their native active conformation (and thus necessitating the use of subcutaneous injections) has remained solely unchanged. The therapeutic anti-HER2 humanized monoclonal immunoglobulin (IgG) Trastuzumab (Herceptin) is a first line of the treatment for breast cancer. Chicken IgY is a commercially important polyclonal antibody (Ab). These Abs were examined for their ability to self-assemble and form ordered aggregates, by several biophysical methods. Atomic force microscopy analyses revealed the formation of multimeric nanostructures. The biological activity of multimeric IgG or IgY particles was retained and restored, in a dilution/time-dependent manner. IgG activity was confirmed by a binding assay using HER2 + human breast cancer cell line, SKBR3, while IgY activity was confirmed by ELISA assay using the VP2 antigen. Competition assay with native Herceptin antibodies demonstrated that the binding availability of the multimer formulation remained unaffected. Under long incubation periods, IgG multimers retained five times more activity than native IgG. In conclusion, the multimeric antibody formulations can serve as a storage depositories and sustained-release particles. These two important characteristics make this formulation promising for future novel administration protocols and altogether bring to light a different conceptual approach for the future use of therapeutic proteins as self-delivery entities rather than conjugated/encapsulated to other bio-compounds.

  15. Enhanced stability of freestanding lipid bilayer and its stability criteria

    NASA Astrophysics Data System (ADS)

    Jeong, Dae-Woong; Jang, Hyunwoo; Choi, Siyoung Q.; Choi, Myung Chul

    2016-12-01

    We present a new strategy to dramatically enhance the stability of freestanding lipid bilayers. We found that an addition of a water in oil emulsion stabilizer, SPAN 80 to a solvent phase guarantees nearly millimeter-scale stable freestanding lipid bilayers. The water permeability, bilayer area, contact angle, and interfacial tension were measured as a function of time and SPAN 80-to-lipid weight ratio (ΦSPAN 80) with several different solvents. Surprisingly, the SPAN 80, instead of remaining in the bilayer, was moved out of the bilayer during the bilayer formation. Also we studied the effect of solvent on freestanding bilayer formation, and found that squalene was the only solvent that was not incorporated into the bilayer. The regime of stable bilayer formation was experimentally determined to be 3/1 < ΦSPAN 80 < 15/1, and we suggest general stability criteria for bilayer formation. This technique and the suggested stability criteria can be potentially helpful to many model membrane-based researches in life sciences, physical sciences and biomedical engineering fields.

  16. Enhanced stability of freestanding lipid bilayer and its stability criteria

    PubMed Central

    Jeong, Dae-Woong; Jang, Hyunwoo; Choi, Siyoung Q.; Choi, Myung Chul

    2016-01-01

    We present a new strategy to dramatically enhance the stability of freestanding lipid bilayers. We found that an addition of a water in oil emulsion stabilizer, SPAN 80 to a solvent phase guarantees nearly millimeter-scale stable freestanding lipid bilayers. The water permeability, bilayer area, contact angle, and interfacial tension were measured as a function of time and SPAN 80-to-lipid weight ratio (ΦSPAN 80) with several different solvents. Surprisingly, the SPAN 80, instead of remaining in the bilayer, was moved out of the bilayer during the bilayer formation. Also we studied the effect of solvent on freestanding bilayer formation, and found that squalene was the only solvent that was not incorporated into the bilayer. The regime of stable bilayer formation was experimentally determined to be 3/1 < ΦSPAN 80 < 15/1, and we suggest general stability criteria for bilayer formation. This technique and the suggested stability criteria can be potentially helpful to many model membrane-based researches in life sciences, physical sciences and biomedical engineering fields. PMID:27982049

  17. The ubiquitin ligase Ubr4 controls stability of podocin/MEC-2 supercomplexes

    PubMed Central

    Rinschen, Markus M.; Bharill, Puneet; Wu, Xiongwu; Kohli, Priyanka; Reinert, Matthäus J.; Kretz, Oliver; Saez, Isabel; Schermer, Bernhard; Höhne, Martin; Bartram, Malte P.; Aravamudhan, Sriram; Brooks, Bernard R.; Vilchez, David; Huber, Tobias B.; Müller, Roman-Ulrich; Krüger, Marcus; Benzing, Thomas

    2016-01-01

    The PHB-domain protein podocin maintains the renal filtration barrier and its mutation is an important cause of hereditary nephrotic syndrome. Podocin and its Caenorhabditis elegans orthologue MEC-2 have emerged as key components of mechanosensitive membrane protein signalling complexes. Whereas podocin resides at a specialized cell junction at the podocyte slit diaphragm, MEC-2 is found in neurons required for touch sensitivity. Here, we show that the ubiquitin ligase Ubr4 is a key component of the podocin interactome purified both from cultured podocytes and native glomeruli. It colocalizes with podocin and regulates its stability. In C. elegans, this process is conserved. Here, Ubr4 is responsible for the degradation of mislocalized MEC-2 multimers. Ubiquitylomic analysis of mouse glomeruli revealed that podocin is ubiquitylated at two lysine residues. These sites were Ubr4-dependent and were conserved across species. Molecular dynamics simulations revealed that ubiquitylation of one site, K301, do not only target podocin/MEC-2 for proteasomal degradation, but may also affect stability and disassembly of the multimeric complex. We suggest that Ubr4 is a key regulator of podocyte foot process proteostasis. PMID:26792178

  18. SdAb heterodimer formation using leucine zippers

    NASA Astrophysics Data System (ADS)

    Goldman, Ellen R.; Anderson, George P.; Brozozog-Lee, P. Audrey; Zabetakis, Dan

    2013-05-01

    Single domain antibodies (sdAb) are variable domains cloned from camel, llama, or shark heavy chain only antibodies, and are among the smallest known naturally derived antigen binding fragments. SdAb derived from immunized llamas are able to bind antigens with high affinity, and most are capable of refolding after heat or chemical denaturation to bind antigen again. We hypothesized that the ability to produce heterodimeric sdAb would enable reagents with the robust characteristics of component sdAb, but with dramatically improved overall affinity through increased avidity. Previously we had constructed multimeric sdAb by genetically linking sdAb that bind non-overlapping epitopes on the toxin, ricin. In this work we explored a more flexible approach; the construction of multivalent binding reagents using multimerization domains. We expressed anti-ricin sdAb that recognize different epitopes on the toxin as fusions with differently charged leucine zippers. When the initially produced homodimers are mixed the leucine zipper domains will pair to produce heterodimers. We used fluorescence resonance energy transfer to confirm heterodimer formation. Surface plasmon resonance, circular dichroism, enzyme linked immunosorbent assays, and fluid array assays were used to characterize the multimer constructs, and evaluate their utility in toxin detection.

  19. Stabilizing brokerage

    PubMed Central

    Stovel, Katherine; Golub, Benjamin; Milgrom, Eva M. Meyersson

    2011-01-01

    A variety of social and economic arrangements exist to facilitate the exchange of goods, services, and information over gaps in social structure. Each of these arrangements bears some relationship to the idea of brokerage, but this brokerage is rarely like the pure and formal economic intermediation seen in some modern markets. Indeed, for reasons illuminated by existing sociological and economic models, brokerage is a fragile relationship. In this paper, we review the causes of instability in brokerage and identify three social mechanisms that can stabilize fragile brokerage relationships: social isolation, broker capture, and organizational grafting. Each of these mechanisms rests on the emergence or existence of supporting institutions. We suggest that organizational grafting may be the most stable and effective resolution to the tensions inherent in brokerage, but it is also the most institutionally demanding. PMID:22198763

  20. STABILIZED OSCILLATOR

    DOEpatents

    Jessen, P.L.; Price, H.J.

    1958-03-18

    This patent relates to sine-wave generators and in particular describes a generator with a novel feedback circuit resulting in improved frequency stability. The generator comprises two triodes having a common cathode circuit connected to oscillate at a frequency and amplitude at which the loop galn of the circutt ls unity, and another pair of triodes having a common cathode circuit arranged as a conventional amplifier. A signal is conducted from the osciliator through a frequency selective network to the amplifier and fed back to the osciliator. The unique feature of the feedback circuit is the amplifier operates in the nonlinear portion of its tube characteristics thereby providing a relatively constant feedback voltage to the oscillator irrespective of the amplitude of its input signal.

  1. Robust Hurwitz Stability and Performance Analysis of H-Infinity Controlled Forward-Velocity Dynamics of UAVs in Close Formation Flight Using Bounded Phase Conditions in a Kharitonov Framework

    NASA Astrophysics Data System (ADS)

    Johnson, Y.; Dasgupta, S.

    2014-07-01

    Multiple unmanned aerial vehicle (UAV) control in formation flight is comparatively a new research area in the field of aerospace engineering. In the proposed work, robust control techniques are implemented to maintain a fixed relative distance in horizontal and vertical direction with uniform pitch orientation in an uncertain leader-follower pattern of close formation flight platform. The forward velocity dynamics is of focal interest in this paper. H-infinity controllers are designed for leader control and its tracking. The robustness of the H-infinity controller is validated with Kharitonov related bounded phase conditions by forming interval polynomials.

  2. Improved stability of recombinant hemagglutinin using a formulation containing sodium thioglycolate.

    PubMed

    Rhodes, David G; Holtz, Kathy; Robinson, Pam; Wang, Keyang; McPherson, Clifton E; Cox, Manon M J; Srivastava, Indresh K

    2015-11-04

    This study was designed to improve the stability of liquid formulations of recombinant influenza hemagglutinin (rHA) and to understand the mechanism of early loss of potency for rHA. The potency of rHA derived from several influenza strains was determined using single radial immunodiffusion (SRID), and the structure of the rHA was characterized using SDS-PAGE and dynamic light scattering. rHA formed disulfide cross-linked multimers, and potency decreased during extended storage. To reduce disulfide-mediated cross-linking and early potency loss, rHA was formulated with sodium thioglycolate (STG) and citrate. Addition of 80 mM STG and 55 mM sodium citrate inhibited disulfide-mediated cross-linking without affecting protein function for each rHA tested. The shelf life of the rHA formulation with STG-citrate, based on potency as determined by SRID, was extended as much as 20-fold, compared to a control formulation without STG-citrate. STG-citrate did not have a significant effect on the immunogenicity of H1 A/California/7/2009 rHA in mice.

  3. Composite stabilizer unit

    SciTech Connect

    Ebaugh, L.R.; Sadler, C.P.; Carter, G.D.

    1990-12-31

    This invention is comprised of an improved fin stabilized projectile including multiple stabilizer fins upon a stabilizer unit situated at the aft end of the projectile is provided, the improvement wherein the stabilizer fins are joined into the stabilizer unit by an injection molded engineering grade polymer.

  4. Composite stabilizer unit

    DOEpatents

    Ebaugh, Larry R.; Sadler, Collin P.; Carter, Gary D.

    1992-01-01

    An improved fin stabilized projectile including multiple stabilizer fins upon a stabilizer unit situated at the aft end of the projectile is provided, the improvement wherein the stabilizer fins are joined into the stabillizer unit by an injection molded engineering grade polymer.

  5. GRAVITATIONAL FRAGMENTATION IN GALAXY MERGERS: A STABILITY CRITERION

    SciTech Connect

    Escala, Andres; Becerra, Fernando; Del Valle, Luciano; Castillo, Esteban

    2013-01-20

    We study the gravitational stability of gaseous streams in the complex environment of a galaxy merger, because mergers are known to be places of ongoing massive cluster formation and bursts of star formation. We find an analytic stability parameter for the case of gaseous streams orbiting around the merger remnant. We test our stability criterion using hydrodynamic simulations of galaxy mergers and obtain satisfactory results. We find that our criterion successfully predicts the streams that will be gravitationally unstable to fragmentation into clumps.

  6. Conditions for equilibrium solid-stabilized emulsions.

    PubMed

    Kraft, Daniela J; de Folter, Julius W J; Luigjes, Bob; Castillo, Sonja I R; Sacanna, Stefano; Philipse, Albert P; Kegel, Willem K

    2010-08-19

    Particular types of solid-stabilized emulsions can be thermodynamically stable as evidenced by their spontaneous formation and monodisperse droplet size, which only depends on system parameters. Here, we investigate the generality of these equilibrium solid-stabilized emulsions with respect to the basic constituents: aqueous phase with ions, oil, and stabilizing particles. From systematic variations of these constituents, we identify general conditions for the spontaneous formation of monodisperse solid-stabilized emulsions droplets. We conclude that emulsion stability is achieved by a combination of solid particles as well as amphiphilic ions adsorbed at the droplet surface, and low interfacial tensions of the bare oil-water interface of order 10 mN/m or below. Furthermore, preferential wetting of the colloidal particles by the oil phase is necessary for thermodynamic stability. We demonstrate the sufficiency of these basic requirements by extending the observed thermodynamic stability to emulsions of different compositions. Our findings point to a new class of colloid-stabilized meso-emulsions with a potentially high impact on industrial emulsification processes due to the associated large energy savings.

  7. Plutonium inventories for stabilization and stabilized materials

    SciTech Connect

    Williams, A.K.

    1996-05-01

    The objective of the breakout session was to identify characteristics of materials containing plutonium, the need to stabilize these materials for storage, and plans to accomplish the stabilization activities. All current stabilization activities are driven by the Defense Nuclear Facilities Safety Board Recommendation 94-1 (May 26, 1994) and by the recently completed Plutonium ES&H Vulnerability Assessment (DOE-EH-0415). The Implementation Plan for accomplishing stabilization of plutonium-bearing residues in response to the Recommendation and the Assessment was published by DOE on February 28, 1995. This Implementation Plan (IP) commits to stabilizing problem materials within 3 years, and stabilizing all other materials within 8 years. The IP identifies approximately 20 metric tons of plutonium requiring stabilization and/or repackaging. A further breakdown shows this material to consist of 8.5 metric tons of plutonium metal and alloys, 5.5 metric tons of plutonium as oxide, and 6 metric tons of plutonium as residues. Stabilization of the metal and oxide categories containing greater than 50 weight percent plutonium is covered by DOE Standard {open_quotes}Criteria for Safe Storage of Plutonium Metals and Oxides{close_quotes} December, 1994 (DOE-STD-3013-94). This standard establishes criteria for safe storage of stabilized plutonium metals and oxides for up to 50 years. Each of the DOE sites and contractors with large plutonium inventories has either started or is preparing to start stabilization activities to meet these criteria.

  8. [Occurrence of Fusarium strains and their mycotoxins in corn silage. 7. Formation of deoxynivalenol (DON) in a silage corn plot artificially inoculated with Fusarium culmorum and the effect of silaging on the stability of the DON formed].

    PubMed

    Lepom, P; Knabe, O; Baath, H

    1990-10-01

    The formation of deoxynivalenol in a maize plot inoculated with Fusarium culmorum was studied over a growing season. Already three weeks after inoculation 4.9 mg/kg of DON were measured in the infected ears. The toxin concentration increased continuously up to harvest after eight weeks to a value of 261 mg/kg. Ensilage experiments in laboratory scale silos have shown that the DON content of naturally contaminated corn-cob-mix was not reduced during the ensilage process. It was concluded that infection of maize plants by toxin-producing Fusarium species followed by DON production in the field seems to be the most probable way of contamination of maize silage with this mycotoxin.

  9. Geological evolution and analysis of confirmed or suspected gas hydrate localities: Volume 10, Basin analysis, formation and stability of gas hydrates of the Aleutian Trench and the Bering Sea

    SciTech Connect

    Krason, J.; Ciesnik, M.

    1987-01-01

    Four major areas with inferred gas hydrates are the subject of this study. Two of these areas, the Navarin and the Norton Basins, are located within the Bering Sea shelf, whereas the remaining areas of the Atka Basin in the central Aleutian Trench system and the eastern Aleutian Trench represent a huge region of the Aleutian Trench-Arc system. All four areas are geologically diverse and complex. Particularly the structural features of the accretionary wedge north of the Aleutian Trench still remain the subjects of scientific debates. Prior to this study, suggested presence of the gas hydrates in the four areas was based on seismic evidence, i.e., presence of bottom simulating reflectors (BSRs). Although the disclosure of the BSRs is often difficult, particularly under the structural conditions of the Navarin and Norton basins, it can be concluded that the identified BSRs are mostly represented by relatively weak and discontinuous reflectors. Under thermal and pressure conditions favorable for gas hydrate formation, the relative scarcity of the BSRs can be attributed to insufficient gas supply to the potential gas hydrate zone. Hydrocarbon gas in sediment may have biogenic, thermogenic or mixed origin. In the four studied areas, basin analysis revealed limited biogenic hydrocarbon generation. The migration of the thermogenically derived gases is probably diminished considerably due to the widespread diagenetic processes in diatomaceous strata. The latter processes resulted in the formation of the diagenetic horizons. The identified gas hydrate-related BSRs seem to be located in the areas of increased biogenic methanogenesis and faults acting as the pathways for thermogenic hydrocarbons.

  10. Evaluation of Cavity Collapse and Surface Crater Formation at the Salut Underground Nuclear Test in U20ak, Nevada National Security Site, and the Impact of Stability of the Ground Surface

    SciTech Connect

    Pawloski, G A

    2012-04-25

    At the request of Jerry Sweeney, the LLNL Containment Program performed a review of nuclear test-related data for the Salut underground nuclear test in U20ak to assist in evaluating this legacy site as a test bed for application technologies for use in On-Site Inspections (OSI) under the Comprehensive Nuclear Test Ban Treaty. Review of the Salut site is complicated because the test experienced a subsurface, rather than surface, collapse. Of particular interest is the stability of the ground surface above the Salut detonation point. Proposed methods for on-site verification include radiological signatures, artifacts from nuclear testing activities, and imaging to identify alteration to the subsurface hydrogeologogy due to the nuclear detonation. Sweeney's proposal requires physical access at or near the ground surface of specific underground nuclear test locations at the Nevada Nuclear Test Site (NNSS, formerly the Nevada Test Site), and focuses on possible activities such as visual observation, multispectral measurements, and shallow, and deep geophysical surveys.

  11. Evaluation of Cavity Collapse and Surface Crater Formation at the Norbo Underground Nuclear Test in U8c, Nevada Nuclear Security Site, and the Impact on Stability of the Ground Surface

    SciTech Connect

    Pawloski, G A

    2012-06-18

    Lawrence Livermore National Laboratory (LLNL) Containment Program performed a review of nuclear test-related data for the Norbo underground nuclear test in U8c to assist in evaluating this legacy site as a test bed for application technologies for use in On-Site Inspections (OSI) under the Comprehensive Nuclear Test Ban Treaty. This request is similar to one made for the Salut site in U8c (Pawloski, 2012b). Review of the Norbo site is complicated because the test first exhibited subsurface collapse, which was not unusual, but it then collapsed to the surface over one year later, which was unusual. Of particular interest is the stability of the ground surface above the Norbo detonation point. Proposed methods for on-site verification include radiological signatures, artifacts from nuclear testing activities, and imaging to identify alteration to the subsurface hydrogeology due to the nuclear detonation. Aviva Sussman from the Los Alamos National Laboratory (LANL) has also proposed work at this site. Both proposals require physical access at or near the ground surface of specific underground nuclear test locations at the Nevada Nuclear Security Site (NNSS), formerly the Nevada Test Site (NTS), and focus on possible activities such as visual observation, multispectral measurements, and shallow and deep geophysical surveys.

  12. Temperature stability of nanocellulose dispersions.

    PubMed

    Heggset, Ellinor B; Chinga-Carrasco, Gary; Syverud, Kristin

    2017-02-10

    Cellulose nanofibrils (CNF) have potential as rheology modifiers of water based fluids, e.g. drilling fluids for use in oil wells or as additives in injection water for enhanced oil recovery (EOR). The temperature in oil wells can be high (>100°C), and the retention time long; days for drilling fluids and months for EOR fluids. Hence, it is important to assess the temperature stability over time of nanocellulose dispersions to clarify their suitability as rheology modifiers of water based fluids at such harsh conditions. Dispersions of CNF produced mechanically, by using TEMPO mediated oxidation and by using carboxymethylation as pretreatment, in addition to cellulose nanocrystals (CNC), have been subjected to heat aging. Temperature stability was best for CNC and for mechanically produced CNF that were stable after heating to 140°C for three days. The effect of additives was evaluated; cesium formate and sodium formate increased the temperature stability of the dispersions, while there was no effect of using phosphate buffer.

  13. Galaxy formation

    SciTech Connect

    Silk, J.

    1984-11-01

    Implications of the isotropy of the cosmic microwave background on large and small angular scales for galaxy formation are reviewed. In primeval adiabatic fluctuations, a universe dominated by cold, weakly interacting nonbaryonic matter, e.g., the massive photino is postulated. A possible signature of photino annihilation in our galactic halo involves production of cosmic ray antiprotons. If the density is near its closure value, it is necessary to invoke a biasing mechanism for suppressing galaxy formation throughout most of the universe in order to reconcile the dark matter density with the lower astronomical determinations of the mean cosmological density. A mechanism utilizing the onset of primordial massive star formation to strip gaseous protogalaxies is described. Only the densest, early collapsing systems form luminous galaxies. (ESA)

  14. Selective Stabilization of Ribose by Borate

    NASA Astrophysics Data System (ADS)

    Furukawa, Yoshihiro; Horiuchi, Mana; Kakegawa, Takeshi

    2013-10-01

    In this study, borate was found to selectively increase the stability of ribose over other aldopentoses. Ribose is the only sugar present in both early RNA-based biochemistry and contemporary DNA-based life, and the stability of ribose is of fundamental concern for determining the origin of early RNA-based biochemistry. The formose reaction is a potential process in the prebiotic synthesis of ribose and its stereoisomers arabinose, xylose, and lyxose. Ribose is the least stable of these aldopentoses, raising the fundamental question of whether it was originally a component of primitive RNA or was selected through biotic processes. Borate is known to increase the stability of aldopentoses, but the specific differences in the stabilization achieved among different stereoisomers remain unclear. In this study, it was found that the stabilities of all of the tested pentoses increased with the concentration of added borate, but notably, the stability of ribose increased the most. The predominant formation of complexes between borate and ribose was verified, in agreement with previous studies. This borate complex formation might have sequestered ribose from the isomerization and decomposition reactions, resulting in its selective stabilization. These findings indicate that ribose could have accumulated in borate-rich environments on the early Earth and suggest that ribose-based nucleotides combined with phosphate and nucleobases formed abiotically.

  15. Comet formation

    NASA Astrophysics Data System (ADS)

    Blum, J.

    2014-07-01

    There has been vast progress in our understanding of planetesimal formation over the past decades, owing to a number of laboratory experiments as well as to refined models of dust and ice agglomeration in protoplanetary disks. Coagulation rapidly forms cm-sized ''pebbles'' by direct sticking in collisions at low velocities (Güttler et al. 2010; Zsom et al. 2010). For the further growth, two model approaches are currently being discussed: (1) Local concentration of pebbles in nebular instabilities until gravitational instability occurs (Johansen et al. 2007). (2) A competition between fragmentation and mass transfer in collisions among the dusty bodies, in which a few ''lucky winners'' make it to planetesimal sizes (Windmark et al. 2012a,b; Garaud et al. 2013). Predictions of the physical properties of the resulting bodies in both models allow a distinction of the two formation scenarios of planetesimals. In particular, the tensile strength (i.e, the inner cohesion) of the planetesimals differ widely between the two models (Skorov & Blum 2012; Blum et al. 2014). While model (1) predicts tensile strengths on the order of ˜ 1 Pa, model (2) results in rather compactified dusty bodies with tensile strengths in the kPa regime. If comets are km-sized survivors of the planetesimal-formation era, they should in principle hold the secret of their formation process. Water ice is the prime volatile responsible for the activity of comets. Thermophysical models of the heat and mass transport close to the comet-nucleus surface predict water-ice sublimation temperatures that relate to maximum sublimation pressures well below the kPa regime predicted for formation scenario (2). Model (1), however, is in agreement with the observed dust and gas activity of comets. Thus, a formation scenario for cometesimals involving gravitational instability is favored (Blum et al. 2014).

  16. Wüstite stability in the presence of a CO2-fluid and a carbonate-silicate melt: Implications for the graphite/diamond formation and generation of Fe-rich mantle metasomatic agents

    NASA Astrophysics Data System (ADS)

    Bataleva, Yuliya V.; Palyanov, Yuri N.; Sokol, Alexander G.; Borzdov, Yuri M.; Bayukov, Oleg A.

    2016-02-01

    Experimental simulation of the interaction of wüstite with a CO2-rich fluid and a carbonate-silicate melt was performed using a multianvil high-pressure split-sphere apparatus in the FeO-MgO-CaO-SiO2-Al2O3-CO2 system at a pressure of 6.3 GPa and temperatures in the range of 1150 °C-1650 °C and with run time of 20 h. At relatively low temperatures, decarbonation reactions occur in the system to form iron-rich garnet (Alm75Prp17Grs8), magnesiowüstite (Mg# ≤ 0.13), and CO2-rich fluid. Under these conditions, magnesiowüstite was found to be capable of partial reducing CO2 to C0 that leads to the formation of Fe3+-bearing magnesiowüstite, crystallization of magnetite and metastable graphite, and initial growth of diamond seeds. At T ≥ 1450 °C, an iron-rich carbonate-silicate melt (FeO ~ 56 wt.%, SiO2 ~ 12 wt.%) forms in the system. Interaction between (Fe,Mg)O, SiO2, fluid and melt leads to oxidation of magnesiowüstite and crystallization of fayalite-magnetite spinel solid solution (1450 °C) as well as to complete dissolution of magnesiowüstite in the carbonate-silicate melt (1550 °C-1650 °C). In the presence of both carbonate-silicate melt and CO2-rich fluid, dissolution (oxidation) of diamond and metastable graphite was found to occur. The study results demonstrate that under pressures of the lithospheric mantle in the presence of a CO2-rich fluid, wüstite/magnesiowüstite is stable only at relatively low temperatures when it is in the absolute excess relative to CO2-rich fluid. In this case, the redox reactions, which produce metastable graphite and diamond with concomitant partial oxidation of wüstite to magnetite, occur. Wüstite is unstable under high concentrations of a CO2-rich fluid as well as in the presence of a carbonate-silicate melt: it is either completely oxidized or dissolves in the melt or fluid phase, leading to the formation of Fe2 +- and Fe3 +-enriched carbonate-silicate melts, which are potential metasomatic agents in the

  17. Shear-stabilized emulsion flooding process

    SciTech Connect

    Carpenter, C.W.; Reed, R.L.

    1982-06-29

    Additional amounts of crude oil are recovered from a subterranean formation by flooding with a translucent emulsion comprising an upper- or middle-phase microemulsion as an external phase and a polymer-containing brine solution as an internal phase. The translucent emulsion tends to coalesce into its component phases under conditions of no shear, but is stabilized by low shears such as those imposed on fluids flowing through a subterranean formation.

  18. Thermal and structural study of the crystal phases and mesophases in the lithium and thallium(i) propanoates and pentanoates binary systems: formation of mixed salts and stabilization of the ionic liquid crystal phase.

    PubMed

    Martínez Casado, F J; Ramos Riesco, M; da Silva, I; Labrador, A; Redondo, M I; García Pérez, M V; López-Andrés, S; Rodríguez Cheda, J A

    2010-08-12

    The temperature and enthalpy vs composition phase diagrams of the binary systems [xC(2)H(5)CO(2)Li + (1 - x)C(2)H(5)CO(2)Tl], and [x(n-C(4)H(9)CO(2)Li) + (1 - x)n-C(4)H(9)CO(2)Tl], where x is the mole fraction, were determined by DSC. Both binary systems display the formation of one 2:1 mixed salt each (at x = 0.667) that appear as a peritectic (incongruent melting) at T(fus) = 512.0 K, and T(fus) = 461.1 K, with Delta(fus)H(m) = 13.76 and 8.08 kJ.mol(-1) for Li-Tl (I) propanoates, and n-pentanoate mixed salts, respectively. The thermotropic liquid crystal of the thallium(I) n-pentanoate transforms into a more stable liquid-crystal phase, which appears in the phase diagram between 380 and 488 K and for x = 0 up to x = 0.56. The crystal structure of thallium(I) propanoate and of the two mixed salts were obtained via X-ray synchrotron radiation diffraction measurements. These compounds present a bilayered structure similar to the two pure lithium salts previously found by our group.

  19. Effect of solvent, temperature and pressure on the stability of chiral and perovskite metal formate frameworks of [NH2NH3][M(HCOO)3] (M = Mn, Fe, Zn).

    PubMed

    Mączka, Mirosław; Pasińska, Katarzyna; Ptak, Maciej; Paraguassu, Waldeci; da Silva, Tercio Almeida; Sieradzki, Adam; Pikul, Adam

    2016-11-23

    We report the synthesis, crystal structure, and thermal, Raman, infrared and magnetic properties of [NH2NH3][M(HCOO)3] (HyM) compounds (M = Mn, Zn, Fe). Our results show that synthesis from methanol solution leads to perovskite polymorphs while that from 1-methyl-2-pyrrolidinone or its mixture with methanol allows obtaining chiral polymorphs. Perovskite HyFe, chiral HyFe and chiral HyMn undergo phase transitions at 347, 336 and 296 K, respectively, with symmetry changes from Pnma to Pna21, P63 to P212121 and P63 to P21. X-ray diffraction and Raman studies show that the phase transitions are governed by dynamics of the hydrazinium ions. Low-temperature magnetic studies show that these compounds exhibit magnetic ordering below 9-12.5 K. Since the low-temperature structures of chiral HyMn and perovskite HyFe are polar, these compounds are possible multiferroic materials. We also report high-pressure Raman scattering studies of chiral and perovskite HyZn, which show much larger stiffness of the latter phase. These studies also show that the ambient pressure polar phases are stable up to at least 1.4 and 4.1 GPa for the chiral and perovskite phase, respectively. Between 1.4 and 2.0 GPa (for chiral HyZn) and 4.1 and 5.2 GPa (for perovskite HyZn) pressure-induced transitions are observed associated with changes in the zinc-formate framework. Strong broadening of Raman bands and the decrease in their number for the high-pressure phase of chiral HyZn suggest that this phase is disordered and has higher symmetry than the ambient pressure one.

  20. Stabilizing multicellularity through ratcheting

    PubMed Central

    Libby, Eric; Conlin, Peter L.; Kerr, Ben; Ratcliff, William C.

    2016-01-01

    The evolutionary transition to multicellularity probably began with the formation of simple undifferentiated cellular groups. Such groups evolve readily in diverse lineages of extant unicellular taxa, suggesting that there are few genetic barriers to this first key step. This may act as a double-edged sword: labile transitions between unicellular and multicellular states may facilitate the evolution of simple multicellularity, but reversion to a unicellular state may inhibit the evolution of increased complexity. In this paper, we examine how multicellular adaptations can act as evolutionary ‘ratchets’, limiting the potential for reversion to unicellularity. We consider a nascent multicellular lineage growing in an environment that varies between favouring multicellularity and favouring unicellularity. The first type of ratcheting mutations increase cell-level fitness in a multicellular context but are costly in a single-celled context, reducing the fitness of revertants. The second type of ratcheting mutations directly decrease the probability that a mutation will result in reversion (either as a pleiotropic consequence or via direct modification of switch rates). We show that both types of ratcheting mutations act to stabilize the multicellular state. We also identify synergistic effects between the two types of ratcheting mutations in which the presence of one creates the selective conditions favouring the other. Ratcheting mutations may play a key role in diverse evolutionary transitions in individuality, sustaining selection on the new higher-level organism by constraining evolutionary reversion. This article is part of the themed issue ‘The major synthetic evolutionary transitions’. PMID:27431522

  1. Enhanced colloidal stability of hydroxyapatite

    NASA Astrophysics Data System (ADS)

    Borum, La Rhonda Terese

    Hydroxyapatite, Ca10(PO4)6(OH) 2 is the most thermodynamically stable calcium phosphate in physiological environments. Hence, it is the main inorganic mineral found in bone and teeth. Its colloidal stability, however, is poor because hydroxyapatite (HAp) particles exhibit sediment formation upon standing at short time periods, where agglomerates form and lead to non-homogeneous suspensions. Surface modification is a promising method to tailor the colloidal stability of hydroxyapatite for biomaterial applications. Three techniques to modify the HAp surface and enhance the colloidal stability of HAp were investigated. Modified particles were characterized by methods sensitive to surface chemistry changes, such as sedimentation studies, diffuse reflectance Fourier transform infrared spectroscopy (DRIFT), Brunauer-Emmett-Teller (BET) surface area, and electrophoresis. Sedimentation studies demonstrated how effective each technique was in improving the colloidal stability of hydroxyapatite particles. Electrophoresis provided information on electrostatic interactions within each system. The first technique entailed an esterification reaction of the HAp surface with dodecyl alcohol at elevated temperatures. DRIFT results showed that dodecyl groups from the alcohol replaced acidic hydroxyl and phosphate sites on the HAp surface, giving rise to enhanced colloidal stability through steric interactions in ethanol suspensions. TGA curves gave insight to the degree of esterification for the esterified particles. Higher reaction temperatures give rise to a higher degree of esterification resulting in better colloidal stability. The second technique applied a silica coating on the HAp surface by the hydrolysis of tetraethyl orthosilicate in ethanol. Silica was coated onto the HAp surface at 5--75 wt% loading amounts. A combination of acid dissolution and x-ray diffraction (XRD), along with BET showed that the silica coating is complete at 50 wt% silica loading. The silica coating

  2. Aqueous foams stabilized by chitin nanocrystals.

    PubMed

    Tzoumaki, Maria V; Karefyllakis, Dimitris; Moschakis, Thomas; Biliaderis, Costas G; Scholten, Elke

    2015-08-21

    The aim of the present study was to explore the potential use of chitin nanocrystals, as colloidal rod-like particles, to stabilize aqueous foams. Chitin nanocrystals (ChN) were prepared by acid hydrolysis of crude chitin and foams were generated mainly by sonicating the respective dispersions. The foamability of the chitin nanocrystals was evaluated and the resulting foams were assessed for their stability, in terms of foam volume reduction and serum release patterns, during storage. Additionally, the samples were studied with light scattering and optical microscopy in order to explore the bubble size distribution and morphology of the foam. Nanocrystal concentration and charge density was varied to alter the packing of the crystals at the interface. At low concentrations of ChNs, foams were stable against coalescence and disproportionation for a period of three hours, whereas at higher concentrations, the foams were stable for several days. The enhanced stability of foams prepared with ChNs, compared to surfactant-stabilized foams, can be mainly attributed to the irreversible adsorption of the ChNs at the air-water interface, thereby providing Pickering stabilization. Both foam volume and stability of the foam were increased with an increase in ChNs concentration, and at pH values around the chitin's pKa (pH 7.0). Under these conditions, the ChNs show minimal electrostatic repulsion and therefore a higher packing of the nanocrystals is promoted. Moreover, decreased electrostatic repulsion enhances network formation between the ChNs in the aqueous films, thereby providing additional stability by gel formation. Overall, ChNs were proven to be effective in stabilizing foams, and may be useful in the design of Pickering-stabilized food grade foams.

  3. Cloud Formation

    NASA Astrophysics Data System (ADS)

    Graham, Mark Talmage

    2004-05-01

    Cloud formation is crucial to the heritage of modern physics, and there is a rich literature on this important topic. In 1927, Charles T.R. Wilson was awarded the Nobel Prize in physics for applications of the cloud chamber.2 Wilson was inspired to study cloud formation after working at a meteorological observatory on top of the highest mountain in Scotland, Ben Nevis, and testified near the end of his life, "The whole of my scientific work undoubtedly developed from the experiments I was led to make by what I saw during my fortnight on Ben Nevis in September 1894."3 To form clouds, Wilson used the sudden expansion of humid air.4 Any structure the cloud may have is spoiled by turbulence in the sudden expansion, but in 1912 Wilson got ion tracks to show up by using strobe photography of the chamber immediately upon expansion.5 In the interim, Millikan's study in 1909 of the formation of cloud droplets around individual ions was the first in which the electron charge was isolated. This study led to his famous oil drop experiment.6 To Millikan, as to Wilson, meteorology and physics were professionally indistinct. With his meteorological physics expertise, in WWI Millikan commanded perhaps the first meteorological observation and forecasting team essential to military operation in history.7 But even during peacetime meteorology is so much of a concern to everyone that a regular news segment is dedicated to it. Weather is the universal conversation topic, and life on land could not exist as we know it without clouds. One wonders then, why cloud formation is never covered in physics texts.

  4. Predicting the Stability of Hypervalent Molecules

    ERIC Educational Resources Information Center

    Mitchell, Tracy A.; Finnocchio, Debbie; Kua, Jeremy

    2007-01-01

    An exercise is described which introduces students to using concepts in thermochemistry to predict relative stability of a hypervalent molecule. Students will compare the energies of formation for both fluoride and the hydride by calculations and they will also explore the issue of partial ionic character in polar covalent bonds.

  5. District Stability Framework (DSF)

    DTIC Science & Technology

    2010-10-01

    systemic causes for the SOI. • Monitoring and Evaluation . Measure change in the stability environment with respect to specific SOI as well as overall...conditions and operating environments  Better stabilization planning  Better stabilization execution • More effective/thorough Monitoring and Evaluation (IMPACT

  6. Limits to Stability

    ERIC Educational Resources Information Center

    Cottey, Alan

    2012-01-01

    The author reflects briefly on what limited degree of global ecological stability and human cultural stability may be achieved, provided that humanity retains hope and does not give way to despair or hide in denial. These thoughts were triggered by a recent conference on International Stability and Systems Engineering. (Contains 5 notes.)

  7. Longitudinal Stability Calculations

    SciTech Connect

    Blaskiewicz,M.

    2009-01-02

    Coupled bunch longitudinal stability in the presence of high frequency impedances is considered. A frequency domain technique is developed and compared with simulations. The frequency domain technique allows for absolute stability tests and is applied to the problem of longitudinal stability in RHIC with the new 56 MHz RF system.

  8. KTKEGV repeat motifs are key mediators of normal α-synuclein tetramerization: Their mutation causes excess monomers and neurotoxicity

    PubMed Central

    Dettmer, Ulf; Newman, Andrew J.; von Saucken, Victoria E.; Bartels, Tim; Selkoe, Dennis

    2015-01-01

    α-Synuclein (αS) is a highly abundant neuronal protein that aggregates into β-sheet–rich inclusions in Parkinson’s disease (PD). αS was long thought to occur as a natively unfolded monomer, but recent work suggests it also occurs normally in α-helix–rich tetramers and related multimers. To elucidate the fundamental relationship between αS multimers and monomers in living neurons, we performed systematic mutagenesis to abolish self-interactions and learn which structural determinants underlie native multimerization. Unexpectedly, tetramers/multimers still formed in cells expressing each of 14 sequential 10-residue deletions across the 140-residue polypeptide. We postulated compensatory effects among the six highly conserved and one to three additional αS repeat motifs (consensus: KTKEGV), consistent with αS and its homologs β- and γ-synuclein all forming tetramers while sharing only the repeats. Upon inserting in-register missense mutations into six or more αS repeats, certain mutations abolished tetramer formation, shown by intact-cell cross-linking and independently by fluorescent-protein complementation. For example, altered repeat motifs KLKEGV, KTKKGV, KTKEIV, or KTKEGW did not support tetramerization, indicating the importance of charged or small residues. When we expressed numerous different in-register repeat mutants in human neural cells, all multimer-abolishing but no multimer-neutral mutants caused frank neurotoxicity akin to the proapoptotic protein Bax. The multimer-abolishing variants became enriched in buffer-insoluble cell fractions and formed round cytoplasmic inclusions in primary cortical neurons. We conclude that the αS repeat motifs mediate physiological tetramerization, and perturbing them causes PD-like neurotoxicity. Moreover, the mutants we describe are valuable tools for studying normal and pathological properties of αS and screening for tetramer-stabilizing therapeutics. PMID:26153422

  9. Feedback stabilization initiative

    SciTech Connect

    1997-06-01

    Much progress has been made in attaining high confinement regimes in magnetic confinement devices. These operating modes tend to be transient, however, due to the onset of MHD instabilities, and their stabilization is critical for improved performance at steady state. This report describes the Feedback Stabilization Initiative (FSI), a broad-based, multi-institutional effort to develop and implement methods for raising the achievable plasma betas through active MHD feedback stabilization. A key element in this proposed effort is the Feedback Stabilization Experiment (FSX), a medium-sized, national facility that would be specifically dedicated to demonstrating beta improvement in reactor relevant plasmas by using a variety of MHD feedback stabilization schemes.

  10. THERMAL STABILITY OF GLASS PLASTICS.

    DTIC Science & Technology

    COMPOSITE MATERIALS, THERMAL STABILITY), (* GLASS TEXTILES, THERMAL STABILITY), (*LAMINATED PLASTICS , THERMAL STABILITY), HEATING, COOLING, MECHANICAL PROPERTIES, FATIGUE(MECHANICS), FLEXURAL STRENGTH, THERMAL STRESSES, USSR

  11. Amphiplex Formation

    NASA Astrophysics Data System (ADS)

    Petersen, Shannon; Laaser, Jennifer; Lodge, Timothy

    2015-03-01

    Polymer-micelle complexes are currently under heavy investigation due to their potential applications in targeted drug delivery and gene therapy, yet the dynamics of the complex formation is still relatively unstudied. By varying the ratios of poly(styrene sulfonate) chains and cationic poly(dimethylaminoethyl methacrylate)-b-poly(styrene) micelles and the ionic strength of the system, we created a variety of complex configurations of different sizes and charges. The complexes were characterized dynamic light scattering and zeta potential measurements which provided information regarding the hydrodynamic radius, distribution of sizes, and effective charge.

  12. Minerals Strategic Impact on Regional Stability in Africa

    DTIC Science & Technology

    2007-03-30

    USAWC STRATEGY RESEARCH PROJECT MINERALS STRATEGIC IMPACT ON REGIONAL STABILITY IN AFRICA by Colonel Lee E...3. DATES COVERED 00-00-2006 to 00-00-2007 4. TITLE AND SUBTITLE Minerals Strategic Impact on Regional Stability in Africa 5a. CONTRACT NUMBER...Lee E. Hansen TITLE: Minerals Strategic Impact on Regional Stability in Africa FORMAT: Strategy Research Project DATE: 30 March 2007

  13. Stability of fluid flow in a cylindrical annulus

    NASA Technical Reports Server (NTRS)

    Ludwieg, H.

    1984-01-01

    Helical flow in an annulus between two coaxial cylinders is investigated with regard to its stability against the formation of helical vortices of the type known as Taylor's annular vortices. Assuming the annulus to be small and the velocities to vary linearly with radius, it is shown that the problem can be reduced to the classical case of flow between two rotating cylinders. An appropriate stability criterion for helical flows is derived from Rayleigh's stability criterion applicable to such flows.

  14. Formation of Transient Lamellipodia

    PubMed Central

    Zimmermann, Juliane; Falcke, Martin

    2014-01-01

    Cell motility driven by actin polymerization is pivotal to the development and survival of organisms and individual cells. Motile cells plated on flat substrates form membrane protrusions called lamellipodia. The protrusions repeatedly appear and retract in all directions. If a lamellipodium is stabilized and lasts for some time, it can take over the lead and determine the direction of cell motion. Protrusions traveling along the cell perimeter have also been observed. Their initiation is in some situations the effect of the dynamics of the pathway linking plasma membrane receptors to actin filament nucleation, e.g. in chemotaxis. However, lamellipodia are also formed in many cells incessantly during motion with a constant state of the signaling pathways upstream from nucleation promoting factors (NPFs), or spontaneously in resting cells. These observations strongly suggest protrusion formation can also be a consequence of the dynamics downstream from NPFs, with signaling setting the dynamic regime but not initiating the formation of individual protrusions. A quantitative mechanism for this kind of lamellipodium dynamics has not been suggested yet. Here, we present a model exhibiting excitable actin network dynamics. Individual lamellipodia form due to random supercritical filament nucleation events amplified by autocatalytic branching. They last for about 30 seconds to many minutes and are terminated by filament bundling, severing and capping. We show the relevance of the model mechanism for experimentally observed protrusion dynamics by reproducing in very good approximation the repetitive protrusion formation measured by Burnette et al. with respect to the velocities of leading edge protrusion and retrograde flow, oscillation amplitudes, periods and shape, as well as the phase relation between protrusion and retrograde flow. Our modeling results agree with the mechanism of actin bundle formation during lamellipodium retraction suggested by Burnette et al. and

  15. Computer simulation of bubble formation.

    SciTech Connect

    Insepov, Z.; Bazhirov, T.; Norman, G.; Stegailov, V.; Mathematics and Computer Science; Institute for High Energy Densities of Joint Institute for High Temperatures of RAS

    2007-01-01

    Properties of liquid metals (Li, Pb, Na) containing nanoscale cavities were studied by atomistic Molecular Dynamics (MD). Two atomistic models of cavity simulation were developed that cover a wide area in the phase diagram with negative pressure. In the first model, the thermodynamics of cavity formation, stability and the dynamics of cavity evolution in bulk liquid metals have been studied. Radial densities, pressures, surface tensions, and work functions of nano-scale cavities of various radii were calculated for liquid Li, Na, and Pb at various temperatures and densities, and at small negative pressures near the liquid-gas spinodal, and the work functions for cavity formation in liquid Li were calculated and compared with the available experimental data. The cavitation rate can further be obtained by using the classical nucleation theory (CNT). The second model is based on the stability study and on the kinetics of cavitation of the stretched liquid metals. A MD method was used to simulate cavitation in a metastable Pb and Li melts and determine the stability limits. States at temperatures below critical (T < 0.5Tc) and large negative pressures were considered. The kinetic boundary of liquid phase stability was shown to be different from the spinodal. The kinetics and dynamics of cavitation were studied. The pressure dependences of cavitation frequencies were obtained for several temperatures. The results of MD calculations were compared with estimates based on classical nucleation theory.

  16. Process for stabilization of coal liquid fractions

    DOEpatents

    Davies, Geoffrey; El-Toukhy, Ahmed

    1987-01-01

    Coal liquid fractions to be used as fuels are stabilized against gum formation and viscosity increases during storage, permitting the fuel to be burned as is, without further expensive treatments to remove gums or gum-forming materials. Stabilization is accomplished by addition of cyclohexanol or other simple inexpensive secondary and tertiary alcohols, secondary and tertiary amines, and ketones to such coal liquids at levels of 5-25% by weight with respect to the coal liquid being treated. Cyclohexanol is a particularly effective and cost-efficient stabilizer. Other stabilizers are isopropanol, diphenylmethanol, tertiary butanol, dipropylamine, triethylamine, diphenylamine, ethylmethylketone, cyclohexanone, methylphenylketone, and benzophenone. Experimental data indicate that stabilization is achieved by breaking hydrogen bonds between phenols in the coal liquid, thereby preventing or retarding oxidative coupling. In addition, it has been found that coal liquid fractions stabilized according to the invention can be mixed with petroleum-derived liquid fuels to produce mixtures in which gum deposition is prevented or reduced relative to similar mixtures not containing stabilizer.

  17. Habit formation

    PubMed Central

    Smith, Kyle S.; Graybiel, Ann M.

    2016-01-01

    Habits, both good ones and bad ones, are pervasive in animal behavior. Important frameworks have been developed to understand habits through psychological and neurobiological studies. This work has given us a rich understanding of brain networks that promote habits, and has also helped us to understand what constitutes a habitual behavior as opposed to a behavior that is more flexible and prospective. Mounting evidence from studies using neural recording methods suggests that habit formation is not a simple process. We review this evidence and take the position that habits could be sculpted from multiple dissociable changes in neural activity. These changes occur across multiple brain regions and even within single brain regions. This strategy of classifying components of a habit based on different brain signals provides a potentially useful new way to conceive of disorders that involve overly fixed behaviors as arising from different potential dysfunctions within the brain's habit network. PMID:27069378

  18. Habit formation.

    PubMed

    Smith, Kyle S; Graybiel, Ann M

    2016-03-01

    Habits, both good ones and bad ones, are pervasive in animal behavior. Important frameworks have been developed to understand habits through psychological and neurobiological studies. This work has given us a rich understanding of brain networks that promote habits, and has also helped us to understand what constitutes a habitual behavior as opposed to a behavior that is more flexible and prospective. Mounting evidence from studies using neural recording methods suggests that habit formation is not a simple process. We review this evidence and take the position that habits could be sculpted from multiple dissociable changes in neural activity. These changes occur across multiple brain regions and even within single brain regions. This strategy of classifying components of a habit based on different brain signals provides a potentially useful new way to conceive of disorders that involve overly fixed behaviors as arising from different potential dysfunctions within the brain's habit network.

  19. Stability of holographic superconductors

    SciTech Connect

    Kanno, Sugumi; Soda, Jiro

    2010-10-15

    We study the dynamical stability of holographic superconductors. We first classify perturbations around black hole background solutions into vector and scalar sectors by means of a 2-dimensional rotational symmetry. We prove the stability of the vector sector by explicitly constructing the positive definite Hamiltonian. To reveal a mechanism for the stabilization of a superconducting phase, we construct a quadratic action for the scalar sector. From the action, we see the stability of black holes near a critical point is determined by the equation of motion for a charged scalar field. We show the effective mass of the charged scalar field in hairy black holes is always above the Breitenlohner-Freedman bound near the critical point due to the backreaction of a gauge field. It implies the stability of the superconducting phase. We also argue that the stability continues away from the critical point.

  20. Stability of holographic superconductors

    NASA Astrophysics Data System (ADS)

    Kanno, Sugumi; Soda, Jiro

    2010-10-01

    We study the dynamical stability of holographic superconductors. We first classify perturbations around black hole background solutions into vector and scalar sectors by means of a 2-dimensional rotational symmetry. We prove the stability of the vector sector by explicitly constructing the positive definite Hamiltonian. To reveal a mechanism for the stabilization of a superconducting phase, we construct a quadratic action for the scalar sector. From the action, we see the stability of black holes near a critical point is determined by the equation of motion for a charged scalar field. We show the effective mass of the charged scalar field in hairy black holes is always above the Breitenlohner-Freedman bound near the critical point due to the backreaction of a gauge field. It implies the stability of the superconducting phase. We also argue that the stability continues away from the critical point.

  1. Stability of compounded thioguanine oral suspensions.

    PubMed

    Aliabadi, Hamidreza Montazeri; Romanick, Marcel; Somayaji, Vishwa; Mahdipoor, Parvin; Lavasanifar, Afsaneh

    2011-05-15

    PURPOSE. Updated information on the stability of compounded thioguanine oral suspensions prepared with currently available ingredients, as well as results of testing to determine if the addition of an antioxidant could extend shelf life by inhibiting formation of guanine, are presented. METHODS. Using triturated thioguanine tablets, three compounded suspensions were prepared: (1) a reference formulation containing methylcellulose and simple syrup, (2) an equivalent formulation using Ora-Plus and Ora-Sweet, and (3) an antioxidant-containing formulation prepared by adding ascorbic acid to the equivalent formulation. The compounded batches were stored at room temperature (19-23 °C). The chemical stability of the suspensions was evaluated immediately after compounding and at weekly intervals by a validated liquid chromatography-mass spectrometry (LCMS) assay method; physical stability was evaluated by regular visual checks and weekly pH testing. RESULTS. As demonstrated by serial LCMS testing, mean thioguanine levels in sampled batches of all three suspensions remained above accepted standards and mean guanine formation remained within acceptable limits for up to 63 days. The addition of ascorbic acid appeared to slow guanine formation but did not significantly extend the shelf life of the suspension. CONCLUSION. Compounded oral suspensions of thioguanine 20 mg/mL exhibited acceptable chemical and physical stability for up to nine weeks at 19-23 °C. The addition of ascorbic acid at a concentration of 0.1% to the suspension was not effective in consistently increasing the shelf life of the thioguanine suspensions.

  2. Stabilized Laser Gravimeter

    DTIC Science & Technology

    1976-11-01

    McMullen, "Stabilized Laser Gravim- eter," Proceedings of the 20th International Instrumentations Symposium, Albuquerque, New Mexico , May 1974. N.D...and N.D. McMullen, "Stabilized Laser Gravimeter," Proceedings of the 20th International Instrumentations Symposium, Albuquerque, New Mexico , May 1974...International Instrumentations *i, Albuquerque, New Mexico , May 1974. 3. J. Levine and J.L. Hall, "Design and Operation of a Methane Absorp- tion Stabilized

  3. Internet Addiction: Stability and Change

    ERIC Educational Resources Information Center

    Huang, Chiungjung

    2010-01-01

    This longitudinal study examined five indices of stability and change in Internet addiction: structural stability, mean-level stability, differential stability, individual-level stability, and ipsative stability. The study sample was 351 undergraduate students from end of freshman year to end of junior year. Convergent findings revealed stability…

  4. Stabilizing Grout Compatibility Study

    SciTech Connect

    HARBOUR, JOHNR.

    2004-05-19

    This report provides data that will be used to formulate the stabilizing grout and includes experimental results for Tc-99 stabilization by two reagents, (1) ground granulated blast furnace slag (GGBFS) and (2) surface treated hydroxyapatite (HA). One or both of these reagents are being considered by CH2M HILL for incorporation in the binder portion (matrix portion without sand) of the stabilizing grout. The technical basis for identifying the grout ingredient(s) for stabilizing technetium (Tc-99) will be provided by researchers at the Savannah River Technology Center (SRTC) in a subsequent report.

  5. Thermodynamic modeling of natural zeolite stability

    SciTech Connect

    Chipera, S.J.; Bish, D.L.

    1997-06-01

    Zeolites occur in a variety of geologic environments and are used in numerous agricultural, commercial, and environmental applications. It is desirable to understand their stability both to predict future stability and to evaluate the geochemical conditions resulting in their formation. The use of estimated thermodynamic data for measured zeolite compositions allows thermodynamic modeling of stability relationships among zeolites in different geologic environments (diagenetic, saline and alkaline lakes, acid rock hydrothermal, basic rock, deep sea sediments). This modeling shows that the relative cation abundances in both the aqueous and solid phases, the aqueous silica activity, and temperature are important factors in determining the stable zeolite species. Siliceous zeolites (e.g., clinoptilolite, mordenite, erionite) present in saline and alkaline lakes or diagenetic deposits formed at elevated silica activities. Aluminous zeolites (e.g., natrolite, mesolite/scolecite, thomsonite) formed in basic rocks in association with reduced silica activities. Likewise, phillipsite formation is favored by reduced aqueous silica activities. The presence of erionite, chabazite, and phillipsite are indicative of environments with elevated potassium concentrations. Elevated temperature, calcic water conditions, and reduced silica activity help to enhance the laumontite and wairakite stability fields. Analcime stability increases with increased temperature and aqueous Na concentration, and/or with decreased silica activity.

  6. Stability of clathrate hydrates in Martian crust

    NASA Astrophysics Data System (ADS)

    Gloesener, Elodie; Karatekin, Özgür; Dehant, Véronique

    2014-05-01

    Clathrate hydrates are crystalline compounds constituted by cages formed by hydrogen-bonded water molecules inside of which guest gas molecules are trapped. These materials are typically stable at high pressure and low temperature and are present on Earth mainly in marine sediments and in permafrost. Moreover, clathrate hydrates are expected to exist on celestial bodies like the icy moons Titan, Europa or Enceladus. Current conditions in the Martian crust are favourable to the presence of clathrate hydrates. In this study, we focused on the stability of methane and carbon dioxide clathrates in the Martian crust. We coupled the stability conditions of clathrates with a 1D thermal model in order to obtain the variations of the clathrate stability zone in the crust of Mars with time and for different crust compositions. Indeed, the type of soil directly controls the geothermal conditions and therefore the depth of clathrates formation. Unconsolidated soil acts as a thermal insulator and prevents the clathrates formation in the crust except on a small part of a few tens of meters thick. In contrast, sandstone or ice-cemented soil allows the clathrates formation with a stability zone of several kilometers. This is explained by the fact that they evacuate heat more efficiently and thus maintain lower temperatures. We also studied the stability zone of clathrates formed from a mixture of methane and hydrogen sulphide as well as from a mixture of methane and nitrogen. Contrary to the addition of N2, the addition of H2S to CH4 clathrates extends the stability zone and thus brings it closer to the surface. Therefore, mixed clathrates CH4-H2S will be more easily destabilized by changes in surface temperature than CH4 clathrates.

  7. Formation of water bells

    NASA Astrophysics Data System (ADS)

    Ybert, Christophe; Clanet, Christophe; Bocquet, Lyderic; Duez, Cyril

    2007-11-01

    We study experimentally the situation that consist in a liquid jet impacting normally onto a fixed solid disk. Depending on the experimental conditions, the thin liquid film that spreads onto the solid surface can either pour along the surface, or detach form the disk and form a so-called water bell. The dynamics and the stability of such bells as a function of the hydrodynamic parameters such as the jet and disk diameters or the jet velocity, have already been the object of detailed characterization [1]. This experiment of bell formation appears as the symmetric situation compared to that of a solid body impacting a quiescent liquid. In the latter case, it was recently shown [2] that despite large Re and We numbers, the solid surface characteristics were dramatically influencing the impact scenario. In the present study, we consequently revisit this problem of water bell formation by systematically varying the solid surface characteristics (roughness, surface properties, etc.). It is shown here again that surface parameters strongly influence the domain of bell existence. Our measurements are rationalized by a subtle balance between inertia versus capillary forces and wetting contributions on the liquid film in the ejection region. [1] C. Clanet, J. Fluid Mech., 430, 111-147 (2001) [2] C. Duez et al., Nature Physics, 3, 180-183 (2007)

  8. Studies of Diesel Fuel Insolubles Formation and Fuel Stabilizer Additives

    DTIC Science & Technology

    1988-08-01

    gel 1-Octadecene 98.6% min Indole 99+%6 * -. ,2-Methyl Indole 98% Benzoic Acid Primary Standard p- Phenylphenol 99+%6 Quinoline Reagent Grade I-Butanol...each sample. Analysis of the precipitate showed that it was p- phenylphenol . During the preparation of the MS-1 samples, difficulty was experienced in...getting the p- phenylphenol to fully dissolve. Also GC/MS analysis of the sediments formed by MS-I showed only the starting reagents. For these reasons

  9. Entropically Stabilized Local Dipole Formation in Lead Chalcogenides

    DTIC Science & Technology

    2010-12-17

    the figure; data for PbS are contained in figs. S1 and S2 in the supporting online material (11). The dramatic effect of tem- perature on the structure...Waller effects (12) from increased thermal motion; however, the extent of the changes is extraordinarily large. In Fig. 1, D and E, we show the PDFs at 15...K and 500 K, respectively; the effect of temperature on the PDFs is anomalous, with notable broadening evident at 500Kcomparedwith 15K. (The scale in

  10. Secularization, Union Formation Practices, and Marital Stability: Evidence from Italy.

    PubMed

    Impicciatore, Roberto; Billari, Francesco C

    2012-05-01

    Descriptive statistics indicate that civil marriages and marriages preceded by premarital cohabitation are more unstable, i.e., more frequently followed by divorce. However, the literature has shown that selectivity plays an important role in the relationship between premarital cohabitation and union dissolution. We do not have evidence to date regarding the selectivity in the effect of civil marriage. The Italian case appears particularly interesting given the recent diffusion of premarital cohabitation and civil marriage. Using micro-level data from a national-level representative survey conducted in 2003, we develop a multiprocess model that allows unobserved heterogeneity to be correlated across the three decisions (premarital cohabitation, civil marriage, and divorce). Our results show that selectivity is the main factor that explains the higher divorce rates among those who experience premarital cohabitation and a civil marriage. Net of selectivity, the causal effect on union dissolution disappears.

  11. Pressure-driven formation and stabilization of superconductive chromium hydrides

    NASA Astrophysics Data System (ADS)

    Yu, Shuyin; Jia, Xiaojing; Frapper, Gilles; Li, Duan; Oganov, Artem R.; Zeng, Qingfeng; Zhang, Litong

    2015-12-01

    Chromium hydride is a prototype stoichiometric transition metal hydride. The phase diagram of Cr-H system at high pressures remains largely unexplored due to the challenges in dealing with the high activation barriers and complications in handing hydrogen under pressure. We have performed an extensive structural study on Cr-H system at pressure range 0 ˜ 300 GPa using an unbiased structure prediction method based on evolutionary algorithm. Upon compression, a number of hydrides are predicted to become stable in the excess hydrogen environment and these have compositions of Cr2Hn (n = 2-4, 6, 8, 16). Cr2H3, CrH2 and Cr2H5 structures are versions of the perfect anti-NiAs-type CrH with ordered tetrahedral interstitial sites filled by H atoms. CrH3 and CrH4 exhibit host-guest structural characteristics. In CrH8, H2 units are also identified. Our study unravels that CrH is a superconductor at atmospheric pressure with an estimated transition temperature (T c) of 10.6 K, and superconductivity in CrH3 is enhanced by the metallic hydrogen sublattice with T c of 37.1 K at 81 GPa, very similar to the extensively studied MgB2.

  12. Incarceration and the Formation and Stability of Marital Unions

    ERIC Educational Resources Information Center

    Lopoo, Leonard M.; Western, Bruce

    2005-01-01

    Rising imprisonment rates and declining marriage rates among low-education African Americans motivate an analysis of the effects of incarceration on marriage. An event history analysis of 2,041 unmarried men from the National Longitudinal Survey of Youth suggests that men are unlikely to marry in the years they serve in prison. A separate analysis…

  13. Pressure-driven formation and stabilization of superconductive chromium hydrides

    PubMed Central

    Yu, Shuyin; Jia, Xiaojing; Frapper, Gilles; Li, Duan; Oganov, Artem R.; Zeng, Qingfeng; Zhang, Litong

    2015-01-01

    Chromium hydride is a prototype stoichiometric transition metal hydride. The phase diagram of Cr-H system at high pressures remains largely unexplored due to the challenges in dealing with the high activation barriers and complications in handing hydrogen under pressure. We have performed an extensive structural study on Cr-H system at pressure range 0 ∼ 300 GPa using an unbiased structure prediction method based on evolutionary algorithm. Upon compression, a number of hydrides are predicted to become stable in the excess hydrogen environment and these have compositions of Cr2Hn (n = 2–4, 6, 8, 16). Cr2H3, CrH2 and Cr2H5 structures are versions of the perfect anti-NiAs-type CrH with ordered tetrahedral interstitial sites filled by H atoms. CrH3 and CrH4 exhibit host-guest structural characteristics. In CrH8, H2 units are also identified. Our study unravels that CrH is a superconductor at atmospheric pressure with an estimated transition temperature (T c) of 10.6 K, and superconductivity in CrH3 is enhanced by the metallic hydrogen sublattice with T c of 37.1 K at 81 GPa, very similar to the extensively studied MgB2. PMID:26626579

  14. Phase stability of nickel and zirconium stannides

    NASA Astrophysics Data System (ADS)

    Berche, A.; Tédenac, J. C.; Jund, P.

    2017-04-01

    Ni-Sn-Zr alloys have many interests in different fields of application going from nuclear material applications to functional materials (such as thermoelectrics). This wide application range requires a good knowledge of the stability of the phases. In the present study, first principles calculations are used to determine the enthalpies of formation of intermediate phases and of the structural defects in some structures. Based on these data and on the literature, the stability of the phases is discussed at low and high temperatures. Finally, for the first time the complete ternary system is described in the whole temperature range.

  15. Improvement of interfacial protein stability by CHAPS.

    PubMed

    Sah, Hongkee; Kim, Kil-Soo

    2006-04-01

    Emulsification of aqueous protein solutions in methylene chloride triggered the formation of water-insoluble aggregates at a water/methylene chloride interface. As a result, the amounts of beta-lactoglobulin and ovalbumin recovered in water were 36 and 44%, respectively. Addition of 5 mM: CHAPS in the aqueous phase raised the degree of beta-lactoglobulin recovery to 96%. Sodium taurocholate, however, failed to improve protein recovery. The stabilizing effect of CHAPS was also protein-specific and concentration-dependent: at >or=5 mM: , the surfactant caused unfolding of ovalbumin to make a water-soluble oligomer. CHAPS thus stabilizes proteins at an interface.

  16. Barrier Formation

    PubMed Central

    Lyaruu, D.M.; Medina, J.F.; Sarvide, S.; Bervoets, T.J.M.; Everts, V.; DenBesten, P.; Smith, C.E.; Bronckers, A.L.J.J.

    2014-01-01

    Enamel fluorosis is an irreversible structural enamel defect following exposure to supraoptimal levels of fluoride during amelogenesis. We hypothesized that fluorosis is associated with excess release of protons during formation of hypermineralized lines in the mineralizing enamel matrix. We tested this concept by analyzing fluorotic enamel defects in wild-type mice and mice deficient in anion exchanger-2a,b (Ae2a,b), a transmembrane protein in maturation ameloblasts that exchanges extracellular Cl− for bicarbonate. Defects were more pronounced in fluorotic Ae2a,b−/− mice than in fluorotic heterozygous or wild-type mice. Phenotypes included a hypermineralized surface, extensive subsurface hypomineralization, and multiple hypermineralized lines in deeper enamel. Mineral content decreased in all fluoride-exposed and Ae2a,b−/− mice and was strongly correlated with Cl−. Exposure of enamel surfaces underlying maturation-stage ameloblasts to pH indicator dyes suggested the presence of diffusion barriers in fluorotic enamel. These results support the concept that fluoride stimulates hypermineralization at the mineralization front. This causes increased release of protons, which ameloblasts respond to by secreting more bicarbonates at the expense of Cl− levels in enamel. The fluoride-induced hypermineralized lines may form barriers that impede diffusion of proteins and mineral ions into the subsurface layers, thereby delaying biomineralization and causing retention of enamel matrix proteins. PMID:24170372

  17. Pattern Formation

    NASA Astrophysics Data System (ADS)

    Hoyle, Rebecca

    2006-03-01

    From the stripes of a zebra and the spots on a leopard's back to the ripples on a sandy beach or desert dune, regular patterns arise everywhere in nature. The appearance and evolution of these phenomena has been a focus of recent research activity across several disciplines. This book provides an introduction to the range of mathematical theory and methods used to analyse and explain these often intricate and beautiful patterns. Bringing together several different approaches, from group theoretic methods to envelope equations and theory of patterns in large-aspect ratio-systems, the book also provides insight behind the selection of one pattern over another. Suitable as an upper-undergraduate textbook for mathematics students or as a fascinating, engaging, and fully illustrated resource for readers in physics and biology, Rebecca Hoyle's book, using a non-partisan approach, unifies a range of techniques used by active researchers in this growing field. Accessible description of the mathematical theory behind fascinating pattern formation in areas such as biology, physics and materials science Collects recent research for the first time in an upper level textbook Features a number of exercises - with solutions online - and worked examples

  18. Effect of PEGylated chitosan as multifunctional stabilizer for deacetyl mycoepoxydience nanosuspension design and stability evaluation.

    PubMed

    Du, Juan; Zhou, Yuqi; Wang, Lulu; Wang, Yancai

    2016-11-20

    Here a series of multifunctional stabilizers was designed and used in a nanosuspension stability enhancement study. Methoxypolyethylene glycol (M PEG)-grafted chitosan, accompanied by space steric hindrance, an electrostatic repulsion function, and a solvation effect, is a multifunctional stabilizer. Deacetyl mycoepoxydience (DM) nanosuspension was prepared using the anti-solvent precipitation approach. The effects of the DM and the multifunctional stabilizer concentration, solvent to anti-solvent ratio, crystallization and storage temperature, and ultrasonic time on drug particle formation during the anti-solvent processing were investigated and the nanosuspension stability was studied. The nanosuspension showed dendritic-like nanostructures and a crystalline state in a morphology and crystalline state study. The optimized drug and multifunctional stabilizer concentration range were selected through the response surface optimization method. The most appropriate and stable nanosuspension could be obtained through the optimal parameters. This study demonstrated that M PEG-grafted chitosan (M PEGC) could be used as a multifunctional stabilizer to control particle size and improve nanosuspension stability.

  19. Factors important in the extraction, stability and in vitro assembly of the hepatitis B surface antigen derived from recombinant plant systems.

    PubMed

    Smith, Mark L; Keegan, Mark E; Mason, Hugh S; Shuler, Michael L

    2002-01-01

    The expression of vaccine antigens in edible plant material together with their delivery by the oral route constitutes a powerful paradigm, with the potential to dramatically reduce the cost of vaccine production and administration, in addition to improving distribution and patient compliance. These products will be subject to many of the same regulations applied to current injectable vaccines, so reliable methods to quantify antigen and ensure stability in crude plant extracts are required. As a model system the hepatitis B surface antigen (HBsAg) was expressed in soybean and tobacco cell cultures. This complex antigen consists of membrane-associated small surface antigen proteins (p24(s)), disulfide cross-linked to yield dimers and higher multimers. Although the total p24(s) extracted from plant cells was relatively unaffected by detergent concentration, the quantification of antigenically reactive product depended strongly on the ratio of detergent to cell concentration. Furthermore, 1-20% w/v sodium ascorbate improved the measured levels of monoclonal-reactive antigen 4- to 12-fold. Detergent also influenced antigen stability in cell lysates stored at 4 degrees C; under optimum conditions stability was maintained for at least 1 month, whereas excess detergent rendered the antigen susceptible to proteolytic degradation. This proteolysis could be counteracted by the addition of skim milk or its protein component, which stabilized antigenically reactive p24(s) for up to 2 months. The immunologically relevant epitopes of HBsAg are critically dependent on disulfide bonding. By altering the sodium ascorbate concentration or buffer pH the proportion of HBsAg displaying the monoclonal reactive epitopes was increased between 8- and 20-fold. In addition, under certain conditions the dimerized p24(s) could be converted to oligomeric aggregates, resembling the form of the serum-derived antigen. These simple in vitro manipulations, compatible with the goal of a minimally

  20. Stabilized radio frequency quadrupole

    DOEpatents

    Lancaster, Henry D.; Fugitt, Jock A.; Howard, Donald R.

    1984-01-01

    A long-vane stabilized radio frequency resonator for accelerating charged particles and including means defining a radio frequency resonator cavity, a plurality of long vanes mounted in the defining means for dividing the cavity into sections, and means interconnecting opposing ones of the plurality of vanes for stabilizing the resonator.

  1. Stabilized radio frequency quadrupole

    DOEpatents

    Lancaster, H.D.; Fugitt, J.A.; Howard, D.R.

    1984-12-25

    Disclosed is a long-vane stabilized radio frequency resonator for accelerating charged particles and including means defining a radio frequency resonator cavity, a plurality of long vanes mounted in the defining means for dividing the cavity into sections, and means interconnecting opposing ones of the plurality of vanes for stabilizing the resonator. 5 figs.

  2. Electrode stabilizing materials

    DOEpatents

    Amine, Khalil; Abouimrane, Ali; Moore, Jeffrey S.; Odom, Susan A.

    2015-11-03

    An electrolyte includes a polar aprotic solvent; an alkali metal salt; and an electrode stabilizing compound that is a monomer, which when polymerized forms an electrically conductive polymer. The electrode stabilizing compound is a thiophene, a imidazole, a anilines, a benzene, a azulene, a carbazole, or a thiol. Electrochemical devices may incorporate such electrolytes.

  3. Interfacial bonding stability

    NASA Technical Reports Server (NTRS)

    Boerio, J.

    1984-01-01

    Interfacial bonding stability by in situ ellipsometry was investigated. It is found that: (1) gamma MPS is an effective primer for bonding ethylene vinyl acetate (EVA) to aluminum; (2) ellipsometry is an effective in situ technique for monitoring the stability of polymer/metal interfaces; (3) the aluminized back surface of silicon wafers contain significant amounts of silicon and may have glass like properties.

  4. Stabilization of Kepler's problem

    NASA Technical Reports Server (NTRS)

    Stokes, A.

    1977-01-01

    A regularization of Kepler's problem due to Moser (1970) is used to stabilize the equations of motion. In other words, a particular solution of Kepler's problem is imbedded in a Liapunov stable system. Perturbations can be introduced into the stabilized equations.

  5. Basic principles of stability.

    PubMed

    Egan, William; Schofield, Timothy

    2009-11-01

    An understanding of the principles of degradation, as well as the statistical tools for measuring product stability, is essential to management of product quality. Key to this is management of vaccine potency. Vaccine shelf life is best managed through determination of a minimum potency release requirement, which helps assure adequate potency throughout expiry. Use of statistical tools such a least squares regression analysis should be employed to model potency decay. The use of such tools provides incentive to properly design vaccine stability studies, while holding stability measurements to specification presents a disincentive for collecting valuable data. The laws of kinetics such as Arrhenius behavior help practitioners design effective accelerated stability programs, which can be utilized to manage stability after a process change. Design of stability studies should be carefully considered, with an eye to minimizing the variability of the stability parameter. In the case of measuring the degradation rate, testing at the beginning and the end of the study improves the precision of this estimate. Additional design considerations such as bracketing and matrixing improve the efficiency of stability evaluation of vaccines.

  6. Rotorcraft aeroelastic stability

    NASA Technical Reports Server (NTRS)

    Ormiston, Robert A.; Warmbrodt, William G.; Hodges, Dewey H.; Peters, David A.

    1988-01-01

    Theoretical and experimental developments in the aeroelastic and aeromechanical stability of helicopters and tilt-rotor aircraft are addressed. Included are the underlying nonlinear structural mechanics of slender rotating beams, necessary for accurate modeling of elastic cantilever rotor blades, and the development of dynamic inflow, an unsteady aerodynamic theory for low-frequency aeroelastic stability applications. Analytical treatment of isolated rotor stability in hover and forward flight, coupled rotor-fuselage stability in hover and forward flight, and analysis of tilt-rotor dynamic stability are considered. Results of parametric investigations of system behavior are presented, and correlation between theoretical results and experimental data from small and large scale wind tunnel and flight testing are discussed.

  7. Formation of the hurricane eye

    NASA Astrophysics Data System (ADS)

    Vigh, Jonathan L.

    This dissertation consists of three distinct studies which investigate aspects of eye formation. The first study reviews eye phenomenon in a variety of vortices ranging from simple vortices to the menagerie of geophysical vortices, emphasizing similarities and differences to the eyes formed in hurricanes. The hurricane eye is found to be a paradoxical structure imposed by conservation of angular momentum and the boundaries of the vortex. A comprehensive definition for hurricane eye formation is proposed and various eye formation mechanisms are summarized. The next study presents a simple theoretical argument to isolate the conditions under which a tropical cyclone can rapidly develop a warm-core thermal structure and subsequently approach a steady state. The theoretical argument is based on the balanced vortex model and, in particular, on the associated transverse circulation equation and the geopotential tendency equation. The transverse circulation and the temperature tendency in a tropical vortex depend not only on the diabatic forcing, but also on the spatial distributions of the static stability, the baroclinity, and the inertial stability. The vortex response to diabatic heating depends critically on whether the heating occurs in the low inertial stability region outside the radius of maximum wind or in the high inertial stability region inside the radius of maximum wind. This result suggests that rapid intensification is favored for storms which have at least some of the eyewall convection inside the radius of maximum wind. The development of an eye partially removes diabatic heating from the high inertial stability region of the storm center, yet rapid intensification may continue if the eyewall heating continues to become more efficient. As the warm core matures and static stability increases over the inner core, conditions there become less favorable for deep upright convection and the storm tends to approach a steady state. The final study characterizes

  8. Stabilizing Agents for Drug Nanocrystals: Effect on Bioavailability

    PubMed Central

    Tuomela, Annika; Hirvonen, Jouni; Peltonen, Leena

    2016-01-01

    Drug nanocrystals are a versatile option for drug delivery purposes, and while the number of poorly soluble drug materials is all the time increasing, more research in this area is performed. Drug nanocrystals have a simple structure—a solid drug core is surrounded by a layer of stabilizing agent. However, despite the considerably simple structure, the selection of an appropriate stabilizer for a certain drug can be challenging. Mostly, the stabilizer selection is based purely on the requirement of physical stability, e.g., maintaining the nanosized particle size as long as possible after the formation of drug nanocrystals. However, it is also worth taking into account that stabilizer can affect the bioavailability in the final formulation via interactions with cells and cell layers. In addition, formation of nanocrystals is only one process step, and for the final formulation, more excipients are often added to the composition. The role of the stabilizers in the final formulation can be more than only stabilizing the nanocrystal particle size. A good example is the stabilizer’s role as cryoprotectant during freeze drying. In this review, the stabilizing effect, role of stabilizers in final nanocrystalline formulations, challenges in reaching in vitro–in vivo correlation with nanocrystalline products, and stabilizers’ effect on higher bioavailability are discussed. PMID:27213435

  9. Ligand-Stabilized Reduced-Dimensionality Perovskites.

    PubMed

    Quan, Li Na; Yuan, Mingjian; Comin, Riccardo; Voznyy, Oleksandr; Beauregard, Eric M; Hoogland, Sjoerd; Buin, Andrei; Kirmani, Ahmad R; Zhao, Kui; Amassian, Aram; Kim, Dong Ha; Sargent, Edward H

    2016-03-02

    Metal halide perovskites have rapidly advanced thin-film photovoltaic performance; as a result, the materials' observed instabilities urgently require a solution. Using density functional theory (DFT), we show that a low energy of formation, exacerbated in the presence of humidity, explains the propensity of perovskites to decompose back into their precursors. We find, also using DFT, that intercalation of phenylethylammonium between perovskite layers introduces quantitatively appreciable van der Waals interactions. These drive an increased formation energy and should therefore improve material stability. Here we report reduced-dimensionality (quasi-2D) perovskite films that exhibit improved stability while retaining the high performance of conventional three-dimensional perovskites. Continuous tuning of the dimensionality, as assessed using photophysical studies, is achieved by the choice of stoichiometry in materials synthesis. We achieve the first certified hysteresis-free solar power conversion in a planar perovskite solar cell, obtaining a 15.3% certified PCE, and observe greatly improved performance longevity.

  10. Stability and precipitation of diverse nanoparticles

    NASA Astrophysics Data System (ADS)

    Desai, Chintal

    Nanotechnology is a rapidly growing industry that is exploiting the novel characteristics of materials manufactured at the nanoscale. Carbon based nanomaterials such as Carbon Nanotubes (CNTs) and Detonation Nanodiamond (DND) possess unique properties and find a wide range of industrial applications. With the advent of mass production of such materials, there is a possibility of contamination of water resources. Depending on the surface properties and structures, they might aggregate and settle down, or be dispersed and transported by the water. Therefore, there is a need to develop an understanding of the fate of such materials in aqueous media. The understanding and effect of solution chemistry is a key to predicting their deposition, transport, reactivity, and bioavailability in aquatic environments. The colloidal behavior of organic dispersed CNTs and water dispersed DNDs is investigated. The aggregation behavior of these two colloidal systems is quite different from that of hydrophilic, water soluble functionalized CNTs (F-CNTs). The values of the Fuchs stability ratio or the critical coagulant concentration are determined experimentally using time-resolved dynamic light scattering and are used to predict the stability of such systems. It is found that the aggregation behavior of the organic dispersed, antisolvent precipitated system does not follow the conventional Derjaguin--Landau--Verwey-- Overbeek (DLVO) theory. But they stabilize in the long term, which is attributed to the supersaturation generated by different solubility of a solute in the solvent/antisolvent. Based on particle size distribution, zeta potential as well as the aggregation kinetics, the water dispersed DNDs are found to be relatively stable in aqueous solutions, but aggregate rapidly in presence of mono and divalent salts. Also, the formation of carboxylic groups on the DND surface does not alter colloidal behavior as dramatically as it does for other nanocarbons especially carbon

  11. Surface controlled blade stabilizer

    DOEpatents

    Russell, Larry R.

    1983-01-01

    Drill string stabilizer apparatus, controllable to expand and retract entirely from the surface by control of drill string pressure, wherein increase of drill string pressure from the surface closes a valve to create a piston means which is moved down by drill string pressure to expand the stabilizer blades, said valve being opened and the piston moving upward upon reduction of drill string pressure to retract the stabilizer blades. Upward and downward movements of the piston and an actuator sleeve therebelow are controlled by a barrel cam acting between the housing and the actuator sleeve.

  12. Life raft stabilizer

    NASA Technical Reports Server (NTRS)

    Radnofsky, M. I.; Barnett, J. H., Jr.; Harrison, F. L.; Marak, R. J. (Inventor)

    1973-01-01

    An improved life raft stabilizer for reducing rocking and substantially precluding capsizing is discussed. The stabilizer may be removably attached to the raft and is defined by flexible side walls which extend a considerable depth downwardly to one another in the water. The side walls, in conjunction with the floor of the raft, form a ballast enclosure. A weight is placed in the bottom of the enclosure and water port means are provided in the walls. Placement of the stabilizer in the water allows the weighted bottom to sink, producing submerged deployment thereof and permitting water to enter the enclosure through the port means, thus forming a ballast for the raft.

  13. Does the market maker stabilize the market?

    NASA Astrophysics Data System (ADS)

    Zhu, Mei; Chiarella, Carl; He, Xue-Zhong; Wang, Duo

    2009-08-01

    The market maker plays an important role in price formation, but his/her behavior and stabilizing impact on the market are relatively unclear, in particular in speculative markets. This paper develops a financial market model that examines the impact on market stability of the market maker, who acts as both a liquidity provider and an active investor in a market consisting of two types of boundedly rational speculative investors-the fundamentalists and trend followers. We show that the market maker does not necessarily stabilize the market when he/she actively manages the inventory to maximize profits, and that rather the market maker’s impact depends on the behavior of the speculators. Numerical simulations show that the model is able to generate outcomes for asset returns and market inventories that are consistent with empirical findings.

  14. The Stability of Galaxy Disks

    NASA Astrophysics Data System (ADS)

    Westfall, Kyle B.; Andersen, D. R.; Bershady, M. A.; Martinsson, T.; Swaters, R. A.; Verheijen, M. A.

    2013-01-01

    Using measurements of velocity dispersion and mass surface density for both the gas and stellar components, we calculate the multi-component stability (Q) for 30 galaxy disks observed by the DiskMass Survey. Despite their sub-maximality (Bershady et al. 2011, ApJL, 739, 47), we find all disks to be stable with roughly 85% falling in the range 1stability calculation is the characterization of the stellar velocity ellipsoid (SVE) in each galaxy. We measure the shape of the SVE using methods developed by Westfall (2009, PhD Thesis) and Westfall et al. (2011, ApJ, 742, 18); these methods primarily hinge on asymmetric-drift measurements determined by our gas and stellar rotation curves. We find high-quality SVE measurements for a third of the galaxies in our sample. Practical (inclination) limitations and/or the requisite dynamical assumptions in these methods currently prevent satisfactory SVE solutions for the remainder of our sample; for these galaxies, we determine Q using reasonable SVE estimates based on our own high-quality results and others gathered from the literature (e.g., van der Kruit & de Grijs 1999, A&A, 352, 129; Gerssen & Shapiro Griffin 2012, MNRAS, 423, 2726). Finally, we explore correlations between disk stability and other galaxy properties such as star-formation rate, gas mass fraction, disk maximality, and Hubble type to understand their interdependencies within the context of the secular evolution of galaxy disks. We acknowledge support for this work from the National Science Foundation (AST-0307417, AST-0607516, OISE-0754437, AST-1009491), The Netherlands Organisation for Scientific Research (grant 614.000.807), the UW Graduate School (PRJ13SL, 050167, and the Vilas Associate award), the Leids Kerkhoven-Bosscha Fonds, and NASA/JPL/Spitzer (GO-30894).

  15. Fibrinogen stability under surfactant interaction.

    PubMed

    Hassan, Natalia; Barbosa, Leandro R S; Itri, Rosangela; Ruso, Juan M

    2011-10-01

    Differential scanning calorimetry (DSC), circular dichroism (CD), difference spectroscopy (UV-vis), Raman spectroscopy, and small-angle X-ray scattering (SAXS) measurements have been performed in the present work to provide a quantitatively comprehensive physicochemical description of the complexation between bovine fibrinogen and the sodium perfluorooctanoate, sodium octanoate, and sodium dodecanoate in glycine buffer (pH 8.5). It has been found that sodium octanoate and dodecanoate act as fibrinogen destabilizer. Meanwhile, sodium perfluorooctanoate acts as a structure stabilizer at low molar concentration and as a destabilizer at high molar concentration. Fibrinogen's secondary structure is affected by all three studied surfactants (decrease in α-helix and an increase in β-sheet content) to a different extent. DSC and UV-vis revealed the existence of intermediate states in the thermal unfolding process of fibrinogen. In addition, SAXS data analysis showed that pure fibrinogen adopts a paired-dimer structure in solution. Such a structure is unaltered by sodium octanoate and perfluoroctanoate. However, interaction of sodium dodecanoate with the fibrinogen affects the protein conformation leading to a complex formation. Taken together, all results evidence that both surfactant hydrophobicity and tail length mediate the fibrinogen stability upon interaction.

  16. Mechanical stability of bipolar spindle assembly

    NASA Astrophysics Data System (ADS)

    Malgaretti, Paolo; Muhuri, Sudipto

    2016-07-01

    Assembly and stability of mitotic spindle are governed by the interplay of various intra-cellular forces, e.g. the forces generated by motor proteins by sliding overlapping anti-parallel microtubules (MTs) polymerized from the opposite centrosomes, the interaction of kinetochores with MTs, and the interaction of MTs with the chromosome arms. We study the mechanical behavior and stability of spindle assembly within the framework of a minimal model which includes all these effects. For this model, we derive a closed-form analytical expression for the force acting between the centrosomes as a function of their separation distance and we show that an effective potential can be associated with the interactions at play. We obtain the stability diagram of spindle formation in terms of parameters characterizing the strength of motor sliding, repulsive forces generated by polymerizing MTs, and the forces arising out of the interaction of MTs with kinetochores. The stability diagram helps in quantifying the relative effects of the different interactions and elucidates the role of motor proteins in formation and inhibition of spindle structures during mitotic cell division. We also predict a regime of bistability for a certain parameter range, wherein the spindle structure can be stable for two different finite separation distances between centrosomes. This occurrence of bistability also suggests the mechanical versatility of such self-assembled spindle structures.

  17. Evolutionary stability on graphs

    PubMed Central

    Ohtsuki, Hisashi; Nowak, Martin A.

    2008-01-01

    Evolutionary stability is a fundamental concept in evolutionary game theory. A strategy is called an evolutionarily stable strategy (ESS), if its monomorphic population rejects the invasion of any other mutant strategy. Recent studies have revealed that population structure can considerably affect evolutionary dynamics. Here we derive the conditions of evolutionary stability for games on graphs. We obtain analytical conditions for regular graphs of degree k > 2. Those theoretical predictions are compared with computer simulations for random regular graphs and for lattices. We study three different update rules: birth-death (BD), death-birth (DB), and imitation (IM) updating. Evolutionary stability on sparse graphs does not imply evolutionary stability in a well-mixed population, nor vice versa. We provide a geometrical interpretation of the ESS condition on graphs. PMID:18295801

  18. Stability and Retention.

    PubMed

    Will, Leslie A

    2016-01-01

    Stability of tooth position in the broader sense considers all the forces that may act on the tooth. Reitan reported that significant forces remained in the periodontium after tooth movement, and he carried out research that demonstrated residual stretching of the crestal periodontal fibers more than 7 months after tooth movement. Brain demonstrated that severing the fibers reduced the relapse in tooth position in dogs. Edwards published a series of papers exploring the effects of surgical transection of the gingival fibers on tooth stability, recommending that circumferential fiberotomy be performed in order to increase posttreatment tooth stability. Other researchers have suggested ways to increase the stability of the incisors, which are typically most prone to relapse. Peck and Peck recommended that interproximal reduction be done to broaden the contact point. Boese also recommended interproximal reduction as part of a four-pronged approach to retention.

  19. Thermal Stabilization Blend Plan

    SciTech Connect

    RISENMAY, H.R.

    2000-05-02

    This Blend Plan documents the feed material items that are stored in 2736-2 vaults, the 2736-ZB 638 cage, the 192C vault, and the 225 vault that will be processed through the thermal stabilization furnaces. The purpose of thermal stabilization is to heat the material to 1000 degrees Celsius to drive off all water and leave the plutonium and/or uranium as oxides. The stabilized material will be sampled to determine the Loss On Ignition (LOI) or percent water. The stabilized material must meet water content or LOI of less than 0.5% to be acceptable for storage under DOE-STD-3013-99 specifications. Out of specification material will be recycled through the furnaces until the water or LOI limits are met.

  20. Spacecraft stability and control

    NASA Technical Reports Server (NTRS)

    Barret, Chris

    1992-01-01

    The Earth's first artificial satellite, Sputnik 1, slowly tumbled in orbit. The first U.S. satellite, Explorer 1, also tumbled out of control. Today, satellite stability and control has become a higher priority. For a satellite design that is to have a life expectancy of 14 years, appropriate spacecraft flight control systems will be reviewed, stability requirements investigated, and an appropriate flight control system recommended in order to see the design process. Disturbance torques, including aerodynamic, magnetic, gravity gradient, solar, micrometeorite, debris, collision, and internal torques, will be assessed to quantify the disturbance environment so that the required compensating torques can be determined. The control torques, including passive versus active, momentum control, bias momentum, spin stabilization, dual spin, gravity gradient, magnetic, reaction wheels, control moment gyros, inertia augmentation techniques, three-axis control, and reaction control systems (RCSs), will be considered. Conditions for stability will also be considered.

  1. Metallic alloy stability studies

    NASA Technical Reports Server (NTRS)

    Firth, G. C.

    1983-01-01

    The dimensional stability of candidate cryogenic wind tunnel model materials was investigated. Flat specimens of candidate materials were fabricated and cryo-cycled to assess relative dimensional stability. Existing 2-dimensional airfoil models as well as models in various stages of manufacture were also cryo-cycled. The tests indicate that 18 Ni maraging steel offers the greatest dimensional stability and that PH 13-8 Mo stainless steel is the most stable of the stainless steels. Dimensional stability is influenced primarily by metallurgical transformations (austenitic to martensitic) and manufacturing-induced stresses. These factors can be minimized by utilization of stable alloys, refinement of existing manufacturing techniques, and incorporation of new manufacturing technologies.

  2. Control of Collagen Triple Helix Stability by Phosphorylation.

    PubMed

    Acevedo-Jake, Amanda M; Ngo, Daniel H; Hartgerink, Jeffrey D

    2017-03-10

    The phosphorylation of the collagen triple helix plays an important role in collagen synthesis, assembly, signaling, and immune response, although no reports detailing the effect this modification has on the structure and stability of the triple helix exist. Here we investigate the changes in stability and structure resulting from the phosphorylation of collagen. Additionally, the formation of pairwise interactions between phosphorylated residues and lysine is examined. In all tested cases, phosphorylation increases helix stability. When charged-pair interactions are possible, stabilization via phosphorylation can play a very large role, resulting inasmuch as a 13.0 °C increase in triple helix stability. Two-dimensional NMR and molecular modeling are used to study the local structure of the triple helix. Our results suggest a mechanism of action for phosphorylation in the regulation of collagen and also expand upon our understanding of pairwise amino acid stabilization of the collagen triple helix.

  3. METHOD FOR STABILIZING KLYSTRONS

    DOEpatents

    Magnuson, D.W.; Smith, D.F.

    1959-04-14

    High-frequency oscillators for the generation of microwaves, particularly a system for stabilizing frequency-modulated klystron oscillators of the reflex type, are described. The system takos advantage of the fact that a change in oscillator frequency will alter the normal phase displacement between the cavity and its modulator, creating an error voltage which is utilized to regulate the frequency of the oscillator and stabilize it.

  4. Factors Influencing Carboxyhemoglobin Stability.

    DTIC Science & Technology

    1985-03-26

    Medical Center, St. Louis, MO. 11. Dennis, R.C., and C.R. Valeri, 1980. Measuring Percent Oxygen Saturation of Hemoglobin, Percent Carboxyhemoglobin and... Carboxyhemoglobin Stability Technical Report 1983 - 1984 6. PERFORMING ORG. REPORT NUMBER 7. AUTNOR(e) S. CONTRACT OR GRANT NUMBER(a) George M. Goldstein...identify by block number) Carboxyhemoglobin Temperature Stability Co-Oxcimieter Heparin Ethylene diamine tetraacetic acid G. 0 ABSTRACT (Ctlze

  5. Food Fortification Stability Study

    NASA Technical Reports Server (NTRS)

    Sirmons, T. A.; Cooper, M. R.; Douglas, G. L.

    2016-01-01

    This study aims to assess the stability of vitamin content, sensory acceptability and color variation in fortified spaceflight foods over a period of 2 years. Findings will identify optimal formulation, processing, and storage conditions to maintain stability and acceptability of commercially available fortification nutrients. Changes in food quality are being monitored to indicate whether fortification affects quality over time (compared to the unfortified control), thus indicating their potential for use on long-duration missions.

  6. Food Fortification Stability Study

    NASA Technical Reports Server (NTRS)

    Sirmons, T. A.; Cooper, M. R.; Douglas, G. L.

    2017-01-01

    This study aimed to assess the stability of vitamin content, sensory acceptability and color variation in fortified spaceflight foods over a period of two years. Findings will help to identify optimal formulation, processing, and storage conditions to maintain stability and acceptability of commercially available fortification nutrients. Changes in food quality were monitored to indicate whether fortification affects quality over time (compared to the unfortified control), thus indicating their potential for use on long-duration missions.

  7. Shearing stability of lubricants

    NASA Technical Reports Server (NTRS)

    Shiba, Y.; Gijyutsu, G.

    1984-01-01

    Shearing stabilities of lubricating oils containing a high mol. wt. polymer as a viscosity index improver were studied by use of ultrasound. The oils were degraded by cavitation and the degradation generally followed first order kinetics with the rate of degradation increasing with the intensity of the ultrasonic irradiation and the cumulative energy applied. The shear stability was mainly affected by the mol. wt. of the polymer additive and could be determined in a short time by mechanical shearing with ultrasound.

  8. Automated RSO Stability Analysis

    NASA Astrophysics Data System (ADS)

    Johnson, T.

    2016-09-01

    A methodology for assessing the attitude stability of a Resident Space Object (RSO) using visual magnitude data is presented and then scaled to run in an automated fashion across the entire satellite catalog. Results obtained by applying the methodology to the Commercial Space Operations Center (COMSpOC) catalog are presented and summarized, identifying objects that have changed stability. We also examine the timeline for detecting the transition from stable to unstable attitude

  9. Tetraphenylborate Solids Stability Tests

    SciTech Connect

    Walker, D.D.

    1997-06-25

    Tetraphenylborate solids are a potentially large source of benzene in the slurries produced in the In-Tank Precipitation (ITP) process. The stability of the solids is an important consideration in the safety analysis of the process and we desire an understanding of the factors that influence the rate of conversion of the solids to benzene. This report discusses current testing of the stability of tetraphenylborate solids.

  10. Stability of Detached Solidification

    NASA Technical Reports Server (NTRS)

    Mazuruk, K.; Volz, M. P.; Croell, A.

    2009-01-01

    Bridgman crystal growth can be conducted in the so-called "detached" solidification regime, where the growing crystal is detached from the crucible wall. A small gap between the growing crystal and the crucible wall, of the order of 100 micrometers or less, can be maintained during the process. A meniscus is formed at the bottom of the melt between the crystal and crucible wall. Under proper conditions, growth can proceed without collapsing the meniscus. The meniscus shape plays a key role in stabilizing the process. Thermal and other process parameters can also affect the geometrical steady-state stability conditions of solidification. The dynamic stability theory of the shaped crystal growth process has been developed by Tatarchenko. It consists of finding a simplified autonomous set of differential equations for the radius, height, and possibly other process parameters. The problem then reduces to analyzing a system of first order linear differential equations for stability. Here we apply a modified version of this theory for a particular case of detached solidification. Approximate analytical formulas as well as accurate numerical values for the capillary stability coefficients are presented. They display an unexpected singularity as a function of pressure differential. A novel approach to study the thermal field effects on the crystal shape stability has been proposed. In essence, it rectifies the unphysical assumption of the model that utilizes a perturbation of the crystal radius along the axis as being instantaneous. It consists of introducing time delay effects into the mathematical description and leads, in general, to stability over a broader parameter range. We believe that this novel treatment can be advantageously implemented in stability analyses of other crystal growth techniques such as Czochralski and float zone methods.

  11. Stability in dynamical astronomy*

    PubMed Central

    Szebehely, Victor

    1978-01-01

    Hill's concept of stability is generalized and its relation to bifurcation theory is shown. A quantitative measure of stability is introduced that allows the comparison of the stability of different astronomical systems. Theoretical stability limits for triple stellar systems, for planetary systems, and for satellite systems are established. The measure of stability is evaluated for several known triple stellar systems as well as for the planets and for the natural satellites of the solar system. The model of the restricted problem of three bodies and values of the Jacobian constant are used to study planetary and satellite systems. The model of the general problem of three bodies is used to establish criteria for triple stellar systems. In general, the results show a hierarchy of stability: the existing triple systems are more stable than the planetary orbits of the solar system. The satellites of the solar system are least stable; in fact, some of the satellites are close to the line of instability (the Earth's Moon) and some are actually unstable (the four outermost satellites of Jupiter). PMID:16592589

  12. Local slope stability analysis

    NASA Astrophysics Data System (ADS)

    Hattendorf, I.; Hergarten, St.; Neugebauer, H. J.

    Mass movements under the influence of gravity occur as result of diverse disturbing and destabilizing processes, for example of climatic or anthropological origin. The stability of slopes is mainly determined by the geometry of the land-surface and designated slip-horizon. Further contributions are supplied by the pore water pressure, cohesion and friction. All relevant factors have to be integrated in a slope stability model, either by measurements and estimations (like phenomenological laws) or derived from physical equations. As result of stability calculations, it's suitable to introduce an expectation value, the factor-of-safety, for the slip-risk. Here, we present a model based on coupled physical equations to simulate hardly measurable phenomenons, like lateral forces and fluid flow. For the displacements of the soil-matrix we use a modified poroelasticity-equation with a Biot-coupling (Biot 1941) for the water pressure. Latter is described by a generalized Boussinesq equation for saturated-unsaturated porous media (Blendinger 1998). One aim of the calculations is to improve the knowledge about stability-distributions and their temporal variations. This requires the introduction of a local factor-of-safety which is the main difference to common stability models with global stability estimations. The reduction of immediate danger is still the emergent task of the most slope and landslide investigations, but this model is also useful with respect to understand the governing processes of landform evolution.

  13. Parallel Estimators and Communication in Spacecraft Formations

    NASA Technical Reports Server (NTRS)

    Smith, Roy S.; Hadaegh, Fred Y.

    2005-01-01

    This paper investigates the closed-loop dynamics of systems controlled via parallel estimators. This structure arises in formation flying problems when each spacecraft bases its control action on an internal estimate of the complete formation state. For LTI systems a separation principle shows that the necessary and sufficient conditions for overall system stability are more stringent than the single controller case; the controllers' open-loop dynamics necessarily appear in the closed-loop dynamics. Communication amongst the spacecraft can be used to specify the complete system dynamics and a framework for integrating the design of the communication links into the formation flying control design problem is presented.

  14. Lycopene stability during food processing.

    PubMed

    Nguyen, M L; Schwartz, S J

    1998-06-01

    Accumulating epidemiological evidence continues to show that lycopene, found in tomatoes, grapefruits and watermelons, is associated with a reduced risk of developing certain chronic diseases and cancers. With respect to lycopene in tomato products, the effect of thermal processing on its stability has not yet been rigorously addressed. This paper assesses the effect of several different heat treatments on lycopene's isomeric distribution in a variety of tomato products, as well as in organic solvent mixtures containing all-trans lycopene. Experimental results indicate that in contrast to beta-carotene, lycopene remained relatively resistant to heat-induced geometrical conversion during typical food processing of tomatoes and related products. The presence of fat, the change in percentage of solids, and the severity of heat treatment were not contributing factors in the formation of lycopene isomers in tomato products, except at extreme conditions not regularly employed in the food industry or during food preparation. However, lycopene in organic solvent isomerized readily as a function of time even in the absence of light and the presence of antioxidants. These findings suggest that while lycopene is stable in the tomato matrix, sample handling techniques should be carefully evaluated to minimize the formation of lycopene cis isomers in organic solutions.

  15. Reactions of stabilized Criegee Intermediates

    NASA Astrophysics Data System (ADS)

    Vereecken, Luc; Harder, Hartwig; Novelli, Anna

    2014-05-01

    Carbonyl oxides (Criegee intermediates) were proposed as key intermediates in the gas phase ozonolysis of alkenes in 1975 by Rudolf Criegee. Despite the importance of ozonolysis in atmospheric chemistry, direct observation of these intermediates remained elusive, with only indirect experimental evidence for their role in the oxidation of hydrocarbons, e.g. through scavenging experiments. Direct experimental observation of stabilized CI has only been achieved since 2008. Since then, a concerted effort using experimental and theoretical means is in motion to characterize the chemistry and kinetics of these reactive intermediates. We present the results of theoretical investigations of the chemistry of Criegee intermediates with a series of coreactants which may be of importance in the atmosphere, in experimental setups, or both. This includes the CI+CI cross-reaction, which proceeds with a rate coefficient near the collision limit and can be important in experimental conditions. The CI + alkene reactions show strong dependence of the rate coefficient depending on the coreactants, but is generally found to be rather slow. The CI + ozone reaction is sufficiently fast to occur both in experiment and the free troposphere, and acts as a sink for CI. The reaction of CI with hydroperoxides, ROOH, is complex, and leads both to the formation of oligomers, as to the formation of reactive etheroxides, with a moderately fast rate coefficient. The importance of these reactions is placed in the context of the reaction conditions in different atmospheric environments ranging from unpolluted to highly polluted.

  16. Stabilization precision control methods of photoelectric aim-stabilized system

    NASA Astrophysics Data System (ADS)

    Song, Xiaoru; Chen, Hua; Xue, Yonggang

    2015-09-01

    To solve the question that photoelectric aim-stabilized system can be controlled with high precision and stability, this paper researches a new photoelectric aim-stabilized control algorithm, analyzes the photoelectric aim-stabilized system architecture, sets up stability control system mathematical model, designs the stability of the photoelectric aim-stabilized LSSVM identification and control system, discusses uncertain factors and calculates the LSSVM parameters by the Chaos theory, gives the predictive controller model by the LSSVM and designs new photoelectric aim-stabilized system. Through the simulation calculation and experimental analysis, new photoelectric aim-stabilized control algorithm was verified; the results show the new photoelectric aim-stabilized control method can meet the demand of high precision control in photoelectric aim-stabilized system.

  17. Physical stability enhancement of theophylline via cocrystallization.

    PubMed

    Trask, Andrew V; Motherwell, W D Sam; Jones, William

    2006-08-31

    The crystal form adopted by the respiratory drug theophylline was modified using a crystal engineering strategy in order to search for a solid material with improved physical stability. Cocrystals, also referred to as crystalline molecular complexes, were prepared with theophylline and one of several dicarboxylic acids. Four cocrystals of theophylline are reported, one each with oxalic, malonic, maleic and glutaric acids. Crystal structures were obtained for each cocrystal material, allowing an examination of the hydrogen bonding and crystal packing features. The cocrystal design scheme was partly based upon a series of recently reported cocrystals of the molecular analogue, caffeine, and comparisons in packing features are drawn between the two cocrystal series. The theophylline cocrystals were subjected to relative humidity challenges in order to assess their stability in relation to crystalline theophylline anhydrate and the equivalent caffeine cocrystals. None of the cocrystals in this study converted into a hydrated cocrystal upon storage at high relative humidity. Furthermore, the theophylline:oxalic acid cocrystal demonstrated superior humidity stability to theophylline anhydrate under the conditions examined, while the other cocrystals appeared to offer comparable stability to that of theophylline anhydrate. The results demonstrate the feasibility of pharmaceutical cocrystal design based upon the crystallization preferences of a molecular analogue, and furthermore show that avoidance of hydrate formation and improvement in physical stability is possible via pharmaceutical cocrystallization.

  18. Electro-hydrodynamic Stability of Electrified Jet

    NASA Astrophysics Data System (ADS)

    Dharmansh, -; Chokshi, Paresh

    2014-11-01

    The axisymmetric stability of the straight jet in electrospinning process is examined for both Newtonian and polymeric fluids using leaky dielectric model. Contrary to previous studies which consider cylindrical jet as the base-state, in the present study the thinning jet profile obtained as steady-state solution of the 1D model is considered as the base-state. The linear stability of the thinning jet is analyzed for axisymmetric disturbances, which are believed to be responsible for the bead formation. The growth rate eigen-specturm is constructed using Chebyshev collocation method. Two different types of axisymmetric instability modes are observed, the Rayleigh mode and the conducting mode. Competition between these two modes is revealed for the thinning jet. The most unstable growth rate for thinning jet is found to be significantly different from that for the uniform jet. The role of various material and process parameters is also investigated. For the viscoelastic fluids, the thinning jet with non-uniform extension rate captures the role of nonlinear rheology of fluid in the stability behavior. The viscoelastic jet profile obtained from steady-state 1D model is analyzed for stability. The role of fluid elasticity on various instability modes is studied. Interestingly, the strain hardening behavior in polymer solution tends to suppress the instability producing smooth fibers. Also, increasing the polymer concentration exhibits stabilizing effect on the axisymmetric instability modes.

  19. Designed metalloprotein stabilizes a semiquinone radical

    NASA Astrophysics Data System (ADS)

    Ulas, Gözde; Lemmin, Thomas; Wu, Yibing; Gassner, George T.; Degrado, William F.

    2016-04-01

    Enzymes use binding energy to stabilize their substrates in high-energy states that are otherwise inaccessible at ambient temperature. Here we show that a de novo designed Zn(II) metalloprotein stabilizes a chemically reactive organic radical that is otherwise unstable in aqueous media. The protein binds tightly to and stabilizes the radical semiquinone form of 3,5-di-tert-butylcatechol. Solution NMR spectroscopy in conjunction with molecular dynamics simulations show that the substrate binds in the active site pocket where it is stabilized by metal-ligand interactions as well as by burial of its hydrophobic groups. Spectrochemical redox titrations show that the protein stabilized the semiquinone by reducing the electrochemical midpoint potential for its formation via the one-electron oxidation of the catechol by approximately 400 mV (9 kcal mol-1). Therefore, the inherent chemical properties of the radical were changed drastically by harnessing its binding energy to the metalloprotein. This model sets the basis for designed enzymes with radical cofactors to tackle challenging chemistry.

  20. Uncertainties in climate stabilization

    SciTech Connect

    Wigley, T. M.; Clarke, Leon E.; Edmonds, James A.; Jacoby, H. D.; Paltsev, S.; Pitcher, Hugh M.; Reilly, J. M.; Richels, Richard G.; Sarofim, M. C.; Smith, Steven J.

    2009-11-01

    We explore the atmospheric composition, temperature and sea level implications of new reference and cost-optimized stabilization emissions scenarios produced using three different Integrated Assessment (IA) models for U.S. Climate Change Science Program (CCSP) Synthesis and Assessment Product 2.1a. We also consider an extension of one of these sets of scenarios out to 2300. Stabilization is defined in terms of radiative forcing targets for the sum of gases potentially controlled under the Kyoto Protocol. For the most stringent stabilization case (“Level 1” with CO2 concentration stabilizing at about 450 ppm), peak CO2 emissions occur close to today, implying a need for immediate CO2 emissions abatement if we wish to stabilize at this level. In the extended reference case, CO2 stabilizes at 1000 ppm in 2200 – but even to achieve this target requires large and rapid CO2 emissions reductions over the 22nd century. Future temperature changes for the Level 1 stabilization case show considerable uncertainty even when a common set of climate model parameters is used (a result of different assumptions for non-Kyoto gases). Uncertainties are about a factor of three when climate sensitivity uncertainties are accounted for. We estimate the probability that warming from pre-industrial times will be less than 2oC to be about 50%. For one of the IA models, warming in the Level 1 case is greater out to 2050 than in the reference case, due to the effect of decreasing SO2 emissions that occur as a side effect of the policy-driven reduction in CO2 emissions. Sea level rise uncertainties for the Level 1 case are very large, with increases ranging from 12 to 100 cm over 2000 to 2300.

  1. Stabilization of compactible waste

    SciTech Connect

    Franz, E.M.; Heiser, J.H. III; Colombo, P.

    1990-09-01

    This report summarizes the results of series of experiments performed to determine the feasibility of stabilizing compacted or compactible waste with polymers. The need for this work arose from problems encountered at disposal sites attributed to the instability of this waste in disposal. These studies are part of an experimental program conducted at Brookhaven National Laboratory (BNL) investigating methods for the improved solidification/stabilization of DOE low-level wastes. The approach taken in this study was to perform a series of survey type experiments using various polymerization systems to find the most economical and practical method for further in-depth studies. Compactible dry bulk waste was stabilized with two different monomer systems: styrene-trimethylolpropane trimethacrylate (TMPTMA) and polyester-styrene, in laboratory-scale experiments. Stabilization was accomplished by wetting or soaking compactible waste (before or after compaction) with monomers, which were subsequently polymerized. Three stabilization methods are described. One involves the in-situ treatment of compacted waste with monomers in which a vacuum technique is used to introduce the binder into the waste. The second method involves the alternate placement and compaction of waste and binder into a disposal container. In the third method, the waste is treated before compaction by wetting the waste with the binder using a spraying technique. A series of samples stabilized at various binder-to-waste ratios were evaluated through water immersion and compression testing. Full-scale studies were conducted by stabilizing two 55-gallon drums of real compacted waste. The results of this preliminary study indicate that the integrity of compacted waste forms can be readily improved to ensure their long-term durability in disposal environments. 9 refs., 10 figs., 2 tabs.

  2. Aquifer stability investigations

    SciTech Connect

    Allen, R.D.; Doherty, T.J.

    1981-09-01

    The study of compressed air energy storage (CAES) in porous rock reservoirs is carried out within the Reservoir Stability Studies Program at Pacific Northwest Laboratory. The goal of the study is to establish criteria for long-term stability of aquifer CAES reservoirs. These criteria are intended to be guidelines and check lists that utilities and architect-engineering firms may use to evaluate reservoir stability at candidate CAES sites. These criteria will be quantitative where possible, qualitative where necessary, and will provide a focal point for CAES relevant geotechnical knowledge, whether developed within this study or available from petroleum, mining or other geotechnical practices using rock materials. The Reservoir Stability Studies Program had four major activities: a state-of-the-art survey to establish preliminary stability criteria and identify areas requiring research and development; numerical modeling; laboratory testing to provide data for use in numerical models and to investigate fundamental rock mechanics, thermal, fluid, and geochemical response of aquifer materials; and field studies to verify the feasibility of air injection and recovery under CAES conditions in an aquifer, to validate and refine the stability criteria, and to evaluate the accuracy and adequacy of the numerical and experimental methodologies developed in previo