Sample records for cations divalent

  1. Condensation of nonstochiometric DNA/polycation complexes by divalent cations. (United States)

    Budker, Vladimir; Trubetskoy, Vladimir; Wolff, Jon A


    This study found that divalent cations induced the further condensation of partially condensed DNA within nonstochiometric polycation complexes. The addition of a few mmol of a divalent cation such as calcium reduced by half the inflection point at which DNA became fully condensed by poly-L-lysine (PLL) and a variety of other polycations. The effect on DNA condensation was initially observed using a new method, which is based on the concentration-dependent self-quenching of fluorescent moieties (e.g., rhodamine) covalently linked to the DNA backbone at relatively high densities. Additional analyses, which employed ultracentrifugation, dynamic light scattering, agarose gel electrophoresis, and atomic force microscopy, confirmed the effect of divalent cations. These results provide an additional accounting of the process by which divalent cations induce greater chromatin compaction that is based on the representation of chromatin fibers as a nonstoichiometric polyelectrolyte complex. They also offer a new approach to assemble nonviral vectors for gene therapy.

  2. Divalent cation shrinks DNA but inhibits its compaction with trivalent cation (United States)

    Tongu, Chika; Kenmotsu, Takahiro; Yoshikawa, Yuko; Zinchenko, Anatoly; Chen, Ning; Yoshikawa, Kenichi


    Our observation reveals the effects of divalent and trivalent cations on the higher-order structure of giant DNA (T4 DNA 166 kbp) by fluorescence microscopy. It was found that divalent cations, Mg(2+) and Ca(2+), inhibit DNA compaction induced by a trivalent cation, spermidine (SPD(3+)). On the other hand, in the absence of SPD(3+), divalent cations cause the shrinkage of DNA. As the control experiment, we have confirmed the minimum effect of monovalent cation, Na(+) on the DNA higher-order structure. We interpret the competition between 2+ and 3+ cations in terms of the change in the translational entropy of the counterions. For the compaction with SPD(3+), we consider the increase in translational entropy due to the ion-exchange of the intrinsic monovalent cations condensing on a highly charged polyelectrolyte, double-stranded DNA, by the 3+ cations. In contrast, the presence of 2+ cation decreases the gain of entropy contribution by the ion-exchange between monovalent and 3+ ions.

  3. Role of Reverse Divalent Cation Diffusion in Forward Osmosis Biofouling. (United States)

    Xie, Ming; Bar-Zeev, Edo; Hashmi, Sara M; Nghiem, Long D; Elimelech, Menachem


    We investigated the role of reverse divalent cation diffusion in forward osmosis (FO) biofouling. FO biofouling by Pseudomonas aeruginosa was simulated using pristine and chlorine-treated thin-film composite polyamide membranes with either MgCl2 or CaCl2 draw solution. We related FO biofouling behavior-water flux decline, biofilm architecture, and biofilm composition-to reverse cation diffusion. Experimental results demonstrated that reverse calcium diffusion led to significantly more severe water flux decline in comparison with reverse magnesium permeation. Unlike magnesium, reverse calcium permeation dramatically altered the biofilm architecture and composition, where extracellular polymeric substances (EPS) formed a thicker, denser, and more stable biofilm. We propose that FO biofouling was enhanced by complexation of calcium ions to bacterial EPS. This hypothesis was confirmed by dynamic and static light scattering measurements using extracted bacterial EPS with the addition of either MgCl2 or CaCl2 solution. We observed a dramatic increase in the hydrodynamic radius of bacterial EPS with the addition of CaCl2, but no change was observed after addition of MgCl2. Static light scattering revealed that the radius of gyration of bacterial EPS with addition of CaCl2 was 20 times larger than that with the addition of MgCl2. These observations were further confirmed by transmission electron microscopy imaging, where bacterial EPS in the presence of calcium ions was globular, while that with magnesium ions was rod-shaped.

  4. Structural Insights into Mitochondrial Calcium Uniporter Regulation by Divalent Cations. (United States)

    Lee, Samuel K; Shanmughapriya, Santhanam; Mok, Mac C Y; Dong, Zhiwei; Tomar, Dhanendra; Carvalho, Edmund; Rajan, Sudarsan; Junop, Murray S; Madesh, Muniswamy; Stathopulos, Peter B


    Calcium (Ca(2+)) flux into the matrix is tightly controlled by the mitochondrial Ca(2+) uniporter (MCU) due to vital roles in cell death and bioenergetics. However, the precise atomic mechanisms of MCU regulation remain unclear. Here, we solved the crystal structure of the N-terminal matrix domain of human MCU, revealing a β-grasp-like fold with a cluster of negatively charged residues that interacts with divalent cations. Binding of Ca(2+) or Mg(2+) destabilizes and shifts the self-association equilibrium of the domain toward monomer. Mutational disruption of the acidic face weakens oligomerization of the isolated matrix domain and full-length human protein similar to cation binding and markedly decreases MCU activity. Moreover, mitochondrial Mg(2+) loading or blockade of mitochondrial Ca(2+) extrusion suppresses MCU Ca(2+)-uptake rates. Collectively, our data reveal that the β-grasp-like matrix region harbors an MCU-regulating acidic patch that inhibits human MCU activity in response to Mg(2+) and Ca(2+) binding.

  5. Competition between kaolinite flocculation and stabilization in divalent cation solutions dosed with anionic polyacrylamides. (United States)

    Lee, Byung Joon; Schlautman, Mark A; Toorman, Erik; Fettweis, Michael


    Divalent cations have been reported to develop bridges between anionic polyelectrolytes and negatively-charged colloidal particles, thereby enhancing particle flocculation. However, results from this study of kaolinite suspensions dosed with various anionic polyacrylamides (PAMs) reveal that Ca(2+) and Mg(2+) can lead to colloid stabilization under some conditions. To explain the opposite but coexisting processes of flocculation and stabilization with divalent cations, a conceptual flocculation model with (1) particle-binding divalent cationic bridges between PAM molecules and kaolinite particles and (2) polymer-binding divalent cationic bridges between PAM molecules is proposed. The particle-binding bridges enhanced flocculation and aggregated kaolinite particles in large, easily-settleable flocs whereas the polymer-binding bridges increased steric stabilization by developing polymer layers covering the kaolinite surface. Both the particle-binding and polymer-binding divalent cationic bridges coexist in anionic PAM- and kaolinite-containing suspensions and thus induce the counteracting processes of particle flocculation and stabilization. Therefore, anionic polyelectrolytes in divalent cation-enriched aqueous solutions can sometimes lead to the stabilization of colloidal particles due to the polymer-binding divalent cationic bridges.

  6. Influence of Divalent Cations on Deformation and Rupture of Adsorbed Lipid Vesicles. (United States)

    Dacic, Marija; Jackman, Joshua A; Yorulmaz, Saziye; Zhdanov, Vladimir P; Kasemo, Bengt; Cho, Nam-Joon


    The fate of adsorbed lipid vesicles on solid supports depends on numerous experimental parameters and typically results in the formation of a supported lipid bilayer (SLB) or an adsorbed vesicle layer. One of the poorly understood questions relates to how divalent cations appear to promote SLB formation in some cases. The complexity arises from the multiple ways in which divalent cations affect vesicle-substrate and vesicle-vesicle interactions as well as vesicle properties. These interactions are reflected, e.g., in the degree of deformation of adsorbed vesicles (if they do not rupture). It is, however, experimentally challenging to measure the extent of vesicle deformation in real-time. Herein, we investigated the effect of divalent cations (Mg(2+), Ca(2+), Sr(2+)) on the adsorption of zwitterionic 1,2-dioleoyl-sn-glycero-3-phosphocholine (DOPC) lipid vesicles onto silicon oxide- and titanium oxide-coated substrates. The vesicle adsorption process was tracked using the quartz crystal microbalance-dissipation (QCM-D) and localized surface plasmon resonance (LSPR) measurement techniques. On silicon oxide, vesicle adsorption led to SLB formation in all cases, while vesicles adsorbed but did not rupture on titanium oxide. It was identified that divalent cations promote increased deformation of adsorbed vesicles on both substrates and enhanced rupture on silicon oxide in the order Ca(2+) > Mg(2+) > Sr(2+). The influence of divalent cations on different factors in these systems is discussed, clarifying experimental observations on both substrates. Taken together, the findings in this work offer insight into how divalent cations modulate the interfacial science of supported membrane systems.

  7. Effect of divalent cations on DMPC/DHPC bicelle formation and alignment. (United States)

    Brindley, Amanda J; Martin, Rachel W


    Many important classes of biomolecules require divalent cations for optimal activity, making these ions essential for biologically relevant structural studies. Bicelle mixtures composed of short-chain and long-chain lipids are often used in solution- and solid-state NMR structure determination; however, the phase diagrams of these useful orienting media and membrane mimetics are sensitive to other solution components. Therefore, we have investigated the effect of varying concentrations of four divalent cations, Ca(2+), Mg(2+), Zn(2+), and Cd(2+), on cholesterol sulfate-stabilized DMPC/DHPC bicelles. We found that low concentrations of all the divalent ions are tolerated with minimal perturbation. At higher concentrations Zn(2+) and Cd(2+) disrupt the magnetically aligned phase while Ca(2+) and Mg(2+) produce more strongly oriented phases. This result indicates that divalent cations are not only required to maintain the biological activity of proteins and nucleic acids; they may also be used to manipulate the behavior of the magnetically aligned phase.

  8. Use of MgO doped with a divalent or trivalent metal cation for removing arsenic from water (United States)

    Moore, Robert C; Holt-Larese, Kathleen C; Bontchev, Ranko


    Systems and methods for use of magnesium hydroxide, either directly or through one or more precursors, doped with a divalent or trivalent metal cation, for removing arsenic from drinking water, including water distribution systems. In one embodiment, magnesium hydroxide, Mg(OH).sub.2 (a strong adsorbent for arsenic) doped with a divalent or trivalent metal cation is used to adsorb arsenic. The complex consisting of arsenic adsorbed on Mg(OH).sub.2 doped with a divalent or trivalent metal cation is subsequently removed from the water by conventional means, including filtration, settling, skimming, vortexing, centrifugation, magnetic separation, or other well-known separation systems. In another embodiment, magnesium oxide, MgO, is employed, which reacts with water to form Mg(OH).sub.2. The resulting Mg(OH).sub.2 doped with a divalent or trivalent metal cation, then adsorbs arsenic, as set forth above. The method can also be used to treat human or animal poisoning with arsenic.

  9. Removal of some divalent cations from water by membrane-filtration assisted with alginate. (United States)

    Fatin-Rouge, Nicolas; Dupont, Alexandra; Vidonne, Alain; Dejeu, Jérome; Fievet, Patrick; Foissy, Alain


    The removal of divalent metal ions from hard waters or galvanic wastewater by polymer-assisted membrane filtration using alginate was investigated. The ability of this natural polymer to form aggregates and gels in presence of metal ions was studied, in order to carry out metal removal by ultra or micro-filtration. Alginate titrations have shown the presence of amine groups in addition to carboxylates onto the polymer backbone. The binding properties of alginate with divalent cations have been studied, showing an increasing affinity for Ca2+ over Mg2+ as polymer concentration increases, and the relative affinity Pb2+ > or = Cu2+ > Zn2+ > Ni2+. The softening of hard natural waters was achieved successfully and easily, but needs an optimal alginate concentration approximately 4 x 10(-2) M. The alginate powder can be directly added to hard waters. Except for Ni2+, metal-removal was efficient. Polymer regeneration has shown that Cu2+-complexes are labiles.

  10. Structural Insights into Divalent Cation Modulations of ATP-Gated P2X Receptor Channels

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    Go Kasuya


    Full Text Available P2X receptors are trimeric ATP-gated cation channels involved in physiological processes ranging widely from neurotransmission to pain and taste signal transduction. The modulation of the channel gating, including that by divalent cations, contributes to these diverse physiological functions of P2X receptors. Here, we report the crystal structure of an invertebrate P2X receptor from the Gulf Coast tick Amblyomma maculatum in the presence of ATP and Zn2+ ion, together with electrophysiological and computational analyses. The structure revealed two distinct metal binding sites, M1 and M2, in the extracellular region. The M1 site, located at the trimer interface, is responsible for Zn2+ potentiation by facilitating the structural change of the extracellular domain for pore opening. In contrast, the M2 site, coupled with the ATP binding site, might contribute to regulation by Mg2+. Overall, our work provides structural insights into the divalent cation modulations of P2X receptors.

  11. Divalent cation and ionic strength effects on Vinca alkaloid-induced tubulin self-association.


    Lobert, S; Boyd, C A; Correia, J J


    We present here a systematic study of ionic strength and divalent cation effects on Vinca alkaloid-induced tubulin spiral formation. We used sedimentation velocity experiments and quantitative fitting of weight-average sedimentation coefficients versus free drug concentrations to obtain thermodynamic parameters under various solution conditions. The addition of 50-150 mM NaCl to our standard buffer (10 mM piperazine-N,N'-bis(2-ethanesulfonic acid), 1 mM Mg, 50 microM GDP or GTP, pH 6.9) enhan...

  12. Cluster-Continuum Calculations of Hydration Free Energies of Anions and Group 12 Divalent Cations

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    Guo, Hao-Bo [ORNL; Liang, Liyuan [ORNL; Parks, Jerry M [ORNL; Smith, Jeremy C [ORNL; Riccardi, Demian M [ORNL; Gu, Baohua [ORNL


    Understanding aqueous phase processes involving group 12 metal cations is relevant to both environmental and biological sciences. Here, quantum chemical methods and polarizable continuum models are used to compute the hydration free energies of a series of divalent group 12 metal cations (Zn2+, Cd2+, and Hg2+) together with Cu2+ and the anions OH , SH , Cl , and F . A cluster-continuum method is employed, in which gas-phase clusters of the ion and explicit solvent molecules are immersed in a dielectric continuum. Two approaches to define the size of the solute-water cluster are compared, in which the number of explicit waters used is either held constant or determined variationally as that of the most favorable hydration free energy. Results obtained with various polarizable continuum models are also presented. Each leg of the relevant thermodynamic cycle is analyzed in detail to determine how different contributions yield the observed mean signed error (MSE) and the standard deviation of the error (STDEV) between theory and experiment. The use of a constant number of water molecules for each set of ions is found to lead to predicted relative trends that benefit from error cancellation. Overall, the best results are obtained with MP2 and the Solvent Model D polarizable continuum model (SMD), with eight explicit water molecules for anions and ten for the metal cations, yielding a STDEV of 2.3 kcal/mol and MSE of 0.9 kcal/mol between theoretical to experimental hydration free energies, which range from -72.4 kcal/mol for SH to -505.9 kcal/mol for Cu2+. Using B3PW91 with DFT-D3 dispersion corrections (B3PW91-D) and SMD yields a STDEV of 3.3 kcal mol 1 and MSE of 1.6 kcal/mol, to which adding MP2 corrections from smaller divalent metal ion water molecule clusters yields very good agreement with the full MP2 results. Using B3PW91-D and SMD, with two explicit water molecules for anions and six for divalent metal cations also yields reasonable agreement with experiment

  13. Adsorptive behaviour of mercury on algal biomass: Competition with divalent cations and organic compounds

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    Carro, Leticia; Barriada, Jose L. [Departamento de Quimica Fisica e Ingenieria Quimica I, Universidad de A Coruna, c/Rua da Fraga 10, 15008 A Coruna (Spain); Herrero, Roberto, E-mail: [Departamento de Quimica Fisica e Ingenieria Quimica I, Universidad de A Coruna, c/Rua da Fraga 10, 15008 A Coruna (Spain); Sastre de Vicente, Manuel E. [Departamento de Quimica Fisica e Ingenieria Quimica I, Universidad de A Coruna, c/Rua da Fraga 10, 15008 A Coruna (Spain)


    Highlights: {yields} Native and protonated macroalga S. muticum are good materials for mercury removal. {yields} Fast kinetic process and high mercury uptakes have been found for those materials. {yields} Diffusion control is the rate limiting step of the process. {yields} Competition effects by organic compounds, inorganic salts and divalent cations were analyzed. {yields} Continuous flow experiments allowed identification of mercury reduction during metal removal. - Abstract: Biosorption processes constitute an effective technique for mercury elimination. Sorption properties of native and acid-treated Sargassum muticum have been studied. Effect of pH, initial mercury concentration and contact time studies provided fundamental information about the sorption process. This information was used as the reference values to analyse mercury sorption under competition conditions. Saline effect has shown little influence in sorption, when only electrostatic modifications took place upon salt addition. On the contrary, if mercury speciation dramatically changed owing to the addition of an electrolyte, such as in the case of chloride salt, very large modifications in mercury sorption were observed. Competition with other divalent cations or organic compounds has shown little or none effect on mercury, indicating that a different mechanism is taking place during the removal of these pollutants. Finally, continuous flow experiments have clearly shown that a reduction process is also taking place during mercury removal. This fact is not obvious to elucidate under batch sorption experiments. Scanning Electron Microscopy analysis of the surface of the materials show deposits of mercury(I) and metallic mercury which is indicative of the reduction process proposed.

  14. Divalent cation-responsive myotonia and muscle paralysis in skeletal muscle sodium channelopathy. (United States)

    Mankodi, Ami; Grunseich, Christopher; Skov, Martin; Cook, Lisa; Aue, Georg; Purev, Enkhtsetseg; Bakar, Dara; Lehky, Tanya; Jurkat-Rott, Karin; Pedersen, Thomas H; Childs, Richard W


    We report a patient with paramyotonia congenita/hyperkalemic periodic paralysis due to Nav1.4 I693T mutation who had worsening of myotonia and muscle weakness in the setting of hypomagnesemia and hypocalcemia with marked recovery after magnesium administration. Computer simulations of the effects of the I693T mutation were introduced in the muscle fiber model by both hyperpolarizing shifts in the Nav1.4 channel activation and a faster recovery from slow channel inactivation. A further shift in the Nav1.4 channel activation in the hyperpolarizing direction as expected with low divalent cations resulted in myotonia that progressed to membrane inexcitability. Shifting the channel activation in the depolarizing direction as would be anticipated from magnesium supplementation abolished the myotonia. These observations provide clinical and biophysical evidence that the muscle symptoms in sodium channelopathy are sensitive to divalent cations. Exploration of the role of magnesium administration in therapy or prophylaxis is warranted with a randomized clinical trial.

  15. High concentrations of divalent cations isolate monosynaptic inputs from local circuits in the auditory midbrain

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    Shobhana eSivaramakrishnan


    Full Text Available Hierarchical processing of sensory information occurs at multiple levels between the peripheral and central pathway. Different extents of convergence and divergence in top down and bottom up projections makes it difficult to separate the various components activated by a sensory input. In particular, hierarchical processing at sub-cortical levels is little understood. Here we have developed a method to isolate extrinsic inputs to the inferior colliculus (IC, a nucleus in the midbrain region of the auditory system, with extensive ascending and descending convergence. By applying a high concentration of divalent cations (HiDi locally within the IC, we isolate a HiDi-sensitive from a HiDi-insensitive component of responses evoked by afferent input in brain slices and in vivo during a sound stimulus. Our results suggest that the HiDi sensitive component is a monosynaptic input to the IC, while the HiDi-insensitive component is a local polysynaptic circuit. Monosynaptic inputs have short latencies, rapid rise times and underlie first spike latencies. Local inputs have variable delays and evoke long-lasting excitation. In vivo, local circuits have variable onset times and temporal profiles. Our results suggest that high concentrations of divalent cations should prove to be a widely useful method of isolating extrinsic monosynaptic inputs from local circuits in vivo.

  16. Modelling how incorporation of divalent cations affects calcite wettability–implications for biomineralisation and oil recovery (United States)

    Andersson, M. P.; Dideriksen, K.; Sakuma, H.; Stipp, S. L. S.


    Using density functional theory and geochemical speciation modelling, we predicted how solid-fluid interfacial energy is changed, when divalent cations substitute into a calcite surface. The effect on wettability can be dramatic. Trace metal uptake can impact organic compound adsorption, with effects for example, on the ability of organisms to control crystal growth and our ability to predict the wettability of pore surfaces. Wettability influences how easily an organic phase can be removed from a surface, either organic compounds from contaminated soil or crude oil from a reservoir. In our simulations, transition metals substituted exothermically into calcite and more favourably into sites at the surface than in the bulk, meaning that surface properties are more strongly affected than results from bulk experiments imply. As a result of divalent cation substitution, calcite-fluid interfacial energy is significantly altered, enough to change macroscopic contact angle by tens of degrees. Substitution of Sr, Ba and Pb makes surfaces more hydrophobic. With substitution of Mg and the transition metals, calcite becomes more hydrophilic, weakening organic compound adsorption. For biomineralisation, this provides a switch for turning on and off the activity of organic crystal growth inhibitors, thereby controlling the shape of the associated mineral phase.

  17. The effect of external divalent cations on spontaneous non-selective cation channel currents in rabbit portal vein myocytes. (United States)

    Albert, A P; Large, W A


    1. The effects of external divalent cations on spontaneous single non-selective cation channel currents were studied in outside-out patches from rabbit portal vein smooth muscle cells in K+-free conditions. 2. In an external medium containing 1.5 mM Ca2+ (Ca2+o) the majority of spontaneous channel currents had a unitary conductance of 23 pS, reversal potential (Vr) of +10 mV and a low open probability (Po) at negative patch potentials. Some channels opened to a lower conductance state of about 13 pS suggesting that the cation channels have two conductance states. Open time and burst duration distributions could both be described by two exponentials with time constants of about of 1 ms and 7 ms for open times and 3 ms and 16 ms for burst durations. 3. In 0 Ca2+o the majority of spontaneous cation channels had a unitary conductance of 13 pS and Vr was shifted to +4 mV. Moreover the longer open time and longer burst duration time constants were both reduced to approximately half the values in 1.5 mM Ca2+o. 4. Compared to 0 Ca2+o the single channel currents in 3 microM and 100 microM Ca2+o had a 5- to 6-fold increase in Po which was accompanied by increases in both open times and burst durations. In 3 microM and 100 microM Ca2+o the unitary conductance of the single channel currents was between 22 and 26 pS. 5. At positive membrane potentials the single channel currents had an increased Po compared to negative potentials which was associated with increased open times and burst durations but these values were similar in 3 microM, 100 microM and 1.5 mM Ca2+o. 6. In 1.5 mM Sr2+o and 1.5 mM Ba2+o channels opened to the higher conductance state of about 22-25 pS and had a 3- to 7-fold greater Po than in 0 Ca2+o. 7. In conclusion, external divalent cations have marked effects on the unitary conductance and kinetic behaviour of non-selective cation channels in rabbit portal vein smooth muscle cells.

  18. Divalent cation tolerance protein binds to β-secretase and inhibits the processing of amyloid precursor protein

    Institute of Scientific and Technical Information of China (English)

    Runzhong Liu; Haibo Hou; Xuelian Yi; Shanwen Wu; Huan Zeng


    The deposition of amyloid-beta is a pathological hallmark of Alzheimer's disease. Amyloid-beta is derived from amyloid precursor protein through sequential proteolytic cleavages by β-secretase (beta-site amyloid precursor protein-cleaving enzyme 1) and γ-secretase. To further elucidate the roles of beta-site amyloid precursor protein-cleaving enzyme 1 in the development of Alzheimer's disease, a yeast two-hybrid system was used to screen a human embryonic brain cDNA library for proteins directly interacting with the intracellular domain of beta-site amyloid precursor protein-cleaving enzyme 1. A potential beta-site amyloid precursor protein-cleaving enzyme 1- interacting protein identified from the positive clones was divalent cation tolerance protein. Immunoprecipitation studies in the neuroblastoma cell line N2a showed that exogenous divalent cation tolerance protein interacts with endogenous beta-site amyloid precursor protein-cleaving enzyme 1. The overexpression of divalent cation tolerance protein did not affect beta-site amyloid precursor protein-cleaving enzyme 1 protein levels, but led to increased amyloid precursor protein levels in N2a/APP695 cells, with a concomitant reduction in the processing product amyloid precursor protein C-terminal fragment, indicating that divalent cation tolerance protein inhibits the processing of amyloid precursor protein. Our experimental findings suggest that divalent cation tolerance protein negatively regulates the function of beta-site amyloid precursor protein-cleaving enzyme 1. Thus, divalent cation tolerance protein could play a protective role in Alzheimer's disease.

  19. Divalent cation and ionic strength effects on Vinca alkaloid-induced tubulin self-association. (United States)

    Lobert, S; Boyd, C A; Correia, J J


    We present here a systematic study of ionic strength and divalent cation effects on Vinca alkaloid-induced tubulin spiral formation. We used sedimentation velocity experiments and quantitative fitting of weight-average sedimentation coefficients versus free drug concentrations to obtain thermodynamic parameters under various solution conditions. The addition of 50-150 mM NaCl to our standard buffer (10 mM piperazine-N,N'-bis(2-ethanesulfonic acid), 1 mM Mg, 50 microM GDP or GTP, pH 6.9) enhances overall vinblastine- or vincristine-induced tubulin self-association. As demonstrated in previous studies, GDP enhances overall self-association more than GTP, although in the presence of salt, GDP enhancement is reduced. For example, in 150 mM NaCl, GDP enhancement is 0.24 kcal/mol for vinblastine and 0.36 kcal/mol for vincristine versus an average enhancement of 0.87 (+/- 0.34) kcal/mol for the same drugs in the absence of salt. Wyman linkage analysis of experiments with vinblastine or vincristine over a range of NaCl concentrations showed a twofold increase in the change in NaCl bound to drug-induced spirals in the presence of GTP compared to GDP. These data indicate that GDP enhancement of Vinca alkaloid-induced tubulin self-association is due in part to electrostatic inhibition in the GTP state. In the absence of NaCl, we found that vinblastine and 1 mM Mn2+ or Ca2+ causes immediate condensation of tubulin. The predominant aggregates observed by electron microscopy are large sheets. This effect was not found with 1 mM Mg2+. At 100 microM cation concentrations (Mn2+, Mg2+, or Ca2+), GDP enhances vinblastine-induced spiral formation by 0.55 (+/- 0.26) kcal/mol. This effect is found only in K2, the association of liganded heterodimers at the ends of growing spirals. There is no GDP enhancement of K1, the binding of drug to heterodimer, although K1 is dependent upon the divalent cation concentration. NaCl diminishes tubulin condensation, probably by inhibiting lateral

  20. Acidic pH and divalent cation sensing by PhoQ are dispensable for systemic salmonellae virulence. (United States)

    Hicks, Kevin G; Delbecq, Scott P; Sancho-Vaello, Enea; Blanc, Marie-Pierre; Dove, Katja K; Prost, Lynne R; Daley, Margaret E; Zeth, Kornelius; Klevit, Rachel E; Miller, Samuel I


    Salmonella PhoQ is a histidine kinase with a periplasmic sensor domain (PD) that promotes virulence by detecting the macrophage phagosome. PhoQ activity is repressed by divalent cations and induced in environments of acidic pH, limited divalent cations, and cationic antimicrobial peptides (CAMP). Previously, it was unclear which signals are sensed by salmonellae to promote PhoQ-mediated virulence. We defined conformational changes produced in the PhoQ PD on exposure to acidic pH that indicate structural flexibility is induced in α-helices 4 and 5, suggesting this region contributes to pH sensing. Therefore, we engineered a disulfide bond between W104C and A128C in the PhoQ PD that restrains conformational flexibility in α-helices 4 and 5. PhoQ(W104C-A128C) is responsive to CAMP, but is inhibited for activation by acidic pH and divalent cation limitation. phoQ(W104C-A128C) Salmonella enterica Typhimurium is virulent in mice, indicating that acidic pH and divalent cation sensing by PhoQ are dispensable for virulence.

  1. Further studies on the formation of cardiolipin and phosphatidylglycerol in rat liver mitochondria. Effect of divalent cations and the fatty acid composition of CDP-diglyceride

    NARCIS (Netherlands)

    Hostetler, Karl Y.; Galesloot, J.M.; Boer, P.; Bosch, H. van den


    The divalent cation requirement for mitochondrial cardiolipin biosynthesis has been further investigated. The relative order of divalent cation activity was Co2+ > Mn2+ > Mg2+. Cardiolipin was not formed in the incubations with Zn2+, Fe2+, Cu2+, Hg2+, and Ca2+. Cardiolipin synthesis in the presence

  2. Modulating macrophage polarization with divalent cations in nanostructured titanium implant surfaces (United States)

    Lee, Chung-Ho; Kim, Youn-Jeong; Jang, Je-Hee; Park, Jin-Woo


    Nanoscale topographical modification and surface chemistry alteration using bioactive ions are centrally important processes in the current design of the surface of titanium (Ti) bone implants with enhanced bone healing capacity. Macrophages play a central role in the early tissue healing stage and their activity in response to the implant surface is known to affect the subsequent healing outcome. Thus, the positive modulation of macrophage phenotype polarization (i.e. towards the regenerative M2 rather than the inflammatory M1 phenotype) with a modified surface is essential for the osteogenesis funtion of Ti bone implants. However, relatively few advances have been made in terms of modulating the macrophage-centered early healing capacity in the surface design of Ti bone implants for the two important surface properties of nanotopography and and bioactive ion chemistry. We investigated whether surface bioactive ion modification exerts a definite beneficial effect on inducing regenerative M2 macrophage polarization when combined with the surface nanotopography of Ti. Our results indicate that nanoscale topographical modification and surface bioactive ion chemistry can positively modulate the macrophage phenotype in a Ti implant surface. To the best of our knowledge, this is the first demonstration that chemical surface modification using divalent cations (Ca and Sr) dramatically induces the regenerative M2 macrophage phenotype of J774.A1 cells in nanostructured Ti surfaces. In this study, divalent cation chemistry regulated the cell shape of adherent macrophages and markedly up-regulated M2 macrophage phenotype expression when combined with the nanostructured Ti surface. These results provide insight into the surface engineering of future Ti bone implants that are harmonized between the macrophage-governed early wound healing process and subsequent mesenchymal stem cell-centered osteogenesis function.

  3. Probing Induced Structural Changes in Biomimetic Bacterial Cell Membrane Interactions with Divalent Cations

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    Holt, Allison M [ORNL; Standaert, Robert F [ORNL; Jubb, Aaron M [ORNL; Katsaras, John [ORNL; Johs, Alexander [ORNL


    Biological membranes, formed primarily by the self-assembly of complex mixtures of phospholipids, provide a structured scaffold for compartmentalization and structural processes in living cells. The specific physical properties of phospholipid species present in a given membrane play a key role in mediating these processes. Phosphatidylethanolamine (PE), a zwitterionic lipid present in bacterial, yeast, and mammalian cell membranes, is exceptional. In addition to undergoing the standard lipid polymorphic transition between the gel and liquid-crystalline phase, it can also assume an unusual polymorphic state, the inverse hexagonal phase (HII). Divalent cations are among the factors that drive the formation of the HII phase, wherein the lipid molecules form stacked tubular structures by burying the hydrophilic head groups and exposing the hydrophobic tails to the bulk solvent. Most biological membranes contain a lipid species capable of forming the HII state suggesting that such lipid polymorphic structural states play an important role in structural biological processes such as membrane fusion. In this study, the interactions between Mg2+ and biomimetic bacterial cell membranes composed of PE and phosphatidylglycerol (PG) were probed using differential scanning calorimetry (DSC), small-angle x-ray scattering (SAXS), and fluorescence spectroscopy. The lipid phase transitions were examined at varying ratios of PE to PG and upon exposure to physiologically relevant concentrations of Mg2+. An understanding of these basic interactions enhances our understanding of membrane dynamics and how membrane-mediated structural changes may occur in vivo.

  4. Modulation by Divalent Cations of GABAρ1 Receptor From Human Retina Expressed in Xenopus Oocytes

    Institute of Scientific and Technical Information of China (English)


    Objective To investigate functional homooligomeric GABAρ1 receptors expressed in Xenopus oocytes and the modulation of divalent cations. Methods GABAρ1 cDNA from human retina was transcribed in vitro to obtain sense ρ1 mRNA, which was microinjected into Xenopus oocytes. Two-electrodes voltage clamp technique was performed to record GABA-induced currents. Results  Expressed receptors were found to have similar properties to GABAC receptors characterized in the retina. Cl-currents induced by GABA were blocked by picrotoxin instead of bicuculline. GABA-induced currents reversed at -19±2.5 mV, and EC50 was 3.3 μmol/L. Zn+ + modulated GABA-induced currents with an IC50=9.6 μ mol/L. Ni+ +, Cu+ + and Cd+ + inhibited GABA ρ1 obviously, too. Their rank order of potency was Zn+ +>Ni+ +>Cu+ +>Cd+ +. Conclusion Zinc(10 μmol/L) inhibited GABA-induced currents in a competitive manner, and its action was sensitive to extracellular pH. Site-directed mutagenesis revealed that substitution of a single histidine residue (H44 and H48) failed to affect zinc sensitivity.

  5. Unexpectedly Enhanced Solubility of Aromatic Amino Acids and Peptides in an Aqueous Solution of Divalent Transition-Metal Cations (United States)

    Shi, Guosheng; Dang, Yaru; Pan, Tingting; Liu, Xing; Liu, Hui; Li, Shaoxian; Zhang, Lijuan; Zhao, Hongwei; Li, Shaoping; Han, Jiaguang; Tai, Renzhong; Zhu, Yiming; Li, Jichen; Ji, Qing; Mole, R. A.; Yu, Dehong; Fang, Haiping


    We experimentally observed considerable solubility of tryptophan (Trp) in a CuCl2 aqueous solution, which could reach 2-5 times the solubility of Trp in pure water. Theoretical studies show that the strong cation-π interaction between Cu2 + and the aromatic ring in Trp modifies the electronic distribution of the aromatic ring to enhance significantly the water affinity of Trp. Similar solubility enhancement has also been observed for other divalent transition-metal cations (e.g., Zn2 + and Ni2 + ), another aromatic amino acid (phenylalanine), and three aromatic peptides (Trp-Phe, Phe-Phe, and Trp-Ala-Phe).

  6. Data in support of the negative influence of divalent cations on (-)-epigallocatechin-3-gallate (EGCG)-mediated inhibition of matrix metalloproteinase-2 (MMP-2). (United States)

    Deb, Gauri; Batra, Sahil; Limaye, Anil M


    In this data article we have provided evidence for the negative influence of divalent cations on (-)-epigallocatechin-3-gallate (EGCG)-mediated inhibition of matrix metalloproteinase-2 (MMP-2) activity in cell-free experiments. Chelating agents, such as EDTA and sodium citrate alone, did not affect MMP-2 activity. While EDTA enhanced, excess of divalent cations interfered with EGCG-mediated inhibition of MMP-2.

  7. Composition dependence of glow peak temperature in KCl{sub 1-x}Br{sub x} doped with divalent cations

    Energy Technology Data Exchange (ETDEWEB)

    Perez-Salas, R [Departamento de Investigacion en FIsica, Universidad de Sonora, Apartado Postal 5-088 Hermosillo, Sonora, 83190 (Mexico); Aceves, R [Departamento de Investigacion en FIsica, Universidad de Sonora, Apartado Postal 5-088 Hermosillo, Sonora, 83190 (Mexico); RodrIguez-Mijangos, R [Departamento de Investigacion en FIsica, Universidad de Sonora, Apartado Postal 5-088 Hermosillo, Sonora, 83190 (Mexico); Riveros, H G [Instituto de FIsica, UNAM, Apartado Postal 20/364, Mexico, DF 01000, Mexico (Mexico); Duarte, C [Departamento de GeologIa, Universidad de Sonora, Rosales y Boulevard Luis E, Hermosillo, Sonora, 83000 (Mexico)


    Thermoluminescence measurements of {beta}-irradiated Eu{sup 2+} - and Ca{sup 2+} - doped KCl{sub 1-x}KBr{sub x} solid solutions excited at room temperature have been carried out to identify the effect of composition on the glow peaks. A typical glow peak has been distinguished for each composition. A linear dependence of its temperature on the composition x has been found. These results indicate that for divalent impurity-doped alkali halide solid solutions these glow peak temperatures are mostly dependent on the lattice constant of the host than on the size of the anion or impurity cation.

  8. Sugar-induced blue membrane: release of divalent cations during phase transition of purple membranes observed in sugar-derived glasses. (United States)

    Rhinow, Daniel; Hampp, Norbert A


    The formation of blue membrane from purple membranes (PM) has been observed in glassy films made from PM and various sugars. The phase transition of PM at about 70 degrees C causes the complexation of divalent cations to be weakened. The vicinal diol structures in sugars are capable to complex divalent cations and delocalize them throughout the matrix as long as its glass transition temperature is lower than the phase transition temperature of PM. The loss of divalent cations from bacteriorhodopsin (BR), the only protein in PM, causes the formation of blue membrane (BM), which is accompanied by a loss of beta-sheet structure observable in the infrared spectrum. Glassy sugars are particular useful to observe this transition, as sugar entrapment does not restrict conformational changes of BR but rather retards them. The material obtained was named sugar-induced blue membrane (SIBM). The formation of SIBM is inhibited by the addition of divalent cations. Furthermore, SIBM is reverted immediately to PM by addition of water. A characteristic time dependence of the thermal reversion of SIBM to PM proves that the phase transition of PM triggers the release and uptake of divalent cations and the corresponding color change.

  9. Protonation of a hydroxide anion bridging two divalent magnesium cations in water probed by first-principles metadynamics simulation. (United States)

    Park, Jung Mee; Boero, Mauro


    The protonation of a hydroxide anion (OH(-)) located between two magnesium cations (Mg(2+)) in aqueous solution has been investigated by first-principles metadynamics simulation. We observe that the complex Mg(2+)-OH(-)-Mg(2+) is stabilized by the coparticipation of the hydroxide anion to the first hydration shells of both the Mg(2+) cations. Contrary to the cases of OH(-) in pure water, the transfer of protons in the presence of the divalent metal ions turns out to be a slow chemical event. This can be ascribed to the decreased proton affinity of the bridging OH(-). Metadynamics simulation, used to overcome the difficulty of the long time scale required by the protonation of the bridging OH(-), has shown that the system possesses a great stability on the reactant state, characterized by a bioctahedral (6,6) solvation structure around the two Mg(2+) cations. The exploration of the free energy landscape shows that this stable bioctahedral configuration converts into a lower coordinated (5,6) structure, leading to a proton transfer from a water molecule belonging to the first solvation shell of the Mg(2+) ion having the lower coordination to the bridging OH(-); the free energy barrier for the protonation reaction is 11 kcal/mol, meaning that the bridging hydroxide is a weak base. During the proton transfer, the bridging OH(-) reverts to an H(2)O molecule, and this breaks the electrostatic coupling of the two Mg(2+) ions, which depart independently with their own hydration shells, one of which is entirely formed by water molecules. The second one carries the newly created OH(-). Our results show that the flexibility in the metal coordination plays a crucial role in both the protonation process of the bridging OH(-) and the separation of the metal cations, providing useful insight into the nature of proton transfer in binuclear divalent metal ions, with several biological implications, such as, for instance, transesterification of catalytic RNA.

  10. The polybasic lysine-rich domain of plasma membrane-resident STIM1 is essential for the modulation of store-operated divalent cation entry by extracellular calcium. (United States)

    Jardin, Isaac; Dionisio, Natalia; Frischauf, Irene; Berna-Erro, Alejandro; Woodard, Geoffrey E; López, José J; Salido, Ginés M; Rosado, Juan A


    STIM1 acts as an endoplasmic reticulum Ca(2+) sensor that communicates the filling state of the intracellular stores to the store-operated channels. In addition, STIM1 is expressed in the plasma membrane, with the Ca(2+) binding EF-hand motif facing the extracellular medium; however, its role sensing extracellular Ca(2+) concentrations in store-operated Ca(2+) entry (SOCE), as well as the underlying mechanism remains unclear. Here we report that divalent cation entry stimulated by thapsigargin (TG) is attenuated by extracellular Ca(2+) in a concentration-dependent manner. Expression of the Ca(2+)-binding defective STIM1(D76A) mutant did not alter the surface expression of STIM1 but abolishes the regulation of divalent cation entry by extracellular Ca(2+). Orai1 and TRPC1 have been shown to play a major role in SOCE. Expression of the STIM1(D76A) mutant did not alter Orai1 phosphoserine content. TRPC1 silencing significantly attenuated TG-induced Mn(2+) entry. Expression of the STIM1(K684,685E) mutant impaired the association of plasma membrane STIM1 with TRPC1, as well as the regulation of TG-induced divalent cation entry by extracellular Ca(2+), which suggests that TRPC1 might be involved in the regulation of divalent cation entry by extracellular Ca(2+) mediated by plasma membrane-resident STIM1. Expression of the STIM1(D76A) or STIM1(K684,685E) mutants reduced store-operated divalent cation entry and resulted in loss of dependence on the extracellular Ca(2+) concentration, providing evidence for a functional role of plasma membrane-resident STIM1 in the regulation of store-operated divalent cation entry, which at least involves the EF-hand motif and the C-terminal polybasic lysine-rich domain.

  11. Modulation of Higher Order Chromatin Conformation in Mammalian Cell Nuclei Can Be Mediated by Polyamines and Divalent Cations.

    Directory of Open Access Journals (Sweden)

    Ashwat Visvanathan

    Full Text Available The organisation of the large volume of mammalian genomic DNA within cell nuclei requires mechanisms to regulate chromatin compaction involving the reversible formation of higher order structures. The compaction state of chromatin varies between interphase and mitosis and is also subject to rapid and reversible change upon ATP depletion/repletion. In this study we have investigated mechanisms that may be involved in promoting the hyper-condensation of chromatin when ATP levels are depleted by treating cells with sodium azide and 2-deoxyglucose. Chromatin conformation was analysed in both live and permeabilised HeLa cells using FLIM-FRET, high resolution fluorescence microscopy and by electron spectroscopic imaging microscopy. We show that chromatin compaction following ATP depletion is not caused by loss of transcription activity and that it can occur at a similar level in both interphase and mitotic cells. Analysis of both live and permeabilised HeLa cells shows that chromatin conformation within nuclei is strongly influenced by the levels of divalent cations, including calcium and magnesium. While ATP depletion results in an increase in the level of unbound calcium, chromatin condensation still occurs even in the presence of a calcium chelator. Chromatin compaction is shown to be strongly affected by small changes in the levels of polyamines, including spermine and spermidine. The data are consistent with a model in which the increased intracellular pool of polyamines and divalent cations, resulting from depletion of ATP, bind to DNA and contribute to the large scale hyper-compaction of chromatin by a charge neutralisation mechanism.

  12. Influence of divalent cations and pH adsorption of a bacterial polysaccharide adhesin

    Digital Repository Service at National Institute of Oceanography (India)

    Bhosle, N.B.; Suci, P.A.; Baty, A.M.; Weiner, R.M.; Geesey, G.G.

    is important. Evidence for significant participation of hydrogen bonding to the oxide surface is lacking. © 1998 Academic Press Key Words: adhesion; bacteria; polysaccharide; adsorption; di- valent cation. INTRODUCTION Attachment of microorganisms to inert....00 Copyright © 1998 by Academic Press All rights of reproduction in any form reserved. cations and of pH on the adsorption behavior of fr2ps in order to further investigate the interactions involved in bonding of this adhesive polysaccharide at an aqueous...

  13. Improving the Performance of Lithium Manganese Phosphate Through Divalent Cation Substitution

    Energy Technology Data Exchange (ETDEWEB)

    Chen, Guoying; Richardson, Thomas J.


    Highly crystalline samples of LiMnPO{sub 4} and its analogs with partial substitution of Mn by divalent Mg, Cu, Zn, and Ni were prepared by hydrothermal synthesis and characterized by x-ray diffraction and infrared spectroscopy. Chemical oxidation produced two-phase mixtures of the initial phases LiMn{sub (1-y)}M{sub y}PO{sub 4} and the delithiated forms, Li{sub y}Mn{sub (1-y)}M{sub y}PO{sub 4}, all with the olivine structure. The extent of oxidation depended upon the quantity of oxidizing agent used and on the identity of the substituent ions. Mg, Ni and Cu were found to increase the level of delithation relative to that in pure LiMnPO{sub 4}. Mg was also shown to reduce the tendency of the oxidized phase to absorb water.

  14. Interfacial binding of divalent cations to calixarene-based Langmuir monolayers. (United States)

    Tulli, Ludovico G; Wang, Wenjie; Lindemann, William R; Kuzmenko, Ivan; Meier, Wolfgang; Vaknin, David; Shahgaldian, Patrick


    The interactions of Langmuir monolayers produced through the self-assembly of an amphiphilic p-carboxycalix[4]arene (1) with a series of divalent, fourth-period transition metals, at the air-water interface, were investigated. Changes in the interfacial behavior of 1 in response to the presence of CuCl2, CoCl2, MnCl2, and NiCl2 were studied by means of Langmuir compression isotherms and Brewster angle microscopy (BAM). The measurements revealed that the self-assembly properties of 1 are significantly affected by Cu(2+) ions. The interactions of 1-based monolayers with Co(2+) and Cu(2+) ions were further investigated by means of synchrotron radiation-based X-ray reflectivity (XRR), X-ray near-total-reflection fluorescence (XNTRF), and grazing incidence X-ray diffraction (GIXD). XNTRF and XRR analyses revealed that the monolayer of 1 binds more strongly to Cu(2+) than Co(2+) ions. In the presence of relatively high concentrations of Cu(2+) ions in the subphase (1.4 × 10(-3) M), XNTRF exhibited anomalous depth profile behavior and GIXD measurements showed considerably strong diffuse scattering. Both measurements suggest the formation of Cu(2+) clusters contiguous to the monolayer of 1.

  15. Divalent cations increase lipid order in erythrocytes and susceptibility to secretory phospholipase A2. (United States)

    Vest, Rebekah S; Gonzales, Laurie J; Permann, Seth A; Spencer, Emily; Hansen, Lee D; Judd, Allan M; Bell, John D


    Elevated concentrations of intracellular calcium in erythrocytes increase membrane order and susceptibility to secretory phospholipase A2. We hypothesize that calcium aids the formation of domains of ordered lipids within erythrocyte membranes by interacting directly with the inner leaflet of the cell membrane. The interface of these domains with regions of more fluid lipids may create an environment with weakened neighbor-neighbor interactions that would facilitate phospholipid migration into the active site of bound secretory phospholipase A2. This hypothesis was investigated by determining the effects of seven other divalent ions on erythrocyte membrane properties. Changes in membrane order were assessed with steady-state fluorescence spectroscopy and two-photon microscopy with an environment-sensitive probe, laurdan. Each ion increased apparent membrane order in model membranes and in erythrocytes when introduced with an ionophore, suggesting that direct binding to the inner face of the membrane accounts for the effects of calcium on membrane fluidity. Furthermore, the degree to which ions affected membrane properties correlated with the ionic radius and electronegativity of the ions. Lastly, erythrocytes became more susceptible to enzyme hydrolysis in the presence of elevated intracellular levels of nickel and manganese, but not magnesium. These differences appeared related to the ability of the ions to induce a transition in erythrocyte shape.

  16. Divalent cations control cell-substrate adhesion and laminin expression in normal and malignant human melanocytes in early and late stages of cellular differentiation. (United States)

    Searles, G E; Dixon, W T; Thomas, P D; Jimbow, K


    Integrins are a class of adhesion molecules that depends on divalent cations for proper function. This study examined whether human normal melanocytes and malignant (metastatic) melanocytes with early and late stages of cellular differentiation (G361 and SK-MEL-23, respectively) would differ in integrin-mediated adhesion to fibronectin, laminin, as well as collagens type I and type IV, and whether divalent cations could influence the strength of adhesion ability. Integrin subunit expression was determined by flow cytometry using integrin subunit-specific antibodies as probes. Integrin-specific adhesion was determined using soluble glycine-arginine-glycine-asparagine-serine peptide and integrin subunit-specific antibodies as functional blocking agents. This study shows that both normal and malignant melanocytes adhere to extracellular matrices in a divalent cation-dependent manner, and adhesion strength varies with the cation species. Integrins can be rapidly activated by small alterations in cation concentration, manganese being the most potent. There were marked differences in substrate adhesion between normal melanocytes and metastatic malignant melanoma cells, but these differences were not related to the stage of cellular differentiation. All the three cell types, however, expressed the same integrin subunits at approximately the same levels. This suggests that substrate adhesion of melanocytes and melanoma cells might involve some integrin-independent mechanisms as well. Manganese, in particular, appears to cause adhesion by activating both integrin-dependent and -independent mechanisms.

  17. Clustered Conserved Cysteines in Hyaluronan Synthase Mediate Cooperative Activation by Mg(2+) Ions and Severe Inhibitory Effects of Divalent Cations. (United States)

    Tlapak-Simmons, Valarie L; Medina, Andria P; Baggenstoss, Bruce A; Nguyen, Long; Baron, Christina A; Weigel, Paul H


    Hyaluronan synthase (HAS) uses UDP-GlcUA and UDP-GlcNAc to make hyaluronan (HA). Streptococcus equisimilis HAS (SeHAS) contains four conserved cysteines clustered near the membrane, and requires phospholipids and Mg(2+) for activity. Activity of membrane-bound or purified enzyme displayed a sigmoidal saturation profile for Mg(2+) with a Hill coefficient of 2. To assess if Cys residues are important for cooperativity we examined the Mg(2+) dependence of mutants with various combinations of Cys-to-Ala mutations. All Cys-mutants lost the cooperative response to Mg(2+). In the presence of Mg(2+), other divalent cations inhibited SeHAS with different potencies (Cu(2+)~Zn(2+) >Co(2+) >Ni(2+) >Mn(2+) >Ba(2+) Sr(2+) Ca(2+)). Some divalent metal ions likely inhibit by displacement of Mg(2+)-UDP-Sugar complexes (e.g. Ca(2+), Sr(2+) and Ba(2+) had apparent Ki values of 2-5 mM). In contrast, Zn(2+) and Cu(2+) inhibited more potently (apparent Ki ≤ 0.2 mM). Inhibition of Cys-null SeHAS by Cu(2+), but not Zn(2+), was greatly attenuated compared to wildtype. Double and triple Cys-mutants showed differing sensitivities to Zn(2+) or Cu(2+). Wildtype SeHAS allowed to make HA prior to exposure to Zn(2+) or Cu(2+) was protected from inhibition, indicating that access of metal ions to sensitive functional groups was hindered in processively acting HA•HAS complexes. We conclude that clustered Cys residues mediate cooperative interactions with Mg(2+) and that transition metal ions inhibit SeHAS very potently by interacting with one or more of these -SH groups.

  18. First O-Glycosylation from Unprotected 1-Thioimidoyl Hexofuranosides Assisted by Divalent Cations


    Euzen, Ronan; Guégan, Jean-Paul; Ferrières, Vincent; Plusquellec, Daniel


    The preparation of O-hexofuranosides was accomplished from unprotected 1-thioimidoyl furanosides as donors. The present methodology was first used for the synthesis of octyl galactofuranoside and further extended to D-galactofuranose-containing disaccharides. Within this study, we emphasized the need for additional complexing cations to maintain the furanose ring in its initial size. After experimentation, calcium ion was first used concomitantly with trimethylsilyl trifluoromethanesulfonate,...

  19. First o-glycosylation from unprotected 1-thioimidoyl hexofuranosides assisted by divalent cations. (United States)

    Euzen, Ronan; Guégan, Jean-Paul; Ferrières, Vincent; Plusquellec, Daniel


    The preparation of O-hexofuranosides was accomplished from unprotected 1-thioimidoyl furanosides as donors. The present methodology was first used for the synthesis of octyl galactofuranoside and further extended to D-galactofuranose-containing disaccharides. Within this study, we emphasized the need for additional complexing cations to maintain the furanose ring in its initial size. After experimentation, calcium ion was first used concomitantly with trimethylsilyl trifluoromethanesulfonate, the latter being able to activate the thioimidate and the former being likely to inhibit ring expansion. Moreover, an improvement was performed by using copper(II) trifluoromethanesulfonate which could then meet the requirements as both promoter and complexing agent.

  20. Metabolic Fingerprinting of Pseudomonas putida DOT-T1E Strains: Understanding the Influence of Divalent Cations in Adaptation Mechanisms Following Exposure to Toluene

    Directory of Open Access Journals (Sweden)

    Ali Sayqal


    Full Text Available Pseudomonas putida strains can adapt and overcome the activity of toxic organic solvents by the employment of several resistant mechanisms including efflux pumps and modification to lipopolysaccharides (LPS in their membranes. Divalent cations such as magnesium and calcium play a crucial role in the development of solvent tolerance in bacterial cells. Here, we have used Fourier transform infrared (FT-IR spectroscopy directly on cells (metabolic fingerprinting to monitor bacterial response to the absence and presence of toluene, along with the influence of divalent cations present in the growth media. Multivariate analysis of the data using principal component-discriminant function analysis (PC-DFA showed trends in scores plots, illustrating phenotypic alterations related to the effect of Mg2+, Ca2+ and toluene on cultures. Inspection of PC-DFA loadings plots revealed that several IR spectral regions including lipids, proteins and polysaccharides contribute to the separation in PC-DFA space, thereby indicating large phenotypic response to toluene and these cations. Finally, the saturated fatty acid ratio from the FT-IR spectra showed that upon toluene exposure, the saturated fatty acid ratio was reduced, while it increased in the presence of divalent cations. This study clearly demonstrates that the combination of metabolic fingerprinting with appropriate chemometric analysis can result in practicable knowledge on the responses of important environmental bacteria to external stress from pollutants such as highly toxic organic solvents, and indicates that these changes are manifest in the bacterial cell membrane. Finally, we demonstrate that divalent cations improve solvent tolerance in P. putida DOT‑T1E strains.

  1. Inhibition of Na(+) -K+ pump activity by divalent cations in intact peritoneal mast cells of the rat

    DEFF Research Database (Denmark)

    Knudsen, T; Berthelsen, Carsten; Johansen, Torben


    1. The inhibition by the divalent cations magnesium, barium and strontium and the trivalent ion lanthanum of the Na(+) -K+ pump in the plasma membrane of rat peritoneal mast cells was studied in pure mast cell populations by measurement of the ouabain-sensitive uptake of the radioactive potassium......-resistant uptake was not changed. Half maximum decrease in the ouabain-sensitive K+(86Rb+)-uptake was observed with 1.8 mM magnesium, 1.2mM barium and 0.7 mM strontium. 4. The trivalent ion lanthanum blocked almost completely the ouabain-sensitive K+(86Rb+)-uptake at a concentration of 1 microM as does 1 m......M calcium. Combining either of these ions with magnesium had no further inhibitory effect on the ouabain-sensitive uptake. 5. In conclusion, in addition to the previously suggested modulation by calcium of the activity of the Na+ (-)K+ pump, evidence is provided in this investigation that the modulation may...

  2. Regulation by divalent cations of /sup 3/H-baclofen binding to GABA/sub B/ sites in rat cerebellar membranes

    Energy Technology Data Exchange (ETDEWEB)

    Kato, K.; Goto, M.; Fukuda, H.


    When investigating the effects of divalent cations (Mg/sup 2 +/, Ca/sup 2 +/, Sr/sup 2 +/, Ba/sup 2 +/, Mn/sup 2 +/ and Ni/sup 2 +/) on /sup 3/H-baclofen binding to rat cerebellar synaptic membranes, we found that the specific binding of /sup 3/H-baclofen was not only dependent on divalent cations, but was increased dose-dependently in the presence of these cations. The effects were in the following order of potency: Mn/sup 2 +/ approx. = Ni/sup 2 +/ > Mg/sup 2 +/ > Ca/sup 2 +/ > Sr/sup 2 +/ > Ba/sup 2 +/. Scatchard analysis of the binding data revealed a single component of the binding sites in the presence of 2.5 mM MgCl/sub 2/, 2.5 mM CaCl/sub 2/ or 0.3 mM MnCl/sub 2/ whereas two components appeared in the presence of 2.5 mM MnCl/sub 2/ or 1 mM NiCl/sub 2/. In the former, divalent cations altered the apparent affinity (K/sub d/) without affecting density of the binding sites (B/sub max/). In the latter, the high-affinity sites showed a higher affinity and lower density of the binding sites than did the single component of the former. As the maximal effects of four cations (Mg/sup 2 +/, Ca/sup 2 +/, Mn/sup 2 +/, and Ni/sup 2 +/) were not additive, there are probably common sites of action of these divalent cations. Among the ligands for GABA/sub B/ sites, the affinity for (-), (+) and (+/-)baclofen, GABA and ..beta..-phenyl GABA increased 2 - 6 fold in the presence of 2.5 mM MnCl/sub 2/, in comparison with that in HEPES-buffered Krebs solution (containing 2.5 mM CaCl/sub 2/ and 1.2 mM MgSO/sub 4/), whereas that for muscimol was decreased to one-fifth. Thus, the affinity of GABA/sub B/ sites for its ligands is probably regulated by divalent cations, through common sites of action.

  3. Changes in BQCA Allosteric Modulation of [(3)H]NMS Binding to Human Cortex within Schizophrenia and by Divalent Cations. (United States)

    Dean, Brian; Hopper, Shaun; Conn, P Jeffrey; Scarr, Elizabeth


    Stimulation of the cortical muscarinic M1 receptor (CHRM1) is proposed as a treatment for schizophrenia, a hypothesis testable using CHRM1 allosteric modulators. Allosteric modulators have been shown to change the activity of CHRMs using cloned human CHRMs and CHRM knockout mice but not human CNS, a prerequisite for them working in humans. Here we show in vitro that BQCA, a positive allosteric CHRM1 modulator, brings about the expected change in affinity of the CHRM1 orthosteric site for acetylcholine in human cortex. Moreover, this effect of BQCA is reduced in the cortex of a subset of subjects with schizophrenia, separated into a discrete population because of a profound loss of cortical [(3)H]pirenzepine binding. Surprisingly, there was no change in [(3)H]NMS binding to the cortex from this subset or those with schizophrenia but without a marked loss of cortical CHRM1. Hence, we explored the nature of [(3)H]pirenzepine and [(3)H]NMS binding to human cortex and showed total [(3)H]pirenzepine and [(3)H]NMS binding was reduced by Zn(2+), acetylcholine displacement of [(3)H]NMS binding was enhanced by Mg(2+) and Zn(2+), acetylcholine displacement of [(3)H]pirenzepine was reduced by Mg(2+) and enhanced by Zn(2+), whereas BQCA effects on [(3)H]NMS, but not [(3)H]pirenzepine, binding was enhanced by Mg(2+) and Zn(2+). These data suggest the orthosteric and allosteric sites on CHRMs respond differently to divalent cations and the effects of allosteric modulation of the cortical CHRM1 is reduced in a subset of people with schizophrenia, a finding that may have ramifications for the use of CHRM1 allosteric modulators in the treatment of schizophrenia.

  4. Solid-State Properties of One-Dimensional Metals Based on bis(oxalato)platinate Anions with Divalent Cations

    DEFF Research Database (Denmark)

    Braude, A.; Carneiro, K.; Jacobsen, Claus Schelde


    The crystal structures, superstructures, dc conductivity, optical properties, and thermopower of six linear-chain conductors of the type M0.8[Pt(C2O4)2]⋅(M=Ni,Co,Zn,Fe,Mg,Mn), where M is a divalent metal (M=Ni,Co,Zn,Fe,Mg,Mn), have been studied. At high temperatures they form a common orthorhombi...

  5. The Geometry and Structural Properties of the 4,8,12-Trioxa-4,8,12,12c-tetrahydrodibenzo[cd,mn]pyrene System in the Cationic State. Structures of a Planar Organic Cation with Various Monovalent- and Divalent Anions

    DEFF Research Database (Denmark)

    Krebs, Frederik C; Laursen, Bo W.; Johannsen, Ib


    The geometry of the 4,8,12-trioxa-4,8,12,12c- tetrahydrodibenzo[cd,mn]pyrene system in the cationic state was established by X-ray structural resolution of the salts formed between the cationand various anions. The geometry was found to be planar for the 4,8,12-trioxa-4,8,12,12c- tetrahydrodibenzo...... [cd,mn]pyrenylium and 2,6,10-tri (tert-butyl)-4,8,12-trioxa-4,8,12,12c-tetrahydrodibenzo[cd,mn]pyre nylium cations with the monovalentanions I-, BF4-, PF6- AsF6-, HNO3. NO3- and CF3SO3-, and the divalent anions S2O62- and Mo6Cl142-. The salts were found to crystallize in distinct space groups...... following a characteristic pattern. Mixed cation-anion stacking resulted in space groups with high symmetry: Pbca in three cases and R (3) over bar c in one; a temperature study of the latter was made at ten different temperatures. The formation of dimers of anions and cations resulted in lower...

  6. Divalent cations and redox conditions regulate the molecular structure and function of visinin-like protein-1.

    Directory of Open Access Journals (Sweden)

    Conan K Wang

    Full Text Available The NCS protein Visinin-like Protein 1 (VILIP-1 transduces calcium signals in the brain and serves as an effector of the non-retinal receptor guanylyl cyclases (GCs GC-A and GC-B, and nicotinic acetyl choline receptors (nAchR. Analysis of the quaternary structure of VILIP-1 in solution reveals the existence of monomeric and dimeric species, the relative contents of which are affected but not exclusively regulated by divalent metal ions and Redox conditions. Using small-angle X-ray scattering, we have investigated the low resolution structure of the calcium-bound VILIP-1 dimer under reducing conditions. Scattering profiles for samples with high monomeric and dimeric contents have been obtained. The dimerization interface involves residues from EF-hand regions EF3 and EF4.Using monolayer adsorption experiments, we show that myristoylated and unmyristoylated VILIP-1 can bind lipid membranes. The presence of calcium only marginally improves binding of the protein to the monolayer, suggesting that charged residues at the protein surface may play a role in the binding process.In the presence of calcium, VILIP-1 undergoes a conformational re-arrangement, exposing previously hidden surfaces for interaction with protein partners. We hypothesise a working model where dimeric VILIP-1 interacts with the membrane where it binds membrane-bound receptors in a calcium-dependent manner.

  7. Reversible CO binding enables tunable CO/H₂ and CO/N₂ separations in metal-organic frameworks with exposed divalent metal cations. (United States)

    Bloch, Eric D; Hudson, Matthew R; Mason, Jarad A; Chavan, Sachin; Crocellà, Valentina; Howe, Joshua D; Lee, Kyuho; Dzubak, Allison L; Queen, Wendy L; Zadrozny, Joseph M; Geier, Stephen J; Lin, Li-Chiang; Gagliardi, Laura; Smit, Berend; Neaton, Jeffrey B; Bordiga, Silvia; Brown, Craig M; Long, Jeffrey R


    Six metal-organic frameworks of the M2(dobdc) (M = Mg, Mn, Fe, Co, Ni, Zn; dobdc(4-) = 2,5-dioxido-1,4-benzenedicarboxylate) structure type are demonstrated to bind carbon monoxide reversibly and at high capacity. Infrared spectra indicate that, upon coordination of CO to the divalent metal cations lining the pores within these frameworks, the C-O stretching frequency is blue-shifted, consistent with nonclassical metal-CO interactions. Structure determinations reveal M-CO distances ranging from 2.09(2) Å for M = Ni to 2.49(1) Å for M = Zn and M-C-O angles ranging from 161.2(7)° for M = Mg to 176.9(6)° for M = Fe. Electronic structure calculations employing density functional theory (DFT) resulted in good agreement with the trends apparent in the infrared spectra and crystal structures. These results represent the first crystallographically characterized magnesium and zinc carbonyl compounds and the first high-spin manganese(II), iron(II), cobalt(II), and nickel(II) carbonyl species. Adsorption isotherms indicate reversible adsorption, with capacities for the Fe, Co, and Ni frameworks approaching one CO per metal cation site at 1 bar, corresponding to loadings as high as 6.0 mmol/g and 157 cm(3)/cm(3). The six frameworks display (negative) isosteric heats of CO adsorption ranging from 52.7 to 27.2 kJ/mol along the series Ni > Co > Fe > Mg > Mn > Zn, following the Irving-Williams stability order. The reversible CO binding suggests that these frameworks may be of utility for the separation of CO from various industrial gas mixtures, including CO/H2 and CO/N2. Selectivities determined from gas adsorption isotherm data using ideal adsorbed solution theory (IAST) over a range of gas compositions at 1 bar and 298 K indicate that all six M2(dobdc) frameworks could potentially be used as solid adsorbents to replace current cryogenic distillation technologies, with the choice of M dictating adsorbent regeneration energy and the level of purity of the resulting gases.

  8. Effects of Divalent Cations and Disulfide Bond Reducing Agents on Specific Binding of Growth Hormone to Liver Membrane Receptors from Snakehead Fish (Ophiocephalus argus, Cantor). (United States)

    Sun, Xun; Zhang, Xin-Na; Zhu, Shang-Quan; Zheng, Han-Qi


    Divalent cations, Ca(2 ), Mg(2 ) and Mn(2 ) enhance the binding of bream growth hormone (brGH) to snakehead fish liver membrane, and their optimum concentration was found to be 8 12 mmol/L, at which Ca(2 ), Mg(2 ) and Mn(2 ) could increase, respectively, the specific binding to 230%, 180%, and 200%, compared with the binding in the absence of ions. The Eadie-Scatchard plot was used for the dynamic analysis of the Ca(2 ) binding site. A low affinity Ca(2 ) binding site was found in the GH-receptor complex with K(m)=0.384 mmol/L, and the affinity constant (K(a)) was increased from 1.045x10(9) L.mol(-1) to 1.295x10(9) L.mol(-1) by the addition of 10 mmol/L CaCl(2). The effects of disulfide bond reducing agents, DTT and ME, on (125)I-brGH binding to growth hormone receptor (GHR) on snakehead fish liver memebrane were also analyzed. The addition of 0.1 20 mmol/L DTT or 0.01% 1% ME to the radioreceptor assay system caused a significant dose dependent increase in the specific binding for (125)I-brGH. In the presence of 0.8 mmol/L DTT or 0.08% ME, the specific binding of (125)I-brGH was increased from 10.2% to 15.5% and 13.2% respectively, and the affinity constant was also increased from 1.265x10(9) L.mol(-1) to 2.185x10(9) L.mol(-1) and 1.625x10(9) L.mol(-1), respectively but no changes in the binding capacity were observed. Further studies showed that the effects of reductants on the specific binding of brGH were due in part to the ligand itself and in part to GHR. In addition, it was observed that one of the three disulfide bonds of brGH could be reduced by 0.8 mmol/L DTT.

  9. Theoretical calculation of the NMR spin-spin coupling constants and the NMR shifts allow distinguishability between the specific direct and the water-mediated binding of a divalent metal cation to guanine. (United States)

    Sychrovský, Vladimír; Sponer, Jirí; Hobza, Pavel


    The calculated intermolecular and intramolecular indirect NMR spin-spin coupling constants and NMR shifts were used for the discrimination between the inner-shell and the outer-shell binding motif of hydrated divalent cations Mg(2+) or Zn(2+) with a guanine base. The intermolecular coupling constants (1)J(X,O6) and (1)J(X,N7) (X = Mg(2+), Zn(2+)) can be unambiguously assigned to the specific inner-shell binding motif of the hydrated cation either with oxygen O6 or with nitrogen N7 of guanine. The calculated coupling constants (1)J(Mg,O6) and (1)J(Zn,O6) were 6.2 and -17.5 Hz, respectively, for the inner-shell complex of cation directly interacting with oxygen O6 of guanine. For the inner-shell coordination of the cation at nitrogen N7, the calculated coupling constants (1)J(Mg,N7) and (1)J(Zn,N7) were 5.6 and -36.5 Hz, respectively. When the binding of the cation is water-mediated, the coupling constant is zero. To obtain reliable shifts in NMR parameters, hydrated guanine was utilized as the reference state. The calculated change of NMR spin-spin coupling constants due to the hydration and coordination of the cation with guanine is caused mainly by the variation of Fermi-contact coupling contribution while the variation of diamagnetic spin-orbit, paramagnetic spin-orbit, and spin-dipolar coupling contributions is small. The change of s-character of guanine sigma bonding, sigma antibonding, and lone pair orbitals upon the hydration and cation coordination (calculated using the Natural Bond Orbital analysis) correlates with the variation of the Fermi-contact term. The calculated NMR shifts delta(N7) of -15.3 and -12.2 ppm upon the coordination of Mg(2+) and Zn(2+) ion are similar to the NMR shift of 19.6 ppm toward the high field measured by Tanaka for N7 of guanine upon the coordination of the Cd(2+) cation (Tanaka, Y.; Kojima, C.; Morita, E. H.; Kasai. Y.; Yamasaki, K.; Ono, A.; Kainosho, M.; Taira, K. J. Am. Chem. Soc. 2002, 124, 4595-4601). The present data

  10. Energy-resolved collision-induced dissociation studies of 1,10-phenanthroline complexes of the late first-row divalent transition metal cations: determination of the third sequential binding energies. (United States)

    Nose, Holliness; Chen, Yu; Rodgers, M T


    The third sequential binding energies of the late first-row divalent transition metal cations to 1,10-phenanthroline (Phen) are determined by energy-resolved collision-induced dissociation (CID) techniques using a guided ion beam tandem mass spectrometer. Five late first-row transition metal cations in their +2 oxidation states are examined including: Fe(2+), Co(2+), Ni(2+), Cu(2+), and Zn(2+). The kinetic energy dependent CID cross sections for loss of an intact Phen ligand from the M(2+)(Phen)3 complexes are modeled to obtain 0 and 298 K bond dissociation energies (BDEs) after accounting for the effects of the internal energy of the complexes, multiple ion-neutral collisions, and unimolecular decay rates. Electronic structure theory calculations at the B3LYP, BHandHLYP, and M06 levels of theory are employed to determine the structures and theoretical estimates for the first, second, and third sequential BDEs of the M(2+)(Phen)x complexes. B3LYP was found to deliver results that are most consistent with the measured values. Periodic trends in the binding of these complexes are examined and compared to the analogous complexes to the late first-row monovalent transition metal cations, Co(+), Ni(+), Cu(+), and Zn(+), previously investigated.

  11. Highly Emissive Divalent-Ion-Doped Colloidal CsPb1–xMxBr3 Perovskite Nanocrystals through Cation Exchange (United States)


    Colloidal CsPbX3 (X = Br, Cl, and I) perovskite nanocrystals (NCs) have emerged as promising phosphors and solar cell materials due to their remarkable optoelectronic properties. These properties can be tailored by not only controlling the size and shape of the NCs but also postsynthetic composition tuning through topotactic anion exchange. In contrast, property control by cation exchange is still underdeveloped for colloidal CsPbX3 NCs. Here, we present a method that allows partial cation exchange in colloidal CsPbBr3 NCs, whereby Pb2+ is exchanged for several isovalent cations, resulting in doped CsPb1–xMxBr3 NCs (M= Sn2+, Cd2+, and Zn2+; 0 50%), sharp absorption features, and narrow emission of the parent CsPbBr3 NCs. The blue-shift in the optical spectra is attributed to the lattice contraction that accompanies the Pb2+ for M2+ cation exchange and is observed to scale linearly with the lattice contraction. This work opens up new possibilities to engineer the properties of halide perovskite NCs, which to date are demonstrated to be the only known system where cation and anion exchange reactions can be sequentially combined while preserving the original NC shape, resulting in compositionally diverse perovskite NCs. PMID:28260380

  12. Respiratory adaptations in carp blood. Influences of hypoxia, red cell organic phosphates, divalent cations and CO2 on hemoglobin-oxygen affinity

    DEFF Research Database (Denmark)

    Weber, Roy E.; Lykkeboe, G.


    This study concerns the adaptation of oxygen transporting function of carp blood to environment hypoxia, tracing the roles played by erythrocytic cofactors, inorganic cations, carbon dioxide and hemoglobin multiplicity. Carp acclimated to hypoxia ( 30 mmHg) display striking increases in blood...

  13. Characterization of the Escherichia coli prsA1-encoded mutant phosphoribosylpyrophosphate synthetase identifies a divalent cation-nucleotide binding site

    DEFF Research Database (Denmark)

    Bower, Stanley G.; Harlow, Kenneth W.; Switzer, Robert L.


    : DLHAXQIQGFFDI/VPI/VD. There was little alteration in the Km for ribose 5-phosphate. The Km for ATP of the mutant enzyme was increased 27-fold when Mg2+ was the activating cation but only 5-fold when Mn2+ was used. Maximal velocities of the wild type and mutant enzymes were the same. The mutant enzyme has a 6...

  14. Electromotive force and impedance studies of cellulose acetate membranes: Evidence for two binding sites for divalent cations and for an alveolar structure of the skin layer

    DEFF Research Database (Denmark)

    Smith Sørensen, T.; Jensen, J.B.; Malmgren-Hansen, B.


    -degrees-C (in some few cases 35-degrees-C). The ions considered were the cations H+, Li+, Na+, K+, Mg++, Ca++, Ba++ and the anions Cl- and F- (Cl- was always present). The >>fixed>variable...... may be found by the latter method. Earlier results are recapitulated, especially the evidence for an alveolar structure found by interpreting the membrane capacitance increase with salt concentration - found by means of impedance measurements - in the light of a combined Trukhan-Bruggemann theory...... of days. The dissociation of Ba++ was followed at 25-degrees-C and at 35-degrees-C and at different external concentrations of NaCl. The slow relaxation seems connected with the Coulomb interaction between the COO- groups and the Ba++ ions, whereas the fast relaxation is probably reflecting dissociation...

  15. X-ray crystal structure of divalent metal-activated ß-xyloisdase, RS223BX (United States)

    We report the first X-ray structure of a glycoside hydrolase family 43 ß-xylosidase, RS223BX, which is strongly activated by the addition of divalent metal cations. The 2.69 Å structure reveals that the Ca2+ cation is located at the back of the active site pocket. The Ca2+ coordinates to H274 to sta...

  16. Stabilization of polymer gels against divalent ion-induced syneresis

    Energy Technology Data Exchange (ETDEWEB)

    Albonico, Paola; Lockhart, Thomas P. [Eniricerche SpA, San Donato, Milan (Italy)


    Polymer solutions and polymer gels are unstable to extended ageing in divalent cation-rich brines at elevated temperature. This paper shows that low-molecular-weight compounds that complex strongly with Ca{sup 2+} and Mg{sup 2+} are capable of neutralizing their destabilizing influence on polymer solubility and of inhibiting the syneresis of crosslinked acrylamide polymer gels in hard brines. The solubility of the inhibitor-divalent ion complexes formed in hard brine at elevated temperature have also been examined. The results obtained offer the possibility to extend significantly the upper temperature limit for the use of polyacrylamides and acrylamide copolymers in brines in both polymer flooding and polymer gel treatments

  17. Divalent counterion-induced condensation of triple-strand DNA. (United States)

    Qiu, Xiangyun; Parsegian, V Adrian; Rau, Donald C


    Understanding and manipulation of the forces assembling DNA/RNA helices have broad implications for biology, medicine, and physics. One subject of significance is the attractive force between dsDNA mediated by polycations of valence ≥ 3. Despite extensive studies, the physical origin of the "like-charge attraction" remains unsettled among competing theories. Here we show that triple-strand DNA (tsDNA), a more highly charged helix than dsDNA, is precipitated by alkaline-earth divalent cations that are unable to condense dsDNA. We further show that our observation is general by examining several cations (Mg(2+), Ba(2+), and Ca(2+)) and two distinct tsDNA constructs. Cation-condensed tsDNA forms ordered hexagonal arrays that redissolve upon adding monovalent salts. Forces between tsDNA helices, measured by osmotic stress, follow the form of hydration forces observed with condensed dsDNA. Probing a well-defined system of point-like cations and tsDNAs with more evenly spaced helical charges, the counterintuitive observation that the more highly charged tsDNA (vs. dsDNA) is condensed by cations of lower valence provides new insights into theories of polyelectrolytes and the biological and pathological roles of tsDNA. Cations and tsDNAs also hold promise as a model system for future studies of DNA-DNA interactions and electrostatic interactions in general.

  18. Divalent Beta’ Aluminas: High Conductivity Solid Electrolytes for Divalent Cations. (United States)


    Seith, Z. Phys., 57, 869 (1929) 45. G. Schwab and G. Eulitz, Z. physik. Chem., 55, 179 (1967) 6. N. Toropov, C.R. Acad. Sci. URSS , I, 147 (1935) 7. K...G. Gottfried, and J. West, Z.Kristallogr., 77, 255 (1931) 10. N.A. Toropov and N.M. Stukalova, C.R. (Dok.) Acad. Sci. URSS , 24, 459 (1939) 11. N.A...Toropov and M.M. Stukalova, C.R. (Dok.) Acad. Sci. URSS , 9 27, 974 (1940) 12. D.B. McWhan, P.D. Dernier. C. Vettier, A.S. Cooper, and’J.P. Remeika, Phys

  19. Trends for isolated amino acids and dipeptides: Conformation, divalent ion binding, and remarkable similarity of binding to calcium and lead

    CERN Document Server

    Ropo, Matti; Baldauf, Carsten


    We derive structural and binding energy trends for twenty amino acids, their dipeptides, and their interactions with the divalent cations Ca$^{2+}$, Ba$^{2+}$, Sr$^{2+}$, Cd$^{2+}$, Pb$^{2+}$, and Hg$^{2+}$. The underlying data set consists of 45,892 first-principles predicted conformers with relative energies up to about 4 eV (about 400kJ/mol). We show that only very few distinct backbone structures of isolated amino acids and their dipeptides emerge as lowest-energy conformers. The isolated amino acids predominantly adopt structures that involve an acidic proton shared between the carboxy and amino function. Dipeptides adopt one of two intramolecular-hydrogen bonded conformations C$_5$ or equatorial C$_7$. Upon complexation with a divalent cation, the accessible conformational space shrinks and intramolecular hydrogen bonding is prevented due to strong electrostatic interaction of backbone and side chain functional groups with cations. Clear correlations emerge from the binding energies of the six divalent ...

  20. Extração da lectina da folha de mandioca (Manihot esculenta Crantz e o efeito de cátions divalentes na atividade hemaglutinante Extraction of the lectin of cassava leaves (Manihot esculenta Crantz and the effect of divalent cations on the hemagglutinating activity

    Directory of Open Access Journals (Sweden)

    Maria Cristina Silva


    Full Text Available Lectinas são proteínas ligantes de carboidratos, capazes de aglutinar eritrócitos, podendo exercer ação antinutricional. O isolamento destas proteínas tóxicas é interessante tanto pela sua ação antinutricional, como pela sua aplicação em biotecnologia. Algumas lectinas necessitam da presença de íons divalentes para exercer sua atividade hemaglutinante (AH. O objetivo neste trabalho foi estudar diferentes métodos de extração da lectina da farinha de folhas de mandioca (FFM e avaliar o efeito dos íons Ca2+ e Mn2+ para sua AH. Foram feitos testes de extração das proteínas utilizando dois extratores, água e solução salina (0,15 mol.L-1, pH 7,4, em quatro tempos de extração, 15, 60, 120 e 180 minutos. Para avaliar o efeito dos íons Ca2+ e Mn2+ na AH da lectina da FFM, o extrato proteico foi dialisado contra EDTA e a AH determinada. O efeito desses cátions na aglutinação de hemácias também foi avaliado isoladamente. O método de extração proteica usando água destilada como extrator por 15 minutos é o mais adequado. Não houve perda da AH na ausência dos íons. Os cátions Ca2+ (5 mmol.L-1, Mn2+ (1, 3 e 5 mmol.L-1 e a mistura de ambos nas mesmas concentrações provocam aglutinação de hemácias, na ausência de lectina.Lectins are carbohydrates binding proteins, capable of agglutinating erythrocytes, which can act as anti-nutritional factors. The isolation of these toxic proteins is interesting both for its anti- nutritional action and for its application in biotechnology. Some lectins need the presence of divalent ions to express hemagglutinating activity (AH. The objective of this work was to investigate different methods of extracting lectins from cassava leaf flour (CLF and to evaluate the effect of the ions Ca2+ and Mn2+ on the AH. Protein extraction tests were performed utilizing two extractors, water and saline solution (0.15 mol.L-1, NaCl pH 7.4, under four extraction times, 15, 60, 120, and 180 minutes

  1. Energy levels scheme simulation of divalent cobalt doped bismuth germanate

    Energy Technology Data Exchange (ETDEWEB)

    Andreici, Emiliana-Laura, E-mail: [Department of Physics, West University of Timisoara, Bd. V. Parvan 4,300223 Timisoara (Romania); Petkova, Petya [Shumen University “Konstantin Preslavsky”, 115 Universitetska street, 9712 Shumen (Bulgaria); Avram, Nicolae M. [Department of Physics, West University of Timisoara, Bd. V. Parvan 4,300223 Timisoara (Romania); Academy of Romanian Scientists, Independentei 54, 050094-Bucharest (Romania)


    The aim of this paper is to simulate the energy levels scheme for Bismuth Germanate (BGO) doped with divalent cobalt, in order to give a reliable explanation for spectral experimental data. In the semiempirical crystal field theory we first modeled the Crystal Field Parameters (CFPs) of BGO:Cr{sup 2+} system, in the frame of Exchange Charge Model (ECM), with actually site symmetry of the impurity ions after doping. The values of CFPs depend on the geometry of doped host matrix and by parameter G of ECM. First, we optimized the geometry of undoped BGO host matrix and afterwards, that of doped BGO with divalent cobalt. The charges effect of ligands and covalence bonding between cobalt cations and oxygen anions, in the cluster approach, also were taken into account. With the obtained values of the CFPs we simulate the energy levels scheme of cobalt ions, by diagonalizing the matrix of the doped crystal Hamiltonian. Obviously, energy levels and estimated Racah parameters B and C were compared with the experimental spectroscopic data and discussed. Comparison of obtained results with experimental data shows quite satisfactory, which justify the model and simulation schemes used for the title system.

  2. Heavy metal cations permeate the TRPV6 epithelial cation channel. (United States)

    Kovacs, Gergely; Danko, Tamas; Bergeron, Marc J; Balazs, Bernadett; Suzuki, Yoshiro; Zsembery, Akos; Hediger, Matthias A


    TRPV6 belongs to the vanilloid family of the transient receptor potential channel (TRP) superfamily. This calcium-selective channel is highly expressed in the duodenum and the placenta, being responsible for calcium absorption in the body and fetus. Previous observations have suggested that TRPV6 is not only permeable to calcium but also to other divalent cations in epithelial tissues. In this study, we tested whether TRPV6 is indeed also permeable to cations such as zinc and cadmium. We found that the basal intracellular calcium concentration was higher in HEK293 cells transfected with hTRPV6 than in non-transfected cells, and that this difference almost disappeared in nominally calcium-free solution. Live cell imaging experiments with Fura-2 and NewPort Green DCF showed that overexpression of human TRPV6 increased the permeability for Ca(2+), Ba(2+), Sr(2+), Mn(2+), Zn(2+), Cd(2+), and interestingly also for La(3+) and Gd(3+). These results were confirmed using the patch clamp technique. (45)Ca uptake experiments showed that cadmium, lanthanum and gadolinium were also highly efficient inhibitors of TRPV6-mediated calcium influx at higher micromolar concentrations. Our results suggest that TRPV6 is not only involved in calcium transport but also in the transport of other divalent cations, including heavy metal ions, which may have toxicological implications.

  3. Hydration of cations: a key to understanding of specific cation effects on aggregation behaviors of PEO-PPO-PEO triblock copolymers. (United States)

    Lutter, Jacob C; Wu, Tsung-yu; Zhang, Yanjie


    This work reports results from the interactions of a series of monovalent and divalent cations with a triblock copolymer, poly(ethylene oxide)-b-poly(propylene oxide)-b-poly(ethylene oxide) (PEO-PPO-PEO). Phase transition temperatures of the polymer in the presence of chloride salts with six monovalent and eight divalent cations were measured using an automated melting point apparatus. The polymer undergoes a two-step phase transition, consisting of micellization of the polymer followed by aggregation of the micelles, in the presence of all the salts studied herein. The results suggest that hydration of cations plays a key role in determining the interactions between the cations and the polymer. The modulation of the phase transition temperature of the polymer by cations can be explained as a balance between three interactions: direct binding of cations to the oxygen in the polymer chains, cations sharing one water molecule with the polymer in their hydration layer, and cations interacting with the polymer via two water molecules. Monovalent cations Na(+), K(+), Rb(+), and Cs(+) do not bind to the polymer, while Li(+) and NH4(+) and all the divalent cations investigated including Mg(2+), Ca(2+), Sr(2+), Ba(2+), Co(2+), Ni(2+), Cu(2+), and Cd(2+) bind to the polymer. The effects of the cations correlate well with their hydration thermodynamic properties. Mechanisms for cation-polymer interactions are discussed.

  4. Competitive Effects of 2+ and 3+ Cations on DNA Compaction

    CERN Document Server

    Tongu, C; Yoshikawa, Y; Zinchenko, A A; Chen, N; Yoshikawa, K


    By using single-DNA observation with fluorescence microscopy, we observed the effects of divalent and trivalent cations on the higher-order structure of giant DNA (T4 DNA with 166 kbp). It was found that divalent cations, such as Mg(2+) and Ca(2+), inhibit DNA compaction induced by a trivalent cation, spermidine (SPD(3+)). On the other hand, in the absence of SPD(3+), divalent cations cause the shrinkage of DNA. These experimental observations are inconsistent with the well-established Debye-Huckel scheme regarding the shielding effect of counter ions, which is given as the additivity of contributions of cations with different valences. We interpreted the competition between 2+ and 3+ cations in terms of the change in the translational entropy of the counter ions before and after the folding transition of DNA. For the compaction with SPD(3+), we considered the increase in translational entropy due to the ion-exchange of the intrinsic monovalent cations condensing on a highly-charged polyelectrolyte, double-st...

  5. Trends for isolated amino acids and dipeptides: Conformation, divalent ion binding, and remarkable similarity of binding to calcium and lead (United States)

    Ropo, M.; Blum, V.; Baldauf, C.


    We derive structural and binding energy trends for twenty amino acids, their dipeptides, and their interactions with the divalent cations Ca2+, Ba2+, Sr2+, Cd2+, Pb2+, and Hg2+. The underlying data set consists of more than 45,000 first-principles predicted conformers with relative energies up to ~4 eV (~400 kJ/mol). We show that only very few distinct backbone structures of isolated amino acids and their dipeptides emerge as lowest-energy conformers. The isolated amino acids predominantly adopt structures that involve an acidic proton shared between the carboxy and amino function. Dipeptides adopt one of two intramolecular-hydrogen bonded conformations C5 or . Upon complexation with a divalent cation, the accessible conformational space shrinks and intramolecular hydrogen bonding is prevented due to strong electrostatic interaction of backbone and side chain functional groups with cations. Clear correlations emerge from the binding energies of the six divalent ions with amino acids and dipeptides. Cd2+ and Hg2+ show the largest binding energies–a potential correlation with their known high acute toxicities. Ca2+ and Pb2+ reveal almost identical binding energies across the entire series of amino acids and dipeptides. This observation validates past indications that ion-mimicry of calcium and lead should play an important role in a toxicological context.

  6. Effects of composition and structure of alginates on adsorption of divalent metals (United States)

    Zheng, Nai-Yu; Zhang, Yan-Xia; Fan, Xiao; Han, Li-Jun


    Results of a series of experiments (on the adsorption of divalent metal ions by dried alginic acid, Na and Ca alginates of different composition and block structure) conducted in this systematic study of the effects of the composition and structure of alginates on the static adsorption equilibrium of divalent metal ions indicate that the properties of alginate adsorption to divalent metal ions are highly different, depending not only on the cations used, but also on the form and structure of the alginates. There is close correlation between the adsorption properties and the structure of the alginates. The selectivity coefficient of Na alginate for Cd-Sr ion exchange tends to increase with the increase of the M/G ratio in alginate, whereas the adsorption capacity of Ca alginate for Cu2+ ion decrease with the increase of the G-block or the average length of the G-block(bar N_G ) and the total adsorption capacity of alginic acid is found to vary in the same order as the F MM(diad frequency) in alginate in the mixed solution of Sr2+, Ba2+ and Cd2+.

  7. Molecular dynamics simulations of the structure and single-particle dynamics of mixtures of divalent salts and ionic liquids

    Energy Technology Data Exchange (ETDEWEB)

    Gómez-González, Víctor; Docampo-Álvarez, Borja; Gallego, Luis J.; Varela, Luis M., E-mail: [Grupo de Nanomateriais e Materia Branda, Departamento de Física da Materia Condensada, Universidade de Santiago de Compostela, Campus Vida s/n, E-15782 Santiago de Compostela (Spain); Cabeza, Oscar [Facultade de Ciencias, Universidade da Coruña, Campus A Zapateira s/n, E-15008 A Coruña (Spain); Fedorov, Maxim [Department of Physics, Scottish University Physics Alliance (SUPA), University of Strathclyde, John Anderson Bldg., 107 Rottenrow East, Glasgow G4 0NG (United Kingdom); Lynden-Bell, Ruth M. [Department of Chemistry, University of Cambridge, Lensfield Road, Cambridge CB2 1EW (United Kingdom)


    We report a molecular dynamics study of the structure and single-particle dynamics of mixtures of a protic (ethylammonium nitrate) and an aprotic (1-butyl-3-methylimidazolium hexaflurophosphate [BMIM][PF{sub 6}]) room-temperature ionic liquids doped with magnesium and calcium salts with a common anion at 298.15 K and 1 atm. The solvation of these divalent cations in dense ionic environments is analyzed by means of apparent molar volumes of the mixtures, radial distribution functions, and coordination numbers. For the protic mixtures, the effect of salt concentration on the network of hydrogen bonds is also considered. Moreover, single-particle dynamics of the salt cations is studied by means of their velocity autocorrelation functions and vibrational densities of states, explicitly analyzing the influence of salt concentration, and cation charge and mass on these magnitudes. The effect of the valency of the salt cation on these properties is considered comparing the results with those for the corresponding mixtures with lithium salts. We found that the main structural and dynamic features of the local solvation of divalent cations in ionic liquids are similar to those of monovalent salts, with cations being localized in the polar nanoregions of the bulk mixture coordinated in monodentate and bidentate coordination modes by the [NO{sub 3}]{sup −} and [PF{sub 6}]{sup −} anions. However, stronger electrostatic correlations of these polar nanoregions than in mixtures with salts with monovalent cations are found. The vibrational modes of the ionic liquid (IL) are seen to be scarcely affected by the addition of the salt, and the effect of mass and charge on the vibrational densities of states of the dissolved cations is reported. Cation mass is seen to exert a deeper influence than charge on the low-frequency vibrational spectra, giving a red shift of the vibrational modes and a virtual suppression of the higher energy vibrational modes for the heavier Ca{sup 2

  8. Cooperation of divalent ions and thiamin diphosphate in regulation of the function of pig heart pyruvate dehydrogenase complex. (United States)

    Czerniecki, J; Czygier, M


    The role of Mg2+, Ca2+, and Mn2+ in regulation of purified pig heart pyruvate dehydrogenase complex (PDC) containing endogenous thiamin diphosphate (TDP) was studied. It was found that the effects of the cations depended on the presence of exogenous TDP. In the absence of added TDP, the divalent cations led to a shortening of a lag phase of the PDC reaction and a strong reduction of the Km value for pyruvate. The relative efficiency of the three types of ions are presented as follows: Mn2+>Ca2+>Mg2+. The other sources claim that in the presence of exogenous TDP, which alone strongly increased the affinity of PDC for pyruvate, any significant additional effects of the cations were not observed. However, Mg2+, Ca2+, and Mn2+ decreased the Km value for CoA in both cases, the absence and presence of exogenous TDP, in approximately a similar extent (about twofold). The affinity of PDC for NAD+ seems to be not sensitive to the presence of the divalent cations. The data obtained suggest that Mg2+, Ca2+, and Mn2+ can cooperate with TDP as positive regulatory effectors of pig heart PDC on the level of pyruvate dehydrogenase and lipoamide acetyltransferase components of the complex.

  9. Instability of some divalent rare earth ions and photochromic effect (United States)

    Egranov, A. V.; Sizova, T. Yu.; Shendrik, R. Yu.; Smirnova, N. A.


    It was shown that the divalent rare earth ions (La, Ce, Gd, Tb, Lu, and Y) in cubic sites in alkaline earth fluorides are unstable with respect to electron autodetachment since its d1(eg) ground state is located in the conduction band which is consistent with the general tendency of these ions in various compounds. The localization of doubly degenerate d1(eg) level in the conduction band creates a configuration instability around the divalent rare earth ion that leading to the formation of anion vacancy in the nearest neighborhood, as was reported in the previous paper [A. Egranov, T. Sizova, Configurational instability at the excited impurity ions in alkaline earth fluorites, J. Phys. Chem. Solids 74 (2013) 530-534]. Thus, the formation of the stable divalent ions as La, Ce, Gd, Tb, Lu, and Y (PC+ centers) in CaF2 and SrF2 crystals during x-ray irradiation occurs via the formation of charged anion vacancies near divalent ions (Re2+va), which lower the ground state of the divalent ion relative to the conductivity band. Photochromic effect occurs under thermally or optically stimulated electron transition from the divalent rare earth ion to the neighboring anion vacancy and reverse under ultraviolet light irradiation. It is shown that the optical absorption of the PC+ centers due to d → d and d → f transitions of the divalent rare-earth ion.

  10. Modeling the sorption kinetics of divalent metal ions onto mineral adsorbent using integral method. (United States)

    Singhal, Nidhi; Prasad, Murari; Gupta, Neelmani; Kumar, Vineet


    A mathematical model has been developed that could predict kinetic parameters for the adsorption of divalent cations (lead, copper and zinc) onto low-grade rock phosphate using experimental data. The experiments were conducted with the initial concentrations of metal ions ranging from 10 to 100 mg/L. The mathematical model is based on application of Freundlich isotherm to mass transfer across the film surrounding the adsorbent. A code in C programming is used to numerically integrate the model equation, and to obtain the best simulated values of Freundlich constants K, N, order of reaction n, and film transfer coefficient, alpha. It is observed that the adsorption of metal ions on rock phosphate is more sensitive to N,n, and alpha in comparison to K, and lead is adsorbed more favorably than copper and zinc.

  11. Effect of divalent ions in acrosome reaction induced by glycosamineglycans in porcine spermatozoa. (United States)

    Delgado, N M; Carranco, A; Merchant, H; Reyes, R


    Magnesium, calcium, and zinc at the concentration of 10 microM are capable of inducing a "true" acrosome reaction in the pig spermatozoa judged by the criteria of the fusion of the acrosome and the plasmatic membrane at the anterior region or the sperm nucleus. The optimal percent of acrosome reaction reached by any of the ions tested as a whole was 50%. When glycosamineglycan sulfate (GAGs) plus 10 microM of Mg++, Ca++, or Zn++ was added, they reach to 70-80% of acrosome reaction. At the electrom microscope, thin sections taken from pig spermatozoa treated with ions, GAGs, or ion + GAGs under optimal experimental conditions revealed the same pattern of acrosomal reaction. Results suggest the important role that divalent cations play in general in the induction of the acrosome reaction and question the so-called essential role of calcium ions.

  12. Instability of some divalent rare earth ions and photochromic effect


    Egranov, A. V.; Sizova, T. Yu.; Shendrik, R. Yu.; Smirnova, N. A.


    It was shown that the divalent rare earth ions (La, Ce, Gd, Tb, Lu, and Y) in cubic sites in alkaline earth fluorides are unstable with respect to electron autodetachment since its d1(eg) ground state is located in the conduction band which is consistent with the general tendency of these ions in various compounds. The localization of doubly degenerate d1(eg) level in the conduction band creates a configuration instability around the divalent rare earth ion that leading to the formation of an...

  13. Salt and divalent cations affect the flexible nature of the natural beaded chromatin structure

    DEFF Research Database (Denmark)

    Christiansen, Gunna; Griffith, J


    A natural chromatin containing simian virus 40 (SV40) DNA and histone has been used to examine changes in chromatin structure caused by various physical and chemical treatments. We find that histone H1 depleted chromatin is more compact in solutions of 0.15M NaCl or 2 mM MgCl2 than in 0.01 M Na......Cl or 0.6M NaCL, and is compact in 0.01 M NaCl solutions if histone H 1 is present. Even high concentrations of urea did not alter the fundamental beaded structure, consisting of 110A beads of 200 base pair content, each joined by thin DNA bridges of 50 base pairs. The physical bead observed by EM...... therefore contains more DNA than the 140 base pair "core particle". The natural variation in the bridge length is consistent with the broad bands observed after nuclease digestion of chromatin. Chromatin prepared for EM without fixation containing long 20A to 30A fibers possibly complexed with protein....

  14. Langmuir and Langmuir-Blodgett films of a maleic anhydride derivative: effect of subphase divalent cations. (United States)

    Martín-García, B; Velázquez, M Mercedes; Pérez-Hernández, J A; Hernández-Toro, J


    We report the study of the equilibrium and dynamic properties of Langmuir monolayers of poly(styrene-co-maleic anhydride) partial 2-buthoxyethyl ester cumene terminated polymer and the effect of the Mg(NO(3))(2) addition in the water subphase on the film properties. Results show that the polymer monolayer becomes more expanded when the electrolyte concentration in the subphase increases. Dense polymer films aggregate at the interface. The aggregates are transferred onto silicon wafers using the Langmuir-Blodgett methodology and the morphology is observed by AFM. The structure of aggregates depends on the subphase composition of the Langmuir film transferred onto the silicon wafer.

  15. Metal Cation Binding to Gas-Phase Pentaalanine: Divalent Ions Restructure the Complex

    NARCIS (Netherlands)

    Dunbar, R. C.; Steill, J. D.; Polfer, N. C.; Oomens, J.


    Ion-neutral complexes of pentaalalanine with several singly- and doubly charged metal ions are examined using conformation analysis by infrared multiple photon dissociation (IRMPD) spectroscopy and density functional theory (DFT) computations. The infrared spectroscopy in the 1500-1800 cm(-1) region

  16. Spectroscopic study of conformational changes in subdomain 1 of G-actin: influence of divalent cations. (United States)

    Nyitrai, M; Hild, G; Belágyi, J; Somogyi, B


    Temperature dependence of the fluorescence intensity and anisotropy decay of N-(iodoacetyl)-N'-(5-sulfo-1-naphthyl)ethylenediamine attached to Cys374 of actin monomer was investigated to characterize conformational differences between Ca- and Mg-G-actin. The fluorescence lifetime is longer in Mg-G-actin than that in Ca-G-actin in the temperature range of 5-34 degrees C. The width of the lifetime distribution is smaller by 30% in Mg-saturated actin monomer at 5 degrees C, and the difference becomes negligible above 30 degrees C. The semiangle of the cone within which the fluorophore can rotate is larger in Ca-G-actin at all temperatures. Electron paramagnetic resonance measurements on maleimide spin-labeled (on Cys374) monomer actin gave evidence that exchange of Ca2+ for Mg2+ induced a rapid decrease in the mobility of the label immediately after the addition of Mg2+. These results suggest that the C-terminal region of the monomer becomes more rigid as a result of the replacement of Ca2+ by Mg2+. The change can be related to the difference between the polymerization abilities of the two forms of G-actin.

  17. Expression and divalent cation binding properties of the novel chemotactic inflammatory protein psoriasin

    DEFF Research Database (Denmark)

    Vorum, H; Madsen, Peder; Rasmussen, H H;


    in Escherichia coli as a fusion protein containing a hexa His tag and a factor Xa cleavage site in the NH2-terminus. The protein was purified by affinity chromatography on Ni(2+)-nitrilotriacetic acid agarose, digested with factor Xa, further purified by ion-exchange chromatography and characterized by two...


    Directory of Open Access Journals (Sweden)

    Elmi Roseida Cen-Cen


    Full Text Available Los agaves son plantas que pertenecen a un género constituido por numerosas especies, adaptadas para crecer en muy diversos hábitats, algunos con condiciones ambientales extremas. Distintas especies de agave crecen sobre distintos tipos de suelos, algunas en suelos con muy bajo contenido de nutrientes minerales y otras en suelos salinos o en suelos contaminados con iones metálicos. La relación planta-suelo ha sido escasamente estudiada en este género por lo que se desconoce, entre otras cuestiones, cuál es la capacidad de los agaves para absorber, transportar y almacenar nutrientes minerales, cuáles son los mecanismos celulares y bioquímicos que utilizan, o si poseen especial sensibilidad o tolerancia a los iones metálicos. Este estudio reporta el efecto de diversas concentraciones de sulfato de cadmio, cobalto, cobre, zinc o de manganeso sobre plántulas deAgave tequilana, bajo condiciones controladas de laboratorio; la concentración mínima de esos iones metálicos requerida para inducir un efecto tóxico visualmente detectable en tiempos cortos (ocho días; describimos los efectos tóxicos que estos metales generan sobre las plántulas de agave; y reportamos la cantidad de Cu2+, Cd2+ y Co2+ que se acumula en las hojas de plántulas de agave tratadas con altas concentraciones (milimolares de esos metales. Nuestros resultados muestran que, en experimentos de toxicidad aguda y bajo las condiciones aquí establecidas, elA. tequilanaposee una notable tolerancia a altas concentraciones de los distintos metales iónicos probados, incluyendo tanto micronutrientes como metales tóxicos, así como la capacidad de transportar en altas cantidades estos metales a tejido aéreo.

  19. Iron oxides, divalent cations, silica, and the early earth phosphorus crisis

    DEFF Research Database (Denmark)

    Jones, C.; Nomosatryo, S.; Crowe, S.A.;


    and silica content of BIFs, we estimate that seawater in the Archean and early Proterozoic Eons likely contained 0.04–0.13 µM phosphorus, on average. These phosphorus limiting conditions could have favored primary production through photoferrotrophy at the expense of oxygenic photosynthesis until upwelling......As a nutrient required for growth, phosphorus regulates the activity of life in the oceans. Iron oxides sorb phosphorus from seawater, and through the Archean and early Proterozoic Eons, massive quantities of iron oxides precipitated from the oceans, producing a record of seawater chemistry...

  20. Modeling the Interaction between Integrin-Binding Peptide (RGD) and Rutile Surface: The Effect of Cation Mediation on Asp Adsorption

    Energy Technology Data Exchange (ETDEWEB)

    Wu, Chunya [Harbin Institute of Technology; Skelton, Adam [Vanderbilt University; Chen, Mingjun [Harbin Institute of Technology; Vlcek, Lukas [ORNL; Cummings, Peter T [ORNL


    The binding of a negatively charged residue, aspartic acid (Asp) in tripeptide arginine-glycine-aspartic acid, onto a negatively charged hydroxylated rutile (110) surface in aqueous solution, containing divalent (Mg{sup 2+}, Ca{sup 2+}, or Sr{sup 2+}) or monovalent (Na{sup +}, K{sup +}, or Rb{sup +}) cations, was studied by molecular dynamics (MD) simulations. The results indicate that ionic radii and charges will significantly affect the hydration, adsorption geometry, and distance of cations from the rutile surface, thereby regulating the Asp/rutile binding mode. The adsorption strength of monovalent cations on the rutile surface in the order Na{sup +} > K{sup +} > Rb{sup +} shows a 'reverse' lyotropic trend, while the divalent cations on the same surface exhibit a 'regular' lyotropic behavior with decreasing crystallographic radii (the adsorption strength of divalent cations: Sr{sup 2+} > Ca{sup 2+} > Mg{sup 2+}). The Asp side chain in NaCl, KCl, and RbCl solutions remains stably H-bonded to the surface hydroxyls and the inner-sphere adsorbed compensating monovalent cations act as a bridge between the COO{sup -} group and the rutile, helping to 'trap' the negatively charged Asp side chain on the negatively charged surface. In contrast, the mediating divalent cations actively participate in linking the COO{sup -} group to the rutile surface; thus the Asp side chain can remain stably on the rutile (110) surface, even if it is not involved in any hydrogen bonds with the surface hydroxyls. Inner- and outer-sphere geometries are all possible mediation modes for divalent cations in bridging the peptide to the rutile surface.

  1. Uptake of photosensitizers by bacteria is influenced by the presence of cations (United States)

    Kishen, A.; George, S.


    This investigation studies the influence of cations on photosensitizer uptake by Enterococcus faecalis (gram positive) and Actinobacillus actinomycetemcomitans (gram negative). Methods- The uptake of Methylene blue (MB) and Indocyanine Green (ICG), by bacteria were studied under the influence of divalent cations (CaCl II & MgCl II) and EDTA. Further, E. faecalis cells subjected to trypsinisation and calcium channel blocker (verapamil) were also analysed for MB and ICG uptake inorder to understand the mechanism of photosensitizer uptake. Results- Uptake of ICG was enhanced in the presence of divalent cations in E. faecalis and A. actinomycetemcomitans. Treating cells with EDTA had no significant effect on the photosensitizer uptake, although the highest concentration tested showed an enhancement of uptake. In contrast to ICG, MB showed a decreased uptake by bacterial cells on subjecting them to divalent cations and EDTA. Calcium channel blocker had no significant inhibitory effect on photosensitizers uptake. However, trypsin treatment resulted in significant reduction of ICG uptake. The result suggested that ICG uptake by bacteria is mediated through specific transporter protein while MB is associated with the outer surface structures of bacterial cells.

  2. Cyclopiazonic Acid Is Complexed to a Divalent Metal Ion When Bound to the Sarcoplasmic Reticulum Ca2+-ATPase

    DEFF Research Database (Denmark)

    Laursen, Mette; Bublitz, Maike; Moncoq, Karine;


    Abstract: We have determined the structure of the sarco(endo) plasmic reticulum Ca2+-ATPase (SERCA) in an E2.P-i-like form stabilized as a complex with MgF42-, an ATP analog, adenosine 5'-(beta,gamma-methylene) triphosphate (AMPPCP), and cyclopiazonic acid (CPA). The structure determined at 2.......5 angstrom resolution leads to a significantly revised model of CPA binding when compared with earlier reports. It shows that a divalent metal ion is required for CPA binding through coordination of the tetramic acid moiety at a characteristic kink of the M1 helix found in all P-type ATPase structures, which...... is expected to be part of the cytoplasmic cation access pathway. Our model is consistent with the biochemical data on CPA function and provides new measures in structure-based drug design targeting Ca2+-ATPases, e. g. from pathogens. We also present an extended structural basis of ATP modulation pinpointing...

  3. Characterization and application of tourmaline and beryl from Brazilian pegmatite in adsorption process with divalent metals

    Institute of Scientific and Technical Information of China (English)

    Denis L.Guerra; Silze P.Oliveira; Ricardo A.R.Silva; Victor Leidens; Adriano C.Batista


    In this study,the original tourmaline and beryl mineral samples have been collected from a Brazilian pegmatite.The objective of this study was to examine the adsorption behavior of Brazilian ciclosilicate sampies,towards divalent metals (Pb2+,Mn2+,and Zn2+) in ethanol solution has been studies by a batch technique.The ciclosilicate samples were characterized by elemental analysis,Fourier transform infrared spectroscopy,helium picnometry,mercury porosity,and nitrogen adsorption-desorption.The Langmuir expression for adsorption isotherm was applied in order to determine the adsorption capacity to form a monolayer and the constant related to the adsorption intensity.In aqueous solution there was a significant adsorption increase with the temperature and pronounced synergistic effects were observed.The maximum number of moles adsorbed was determined to be 12.48 and 11.49 mmol/g for systems Pb2+/beryl and Pb2+/tourmaline,respectively.The energetic effects caused by metal cations adsorption were determined through calorimetric titrations.Thermodynamics indicated the existence of favorable conditions for such Pb2+-,Mn2+-,and Zn2+-OH interactions.

  4. CE-ESI-MS separation of divalent organic and inorganic anions using a tricationic complexing reagent. (United States)

    Gerardi, Anthony R; Lin, Xiuli; Breitbach, Zachary S; Armstrong, Daniel W; Colyer, Christa L


    A tricationic ion-pairing reagent, 1,3,5-1-butyl-3-methyl-1H-imidazol-3-ium-2,4,6-trimethylbenzene, was used to form complexes with doubly charged anions for their subsequent analysis by capillary electrophoresis-electrospray ionization-mass spectrometry (CE-ESI-MS) in the positive-ion mode. This methodology offers the advantages of greater versatility and sensitivity relative to direct detection of the anions in negative-ion mode, and it can be realized by a number of possible complexation strategies, including pre-column, on-column, and post-column modes. Three model anions, sulfate [SO₄²⁻], thiosulfate [TSFA, S₂O₃²⁻], and benzenedisulfonate [BZDS, C₆H₄(SO₃)₂²⁻], were amenable to complexation with the tricationic reagent, yielding singly charged cations with greater mass-to-charge (m/z) ratios than the native analytes. By utilizing optimized parameters obtained through previous work with dicationic reagents and singly charged anions, including the CE separation buffer composition and pH, the concentration of the dicationic reagent, the mode of complexation, the nebulizing gas pressure, and the sheath liquid composition, it was possible to develop a robust CE-ESI-MS method appropriate for the analysis of divalent anions in a mixture.

  5. Characterization of the interactions between the active site of a protein tyrosine kinase and a divalent metal activator

    Directory of Open Access Journals (Sweden)

    Ayrapetov Marina K


    Full Text Available Abstract Background Protein tyrosine kinases are important enzymes for cell signalling and key targets for anticancer drug discovery. The catalytic mechanisms of protein tyrosine kinase-catalysed phosphorylation are not fully understood. Protein tyrosine kinase Csk requires two Mg2+ cations for activity: one (M1 binds to ATP, and the other (M2 acts as an essential activator. Results Experiments in this communication characterize the interaction between M2 and Csk. Csk activity is sensitive to pH in the range of 6 to 7. Kinetic characterization indicates that the sensitivity is not due to altered substrate binding, but caused by the sensitivity of M2 binding to pH. Several residues in the active site with potential of binding M2 are mutated and the effect on metal activation studied. An active mutant of Asn319 is generated, and this mutation does not alter the metal binding characteristics. Mutations of Glu236 or Asp332 abolish the kinase activity, precluding a positive or negative conclusion on their role in M2 coordination. Finally, the ability of divalent metal cations to activate Csk correlates to a combination of ionic radius and the coordination number. Conclusion These studies demonstrate that M2 binding to Csk is sensitive to pH, which is mainly responsible for Csk activity change in the acidic arm of the pH response curve. They also demonstrate critical differences in the metal activator coordination sphere in protein tyrosine kinase Csk and a protein Ser/Thr kinase, the cAMP-dependent protein kinase. They shed light on the physical interactions between a protein tyrosine kinase and a divalent metal activator.

  6. Enhanced Retention of Chelating Reagents in Octadecylsilyl Silica Phase by Interaction with Residual Silanol Groups in Solid Phase Extraction of Divalent Metal Ions. (United States)

    Ohmuro, Satoshi; Fujii, Kan; Yasui, Takashi; Takada, Kazutake; Yuchi, Akio; Kokusen, Hisao


    Solid-phase extraction (SPE) of divalent metal ions with a lipophilic and potentially divalent hexadentate chelating reagent (H2L), with which octadecylsilyl silica (ODS), was impregnated with was studied to gain more insight into and develop the potential of this methodology. This is the first time to demonstrate that this reagent as well as other common nitrogen-containing reagents were retained both by adsorption due to hydrogen bonding between nitrogen atoms of the reagent and residual silanol groups in the ODS phase and by simple distribution into the hydrophobic space. An appreciably large amount of this reagent could be retained by the adsorption mechanism even with a relatively thin loading solution. The divalent metal ions of Mn(2+), Co(2+) and Zn(2+) were extracted as 1:1 neutral complexes ([ML]), while Ni(2+) and Cu(2+) as ion-pairs of 1:1 cationic complex ([MHL](+)) with anion in SPE with H2L. The extractability and selectivity were substantially the same as that in liquid-liquid extraction.

  7. Evaluation of the effect of divalent metal transporter 1 gene polymorphism on blood iron, lead and cadmium levels

    Energy Technology Data Exchange (ETDEWEB)

    Kayaaltı, Zeliha, E-mail:; Akyüzlü, Dilek Kaya; Söylemezoğlu, Tülin


    Divalent metal transporter 1 (DMT1), a member of the proton-coupled metal ion transporter family, mediates transport of ferrous iron from the lumen of the intestine into the enterocyte and export of iron from endocytic vesicles. It has an affinity not only for iron but also for other divalent cations including manganese, cobalt, nickel, cadmium, lead, copper, and zinc. DMT1 is encoded by the SLC11a2 gene that is located on chromosome 12q13 in humans and express four major mammalian isoforms (1A/+IRE, 1A/-IRE, 2/+IRE and 2/-IRE). Mutations or polymorphisms of DMT1 gene may have an impact on human health by disturbing metal trafficking. To study the possible association of DMT1 gene with the blood levels of some divalent cations such as iron, lead and cadmium, a single nucleotide polymorphism (SNP) (IVS4+44C/A) in DMT1 gene was investigated in 486 unrelated and healthy individuals in a Turkish population by method of polymerase chain reaction–restriction fragment length polymorphism (PCR–RFLP). The genotype frequencies were found as 49.8% homozygote typical (CC), 38.3% heterozygote (CA) and 11.9% homozygote atypical (AA). Metal levels were analyzed by dual atomic absorption spectrometer system and the average levels of iron, lead and cadmium in the blood samples were 446.01±81.87 ppm, 35.59±17.72 ppb and 1.25±0.87 ppb, respectively. Individuals with the CC genotype had higher blood iron, lead and cadmium levels than those with AA and CA genotypes. Highly statistically significant associations were detected between IVS4+44 C/A polymorphism in the DMT1 gene and iron and lead levels (p=0.001 and p=0.036, respectively), but no association was found with cadmium level (p=0.344). This study suggested that DMT1 IVS4+44 C/A polymorphism is associated with inter-individual variations in blood iron, lead and cadmium levels. - Highlights: • DMT1 IVS4+44 C/A polymorphism is associated with inter-individual variations in blood iron, cadmium and lead levels.

  8. Adsorption of Metsulfuron and Bensulfuron on a Cationic Surfactant-Modified Paddy Soil

    Institute of Scientific and Technical Information of China (English)

    LIAO Min; XIE Xiao-Mei


    Adsorption isotherms of metsulfuron and bensulfuron on a hexadecyltrimethylammonium (HDTMA) bromide-modified paddy soil under different ionic strengths, with divalent cation Cu2+, or having different pH were studied to describe their adsorptive behavior, and to try to explain the adsorption process of a sulfonylurea compound with a carbamoylsulfamoyl group in the modified soil environment. All the adsorption isotherms fitted the Freundlich equation well, and the HDTMA treatment of paddy soil dramatically enhanced adsorption capacity of metsulfuron or bensulfuron. Also, an increase of ionic strength and the addition of divalent heavy metal cation Cu2+ on the HDTMA-modified paddy soil increased the adsorption of metsulfuron or bensulfuron. Additionally, for metsulfuron and bensulfuron in the aqueous phase, adsorption capacity of the HDTMA-modified paddy soil gradually increased with decreasing pH.

  9. Effect of initial ion positions on the interactions of monovalent and divalent ions with a DNA duplex as revealed with atomistic molecular dynamics simulations. (United States)

    Robbins, Timothy J; Wang, Yongmei


    Monovalent (Na(+)) and divalent (Mg(2+)) ion distributions around the Dickerson-Drew dodecamer were studied by atomistic molecular dynamics (MD) simulations with AMBER molecular modeling software. Different initial placements of ions were tried and the resulting effects on the ion distributions around DNA were investigated. For monovalent ions, results were found to be nearly independent of initial cation coordinates. However, Mg(2+) ions demonstrated a strong initial coordinate dependent behavior. While some divalent ions initially placed near the DNA formed essentially permanent direct coordination complexes with electronegative DNA atoms, Mg(2+) ions initially placed further away from the duplex formed a full, nonexchanging, octahedral first solvation shell. These fully solvated cations were still capable of binding with DNA with events lasting up to 20 ns, and in comparison were bound much longer than Na(+) ions. Force field parameters were also investigated with modest and little differences arising from ion (ions94 and ions08) and nucleic acid description (ff99, ff99bsc0, and ff10), respectively. Based on known Mg(2+) ion solvation structure, we conclude that in most cases Mg(2+) ions retain their first solvation shell, making only solvent-mediated contacts with DNA duplex. The proper way to simulate Mg(2+) ions around DNA duplex, therefore, should begin with ions placed in the bulk water.

  10. Paddle-wheel versus percolation mechanism for cation transport in some sulphate phases

    DEFF Research Database (Denmark)

    Andersen, N.H.; Bandaranyake, P.W.S.K.; Careem, M.A.;


    Lithium sulphate and a few other compounds have high temperature phases which are both solid electrolytes and plastic crystals (rotor phases). Three types of experiments are here considered in order to test the validity of a "paddle-wheel mechanism" that has been proposed for cation conductivity...... and interdiffusion, all studied mono- and divalent cations are very mobile in the rotor phases, which lack the pronounced correlation with ionic radii that is characteristic for diffusion in other classes of solid electrolytes. The quoted studies are to be considered as strong evidence against a percolation model...

  11. Periodic model of LTA framework containing various non-tetrahedral cations. (United States)

    Koleżyński, A; Mikuła, A; Król, M


    A simplified periodic model of Linde Type A zeolite (LTA) structure with various selected mono- and di-valent extra-framework cations was formulated. Ab initio calculations (geometry optimization and vibrational spectra calculations) using the proposed model were carried out by means of Crystal09 program. The resulting structures and simulated spectra were analyzed in detail and compared with the experimental ones. The presented results show that in most cases the proposed model agrees well with experimental results. Individual bands were assigned to respective normal modes of vibration and the changes resulting from the selective substitution of extra framework cations were described and explained.

  12. Periodic model of LTA framework containing various non-tetrahedral cations (United States)

    Koleżyński, A.; Mikuła, A.; Król, M.


    A simplified periodic model of Linde Type A zeolite (LTA) structure with various selected mono- and di-valent extra-framework cations was formulated. Ab initio calculations (geometry optimization and vibrational spectra calculations) using the proposed model were carried out by means of Crystal09 program. The resulting structures and simulated spectra were analyzed in detail and compared with the experimental ones. The presented results show that in most cases the proposed model agrees well with experimental results. Individual bands were assigned to respective normal modes of vibration and the changes resulting from the selective substitution of extra framework cations were described and explained.

  13. Sorption of the organic cation metoprolol on silica gel from its aqueous solution considering the competition of inorganic cations. (United States)

    Kutzner, Susann; Schaffer, Mario; Börnick, Hilmar; Licha, Tobias; Worch, Eckhard


    Systematic batch experiments with the organic monovalent cation metoprolol as sorbate and the synthetic material silica gel as sorbent were conducted with the aim of characterizing the sorption of organic cations onto charged surfaces. Sorption isotherms for metoprolol (>99% protonated in the tested pH of around 6) in competition with mono- and divalent inorganic cations (Na(+), NH4(+), Ca(2+), and Mg(2+)) were determined in order to assess their influence on cation exchange processes and to identify the role of further sorptive interactions. The obtained sorption isotherms could be described well by an exponential function (Freundlich isotherm model) with consistent exponents (about 0.8). In general, a decreasing sorption of metoprolol with increasing concentrations in inorganic cations was observed. Competing ions of the same valence showed similar effects. A significant sorption affinity of metoprolol with ion type dependent Freundlich coefficients KF,0.77 between 234.42 and 426.58 (L/kg)(0.77) could still be observed even at very high concentrations of competing inorganic cations. Additional column experiments confirm this behavior, which suggests the existence of further relevant interactions beside cation exchange. In subsequent batch experiments, the influence of mixtures with more than one competing ion and the effect of a reduced negative surface charge at a pH below the point of zero charge (pHPZC ≈ 2.5) were also investigated. Finally, the study demonstrates that cation exchange is the most relevant but not the sole mechanism for the sorption of metoprolol on silica gel.

  14. Titration kinetics of Asp-85 in bacteriorhodopsin: exclusion of the retinal pocket as the color-controlling cation binding site. (United States)

    Fu, X; Bressler, S; Ottolenghi, M; Eliash, T; Friedman, N; Sheves, M


    The spectrum (the purple blue transition) and function of the light-driven proton pump bacteriorhodopsin are determined by the state of protonation of the Asp-85 residue located in the vicinity of the retinal chromophore. The titration of Asp-85 is controlled by the binding/unbinding of one or two divalent metal cations (Ca2+ or Mg2+). The location of such metal binding site(s) is approached by studying the kinetics of the cation-induced titration of Asp-85 using metal ions and large molecular cations, such as quaternary ammonium ions, R4N+ (R = Et, Pr, a divalent 'bolaform ion' [Et3N+-(CH2)4-N+Et3] and the 1:3 molecular complex formed between Fe2+ and 1,10-phenanthroline (OP). The basic multi-component kinetic features of the titration, extending from 10(-2) to 10(4) s, are unaffected by the charge and size of the cation. This indicates that cation binding to bR triggers the blue --> purple titration in a fast step, which is not rate-determining. In view of the size of the cations involved, these observations indicate that the cation binding site is in an exposed location on, or close to, the membrane surface. This excludes previous models, which placed the color-controlling Ca2+ ion in the retinal binding pocket.

  15. Effect of divalent anions on photodegradation kinetics and pathways of riboflavin in aqueous solution. (United States)

    Ahmad, Iqbal; Ahmed, Sofia; Sheraz, Muhammad Ali; Vaid, Faiyaz H M; Ansari, Izhar A


    The present investigation is based on a study of the effect of buffer and non-buffer divalent anions (phosphate, sulphate, tartrate, succinate, malonate) on the kinetics, product distribution and photodegradation pathways of riboflavin (RF) at pH 6.0-8.0. RF solutions (5x10(-5)M) were photodegraded in the presence of divalent anions (0.2-1.0M) using a visible light source and the photoproducts, cyclodehydroriboflavin (CDRF), formylmethylflavin (FMF), lumichrome (LC) and lumiflavin (LF) were assayed by a specific multicomponent spectrophotometric method. RF degradation in the presence of divalent anions follows parallel first-order kinetics to give CDRF and LC as the final products through photoaddition and photoreduction reactions, respectively. The divalent anion-catalysed CDRF formation is affected in the order: phosphate>sulphate>tartrate>succinate>malonate, showing maximum activity of the anions around pH 7. The divalent anions cause deviation of the photoreduction pathway in favour of the photoaddition pathway to form CDRF. The first- and second-order rate constants for the reactions involved in the photodegradation of RF have been determined and the rate-pH profiles and pathway relationships discussed. The catalytic activity of the divalent anions appears to be a function of the relative strength and chemical reactivity of the RF-divalent anion complex acting as a mediator in the photoaddition reaction.

  16. Reductive spectrophotometry of divalent tin sensitization on soda lime glass (United States)

    Bejugam, Vinith; Wei, Xingfei; Roper, D. Keith


    Rapid and facile evaluation of tin (II) sensitization could lead to improved understanding of metal deposition in electroless (EL) plating. This report used a balanced redox reaction between 3,3‧,5,5‧-tetramethylbenzidine dihydrochloride (TMB-HCL) and N-bromosuccinimide (NBS) to evaluate effects of sensitization conditions (i.e., sensitization time, analyte concentration, aqueous immersion, and acid content) on the accumulated mass of surface-associated divalent tin ion. The accumulated mass of tin (II) increased as the sensitization time increased up to 30 s in proportion to aqueous tin (II) chloride concentrations between 2.6 and 26 mM at a trifluoroacetic acid (TFA) content of 68 mM. The average mass peaked at 7.3 nanomoles (nmol) per cm2 after a 5 s aqueous immersion post-sensitization, and then decreased with increasing aqueous immersion post-sensitization. The total average tin (II) + tin (IV) accumulated on soda lime glass measured by inductively coupled plasma optical emission spectrometry (ICP-OES) was 17% higher at 30 s sensitization, suggesting a fraction of the tin (II) present may have oxidized to tin (IV). These results indicated that in situ spectrophotometric evaluation of tin (II) could support development of EL plating for electronics, catalysis, and solar cells.

  17. Hall transport of divalent metal ion modified DNA lattices

    Energy Technology Data Exchange (ETDEWEB)

    Dugasani, Sreekantha Reddy; Lee, Keun Woo; Yoo, Sanghyun; Gnapareddy, Bramaramba; Bashar, Saima; Park, Sung Ha, E-mail: [Department of Physics and Sungkyunkwan Advanced Institute of Nanotechnology (SAINT), Sungkyunkwan University, Suwon 440-746 (Korea, Republic of); Kim, Si Joon; Jung, Joohye; Jung, Tae Soo; Kim, Hyun Jae, E-mail: [School of Electrical and Electronic Engineering, Yonsei University, Seoul 120-749 (Korea, Republic of)


    We investigate the Hall transport characteristics of double-crossover divalent metal ion (Cu{sup 2+}, Ni{sup 2+}, Zn{sup 2+}, and Co{sup 2+})-modified DNA (M-DNA) lattices grown on silica via substrate-assisted growth. The electronic characteristics of the M-DNA lattices are investigated by varying the concentration of the metal ions and then conducting Hall measurements, including resistivity, Hall mobility, carrier concentration, and magneto resistance. The tendency of the resistivity and Hall mobility was to initially decrease as the ion concentration increased, until reaching the saturation concentration (C{sub s}) of each metal ion, and then to increase as the ion concentration increased further. On the other hand, the carrier concentration revealed the opposite tendency as the resistivity and Hall mobility. The specific binding (≤C{sub s}) and the nonspecific aggregates (>C{sub s}) of the ions into the DNA lattices were significantly affected by the Hall characteristics. The numerical ranges of the Hall parameters revealed that the M-DNA lattices with metal ions had semiconductor-like characteristics. Consequently, the distinct characteristics of the electrical transport through M-DNA lattices will provide useful information on the practical use of such structures in physical devices and chemical sensors.

  18. Divalent Cu, Cd, and Pb Biosorption in Mixed Solvents

    Directory of Open Access Journals (Sweden)

    M. H. Al-Qunaibit


    Full Text Available Dead dried Chlorella vulgaris was studied in terms of its performance in binding divalent copper, cadmium, and lead ions from their aqueous or 50% v/v methanol, ethanol, and acetone solutions. The percentage uptake of cadmium ions exhibited a general decrease with decrease in dielectric constant values, while that of copper and lead ions showed a general decrease with increase in donor numbers. Uptake percentage becomes less sensitive to solvent properties the larger the atomic radius of the biosorbed ion, and uptake of copper was the most affected. FT-IR analyses revealed stability of the biomass in mixed solvents and a shift in vibrations of amide(I and (II, carboxylate, glucose ring, and metal oxygen upon metal binding in all media. ΔνCOO values (59–69 cm−1 confirmed bidentate metal coordination to carboxylate ligands. The value of νasCOO increased slightly upon Cu, Cd, and Pb biosorption from aqueous solutions indicating lowering of symmetry, while a general decrease was noticed in mixed solvents pointing to the opposite. M–O stretching frequencies increased unexpectedly with increase in atomic mass as a result of solvent effect on the nature of binding sites. Lowering polarity of the solvent permits variations in metal-alga bonds strengths; the smaller the metal ion, the more affected.

  19. Cu Vacancies Boost Cation Exchange Reactions in Copper Selenide Nanocrystals. (United States)

    Lesnyak, Vladimir; Brescia, Rosaria; Messina, Gabriele C; Manna, Liberato


    We have investigated cation exchange reactions in copper selenide nanocrystals using two different divalent ions as guest cations (Zn(2+) and Cd(2+)) and comparing the reactivity of close to stoichiometric (that is, Cu2Se) nanocrystals with that of nonstoichiometric (Cu(2-x)Se) nanocrystals, to gain insights into the mechanism of cation exchange at the nanoscale. We have found that the presence of a large density of copper vacancies significantly accelerated the exchange process at room temperature and corroborated vacancy diffusion as one of the main drivers in these reactions. Partially exchanged samples exhibited Janus-like heterostructures made of immiscible domains sharing epitaxial interfaces. No alloy or core-shell structures were observed. The role of phosphines, like tri-n-octylphosphine, in these reactions, is multifaceted: besides acting as selective solvating ligands for Cu(+) ions exiting the nanoparticles during exchange, they also enable anion diffusion, by extracting an appreciable amount of selenium to the solution phase, which may further promote the exchange process. In reactions run at a higher temperature (150 °C), copper vacancies were quickly eliminated from the nanocrystals and major differences in Cu stoichiometries, as well as in reactivities, between the initial Cu2Se and Cu(2-x)Se samples were rapidly smoothed out. These experiments indicate that cation exchange, under the specific conditions of this work, is more efficient at room temperature than at higher temperature.

  20. Adsorption of 2,4-dinitrophenol and 2,4-dichlorohpenol on Cationic Surfactant Modified Red Soil

    Institute of Scientific and Technical Information of China (English)



    Adsorption isotherms of 2,4-dinitrophenol and 2,4-dichlorophenol on hexadecyltrimethylammonium (HDTMA) bromide modified red soil under different ionic strength, divalent cation Cu+2 or different pH conditions were studied. All the adsorption isotherms were well fitted to the Freundlich equation. The adsorption capacities of 2,4-dinitrophenol or 2,4-dichlorophenol were dramatically enhanced by HDTMA treatment of red soil. The increase of ionic strength and the addition of divalent heavy metal cation Cu+2 significantly enhanced the adsorption of 2,4-dinitrophenol or 2,4-dichlorophenol on the HDTMA-modified red soil. Adsorption capacities of HDTMA-modified red soil for 2,4-dinitrophenol and 2,4-dichlorophenol gradually increased with decreasing pH in the aqueous phase.

  1. A study on the relation between sex steroids and divalent cations in women of menopausal and reproductive age group

    Directory of Open Access Journals (Sweden)

    Seena Sukumaran


    Conclusions: A low level of estrogen supplementation may be more acceptable, because of its negative correlation with serum magnesium, and thus helping to maintain an adequate protective level of Mg2+ circulating in the blood. Therefore, it is necessary for maintaining optimum Ca2+/Mg2+ ratio, to increase the efficacy of HRT and decrease the complications of high calcium intake in women after menopause. [Int J Res Med Sci 2016; 4(1.000: 89-94

  2. Comparative Study of Cyanobacterial and E. coli RNA Polymerases: Misincorporation, Abortive Transcription, and Dependence on Divalent Cations

    Directory of Open Access Journals (Sweden)

    Masahiko Imashimizu


    Full Text Available If Mg2+ ion is replaced by Mn2+ ion, RNA polymerase tends to misincorporate noncognate nucleotide, which is thought to be one of the reasons for the toxicity of Mn2+ ion. Therefore, most cells have Mn2+ ion at low intracellular concentrations, but cyanobacteria need the ion at a millimolar concentration to maintain photosynthetic machinery. To analyse the mechanism for resistance against the abundant Mn2+ ion, we compared the properties of cyanobacterial and E. coli RNA polymerases. The cyanobacterial enzyme showed a lower level of abortive transcription and less misincorporation than the E. coli enzyme. Moreover, the cyanobacterial enzyme showed a slower rate of the whole elongation by an order of magnitude, paused more frequently, and cleaved its transcript faster in the absence of NTPs. In conclusion, cyanobacterial RNA polymerase maintains the fidelity of transcription against Mn2+ ion by deliberate incorporation of a nucleotide at the cost of the elongation rate. The cyanobacterial and the E. coli enzymes showed different sensitivities to Mg2+ ion, and the physiological role of the difference is also discussed.

  3. Impacts of some divalent cations on periplasmic nitrate reductase and dehydrogenase enzymes of Escherichia, Pseudomonas and Acinetobacter species

    Directory of Open Access Journals (Sweden)

    Christian E. Nwanyanwu


    Full Text Available The impacts of Hg2+, Cd2+ and Zn2+ on the activities of periplasmic nitrate reductase (NAP and dehydrogenase (DHA enzymes of three organisms isolated from soil and sediment-water interface were analysed in liquid culture studies. NAP and DHA activities were estimated from nitrite and triphenyl formazan were produced respectively after 4h incubation at 28 ± 2oC. Hg2+ completely inhibited NAP activity in Escherichia and Pseudomonas spp at all the concentrations (0.2 – 1mM while progressive inhibitions of NAP activity were observed in Escherichia and Pseudomonas spp with increasing concentrations of Zn2+ and Cd2+. Both metals were stimulatory to NAP of Acinetobacter sp at 0.2 – 1mM. Apart from stimulation of DHA activity by Zn2+ (0.2 – 1mM in Escherichia sp, Cd2+ (0.4 -1.0mM in Acinetobacter sp and (1.0mM in Pseudomonas sp, all the metals progressively inhibited DHA activities in the three organisms. In Escherichia sp, the activities of the two enzymes were negatively correlated on exposure to Zn2+ (r = -0.91 and positively correlated (r = >0.90 on exposure to Cd2+ and Hg2+. Based on IC50 values of the metals for the DHA and NAP enzymes, the most resistant of the three organisms were Escherichia sp and Acinetobacter sp respectively. Quantitatively, NAP with its lower IC50 values than DHA was a more sensitive toxicity measure for Hg2+ in all the organisms. The sensitivity of microbial metabolic enzymes to the toxic effects of metals varies with the type of enzyme, metal and the microorganism involved.

  4. Aggregation and Stability of Reduced Graphene Oxide: Complex Roles of Divalent Cations, pH, and Natural Organic Matter (United States)

    The aggregation and stability of graphene oxide (GO) and three successively reduced GO (rGO) nanomaterials were investigated. Reduced GO species were partially reduced GO (rGO-1h), intermediately reduced GO (rGO-2h), and fully reduced GO (rGO-5h). Specifically, influence of pH, i...

  5. Study of cation distribution of spinel zinc nano-ferrite by X-ray (United States)

    Najafi Birgani, Azadeh; Niyaifar, Mohammad; Hasanpour, Ahmad


    A set of zinc ferrite samples with ZnFe2O4 chemical composition were synthesized in 400, 500, and 1100 °C using conventional solid state synthesis method. The X-ray diffraction pattern of all the three samples was studied at room temperature. This diffraction pattern confirmed the existence of a single-phase cubic spinel structure with lattice parameters of 8.451, 8.448, and 8.437 Å, respectively. Oxygen position and cation distribution of the samples between the tetrahedral site, A and the octahedral site, B were examined using R-Factor method. The results showed that cation distribution of zinc ferrite samples changes from a normal spinel mode into a mixed spinel mode with the decrease of particle size. Moreover, the ratio of zinc divalent cations migrating from the tetrahedral site to the octahedral site was calculated.

  6. Driving force for the hydration of the swelling clays: case of montmorillonites saturated with alkaline-earth cations. (United States)

    Salles, Fabrice; Douillard, Jean-Marc; Bildstein, Olivier; Gaudin, Cedric; Prelot, Benedicte; Zajac, Jerzy; Van Damme, Henri


    Important structural modifications occur in swelling clays upon water adsorption. The multi-scale evolution of the swelling clay structure is usually evidenced by various experimental techniques. However, the driving force behind such phenomena is still not thoroughly understood. It appears strongly dependent on the nature of the interlayer cation. In the case of montmorillonites saturated with alkaline cations, it was inferred that the compensating cation or the layer surface could control the hydration process and thus the opening of the interlayer space, depending on the nature of the interlayer cation. In the present study, emphasis is put on the impact of divalent alkaline-earth cations compensating the layer charge in montmorillonites. Since no experimental technique offers the possibility of directly determining the hydration contributions related to interlayer cations and layer surfaces, an approach based on the combination of electrostatic calculations and immersion data is developed here, as already validated in the case of montmorillonites saturated by alkaline cations. This methodology allows to estimate the hydration energy for divalent interlayer cations and therefore to shed a new light on the driving force for hydration process occurring in montmorillonites saturated with alkaline-earth cations. Firstly, the surface energy values obtained from the electrostatic calculations based on the Electronegativity Equalization Method vary from 450 mJ m(-2) for Mg-montmorillonite to 1100 mJ m(-2) for Ba-montmorillonite. Secondly, considering both the hydration energy for cations and layer surfaces, the driving force for the hydration of alkaline-earth saturated montmorillonites can be attributed to the interlayer cation in the case of Mg-, Ca-, Sr-montmorillonites and to the interlayer surface in the case of Ba-montmorillonites. These results explain the differences in behaviour upon water adsorption as a function of the nature of the interlayer cation

  7. Impact of cationic diffusion on properties of iron-bearing glass fibres

    DEFF Research Database (Denmark)

    Smedskjaer, Morten M.; Yue, Yuanzheng; Deubener, Joachim;


    A silica-rich surface layer of Fe3+-containing aluminosilicate glass fibres is created by means of an inward diffusion process of divalent network modifying cations. The latter is caused by the reduction of Fe3+ to Fe2+ when the fibres undergo a heat treatment at temperatures around the glass...... transition temperature (Tg) in a reducing H2/N2 atmosphere. The thickness of the surface layer can be adjusted by varying the temperature or the duration of the heat treatment. The reduction process has a significant impact on the glass transition and crystallization behaviour, high temperature stability...

  8. The effect of divalent salt in chondroitin sulfate solutions (United States)

    Aranghel, D.; Badita, C. R.; Radulescu, A.; Moldovan, L.; Craciunescu, O.; Balasoiu, M.


    Chondroitin-4 sulfate (CS4) is the main glycosaminoglycan extracted from bovine trachea. CS4 play an important role in osteoarthritis treatment, anticoagulant activity, reduces the degradation of cartilage matrix components, reduces necrosis and apoptosis of chondrocytes and reduces the activity of collagenase. Chondroitin sulfate is also responsible for proteoglycans degradation. Chondroitin sulfate can bind calcium ions with different affinities, depending on their sulfation position. The purpose of this study was to determine the structural properties and the influence of Ca2+ cations. We carried out measurements on CS4 solutions and mixtures of liquid CS4 with Ca2+ by Small-Angle Neutron Scattering (SANS). CS4 have a mass fractal behavior and the addition of a salt (CaCl2) in CS4 solutions generates the appearance of a correlation peak due to local ordering between adjacent chains with inter-chain distances between 483 Å and 233 Å for a calcium concentration of 0.01% w/w.

  9. Radial variations in cation exchange capacity and base saturation rate in the wood of pedunculate oak and European beech

    Energy Technology Data Exchange (ETDEWEB)

    Herbauts, J.; Penninckx, V.; Gruber, W.; Meerts, P. [Universite Libre de Bruxelles, Laboratoire de genetique et d' ecologie vegetales, Brussels (Belgium)


    Visual observation of pedunculate oak trees and European beech trees in a mixed forest stand in the Belgian Ardennes revealed decreasing cation concentration profiles in wood. In order to determine whether these profiles are attributable to endogenous factors or to decreased availability of cations in the soil, radial profiles of water-soluble, exchangeable and total cations were investigated. Cation exchange capacity of wood was also determined. Results showed wood cation exchange capacity to decrease from pith to bark in European beech and from pith to outer heartwood in pedunculate oak. Decreasing profiles of exchangeable calcium and magnesium in peduncular oak and exchangeable calcium in European beech were found to be strongly constrained by cation exchange capacity, and thus not related to environmental change. Base cation saturation rate showed no consistent radial change in either species. It was concluded that the results did not provide convincing evidence to attribute the decrease in divalent cation concentration in pedunculate oak and European beech in this location to be due to atmospheric pollution. 42 refs., 1 tab., 4 figs.

  10. Enhancement of Exciton Emission in Lead Halide-Based Layered Perovskites by Cation Mixing. (United States)

    Era, Masanao; Komatsu, Yumeko; Sakamoto, Naotaka


    Spin-coated films of a lead halide, PbX: X = I and Br, layered perovskites having cyclohexenylethyl ammonium molecule as an organic layer, which were mixed with other metal halide-based layered perovskites consisting of various divalent metal halides (for example, Ca2, Cdl2, FeI2, SnBr2 and so on), were prepared. The results of X-ray diffraction measurements exhibited that solid solution formation between PbX-based layered perovskite and other divalent metal halide-based layered perovskites was observed up to very high molar concentration of 50 molar% in the mixed film samples when divalent cations having ionic radius close to that of Pb2+ were employed. In the solid solution films, the exciton emission was much enhanced at room temperature. Exciton emission intensity of Pbl-based layered perovskite mixed with Cal-based layered perovskite (20 molar%) is about 5 times large that of the pristine Pbl-based layered perovskite, and that of PbBr-based layered perovskite mixed with SnBr-based layered perovskite (20 molar%) was also about 5 times large that of the pristine PbBr-based layered perovskite at room temperature.

  11. Cloning and divalent-metal activation of a ß-xylosidase, RUM630-BX (United States)

    The gene encoding RUM630-BX, a ß-xylosidase/arabinofuranosidase, was identified from activity-based screening of a cow rumen metagenomic library. The recombinant enzyme is activated as much as 14-fold (kcat) by divalent metals Mg2+, Mn2+ and Co2+ but not by Ca2+, Ni2+, and Zn2+. Activation of RUM6...

  12. 8-aminoquinoline functionalized silica nanoparticles: a fluorescent nanosensor for detection of divalent zinc in aqueous and in yeast cell suspension. (United States)

    Rastogi, Shiva K; Pal, Parul; Aston, D Eric; Bitterwolf, Thomas E; Branen, A Larry


    Zinc is one of the most important transition metal of physiological importance, existing primarily as a divalent cation. A number of sensors have been developed for Zn(II) detection. Here, we present a novel fluorescent nanosensor for Zn(II) detection using a derivative of 8-aminoquinoline (N-(quinolin-8-yl)-2-(3 (triethoxysilyl)propylamino)acetamide (QTEPA) grafted on silica nanoparticles (SiNPs). These functionalized SiNPs were used to demonstrate specific detection of Zn(II) in tris-HCl buffer (pH 7.22), in yeast cell (Saccharomyces cerevisiae) suspension, and in tap water. The silane QTEPA, SiNPs and final product were characterized using solution and solid state nuclear magnetic resonance, Fourier transform infrared, ultraviolet-visible absorption spectroscopy, transmission electron microscopy, elemental analysis, thermogravimetric techniques, and fluorescence spectroscopy. The nanosensor shows almost 2.8-fold fluorescence emission enhancement and about 55 nm red-shift upon excitation with 330 ± 5 nm wavelength in presence of 1 μM Zn(II) ions in tris-HCl (pH 7.22). The presence of other metal ions has no observable effect on the sensitivity and selectivity of nanosensor. This sensor selectively detects Zn(II) ions with submicromolar detection to a limit of 0.1 μM. The sensor shows good applicability in the determination of Zn(II) in tris-HCl buffer and yeast cell environment. Further, it shows enhancement in fluorescence intensity in tap water samples.

  13. Tuning of the magnetostrictive properties of cobalt ferrite by forced distribution of substituted divalent metal ions at different crystallographic sites (United States)

    Anantharamaiah, P. N.; Joy, P. A.


    Comparative studies have been made to understand the role of different crystallographic site preferences of the substituted non-magnetic divalent metal ions in the magnetostrictive properties of cobalt ferrite, by substitution of Zn2+ and/or Mg2+ for Fe3+ in CoMgxFe2-xO4, CoZnxFe2-xO4, and CoMgx/2Znx/2Fe2-xO4 (0.0 ≤ x ≤ 0.2). Detailed Raman spectral and magnetic characterizations are made to extract the information on the tetrahedral/octahedral site preferences of Zn and Mg in the spinel lattice of cobalt ferrite. The structural, microstructural, magnetic, Raman spectral, and magnetostrictive parameters of the studied compositions show distinguishable variations for x < 0.1 and x ≥ 0.1. Co-substitution of a small amount of Mg and Zn for Fe in CoMgx/2Znx/2Fe2-xO4 (x < 0.1) showed relatively larger strain sensitivity, [dλ/dH]max (-2.6 × 10-9 mA-1 for x = 0.05), higher than that for the Mg-substituted samples (-2.05 × 10-9 mA-1 for x = 0.05) and comparable to that for the Zn-substituted samples (-2.47 × 10-9 mA-1 for x = 0.05), without much drop in the maximum value of magnetostriction, λmax (-189 ppm for x = 0.05) compared to that for the unsubstituted counterpart (-221 ppm). The results show that it is possible to obtain high strain sensitivity (at fields <50 kA/m), along with high magnetostriction strain at low magnetic fields (˜250 kA/m), by tuning the distribution of the substituted cations in the tetrahedral and octahedral sites of the cobalt ferrite lattice.

  14. Protection of Mice with a Divalent Tuberculosis DNA Vaccine Encoding Antigens Ag85B and MPT64

    Institute of Scientific and Technical Information of China (English)

    Xia TIAN; Hong CAI; Yu-Xian ZHU


    DNA vaccine may be a promising tool for controlling tuberculosis development. However,vaccines encoding single antigens of mycobacterium did not produce protective effect as BCG did. In the present study, we evaluated the immunogenicity and protective efficacy of a divalent DNA vaccine encoding two immunodominant antigens Ag85B and MPT64 of Mycobacterium tuberculosis. We found that both humoral and Th1-type (high IFN-γ, low IL-4) cellular responses obtained from the divalent DNA vaccine group were significantly higher than that conferred by BCG. RT-PCR results showed that antigens were expressed differentially in various organs in divalent DNA vaccine group. The survival rate for mice treated with the divalent DNA vaccine after challenging with high doses of virulent M. tuberculosis H37Rv was significantly higher than that of the BCG group or any of the single DNA vaccine group. Significant differences were also found between the single and divalent DNA vaccinated mice in terms of body, spleen and lung weight. Bacterial loading decreased about 2000-fold in lungs and about 100-fold in spleens of divalent DNA vaccinated mice when compared with that of the control group. We conclude that our divalent DNA vaccine may be a better choice for controlling tuberculosis disease in animals.

  15. Removal of divalent heavy metals (Cd, Cu, Pb, and Zn) and arsenic(III) from aqueous solutions using scoria: kinetics and equilibria of sorption. (United States)

    Kwon, Jang-Soon; Yun, Seong-Taek; Lee, Jong-Hwa; Kim, Soon-Oh; Jo, Ho Young


    Kinetic and equilibrium sorption experiments were conducted on removal of divalent heavy metals (Pb(II), Cu(II), Zn(II), Cd(II)) and trivalent arsenic (As(III)) from aqueous solutions by scoria (a vesicular pyroclastic rock with basaltic composition) from Jeju Island, Korea, in order to examine its potential use as an efficient sorbent. The removal efficiencies of Pb, Cu, Zn, Cd, and As by the scoria (size=0.1-0.2mm, dose=60gL(-1)) were 94, 70, 63, 59, and 14%, respectively, after a reaction time of 24h under a sorbate concentration of 1mM and the solution pH of 5.0. A careful examination on ionic concentrations in sorption batches suggested that sorption behaviors of heavy metals onto scoria are mainly controlled by cation exchange. On the other hand, arsenic appeared to be sensitive to specific sorption onto hematite (a minor constituent of scoria). Equilibrium sorption tests indicated that the removal efficiency for heavy metals increases with increasing pH of aqueous solutions, which is resulted from precipitation as hydroxides. Similarly, multi-component systems containing heavy metals and arsenic showed that the arsenic removal increases with increasing pH of aqueous solutions, which can be attributed to coprecipitation with metal hydroxides. The empirically determined sorption kinetics were well fitted to a pseudo-second order model, while equilibrium sorption data for heavy metals and arsenic onto scoria were consistent with the Langmuir and Freundlich isotherms, respectively. Natural scoria studied in this work is an efficient sorbent for concurrent removal of divalent heavy metals and arsenic.

  16. Change Color Effect and Spectral Properties of Gold Nanoparticle-cationic Surfactants System

    Institute of Scientific and Technical Information of China (English)

    JIANG Zhi-liang; PAN Hong-cheng; YUAN Wei-en


    The change color effect of gold nanoparticle solutions was studied by means of resonance scattering and absorption spectrometry and scan electron microscopy. The red Au nanoparticles with a size of 10 nm exhibit a resonance absorption peak and a resonance scattering peak all at 525 nm. After some inorganic electrolyte was added to a red Au nanoparticles solution, the color of the solution became blue and the absorbance at 600-700 nm was significantly increased. The ratio of the concentration of monovalent cations, at which the resonance scattering of the system at 525 nm is maximal to that of divalent cations, is in the range of 100 : 1 -100 : 1.8. It is in good agreement with the Schulze-Hardy rule of the coagulation value of electrolyte. After adding some cationic surfactants to the above solution, the color of the solution is in deep blue, with two resonance absorption peaks at 550 and 680 nm, and a greatly enhanced resonance scattering peak at 525 nm.The experiments demonstrate that the stronger the hydrophobicity of the cationic surfactant is, the stronger the change color effect of the Au nanoparticle solution promoted by cationic surfactant is. The change color effect of Au nanoparticle solution is resulted from the increased diameter of Au nanoparticles, and the changes of resonance absorption peak and resonance scattering.

  17. Cationic schiff base amphiphiles and their metal complexes: Surface and biocidal activities against bacteria and fungi. (United States)

    Negm, N A; Zaki, M F; Salem, M A I


    A series of cationic surfactants containing schiff base groups was synthesized by condensation of four fatty amines namely: dodecyl, tetradecyl, hexadecyl and octadecyl amine and 4-diethyl aminobenzaldehyde (1-4), as well as their metal complexes with divalent transition metal ions including Co, Cu and Mn (5-16). The surface activities of the synthesized surfactants were influenced by their chemical structures and the type of the transition metals. The biological activity measurements of the parent cationic schiff bases showed high efficacy against Gram positive and Gram negative bacterial strains and fungi. While on complexation, the biocidal activity was increased remarkably. The biocidal activity of the tested compounds against sulfur reducing bacteria showed promising results in the field of biocide applications.

  18. Influence of competing inorganic cations on the ion exchange equilibrium of the monovalent organic cation metoprolol on natural sediment. (United States)

    Niedbala, Anne; Schaffer, Mario; Licha, Tobias; Nödler, Karsten; Börnick, Hilmar; Ruppert, Hans; Worch, Eckhard


    The aim of this study was to systematically investigate the influence of the mono- and divalent inorganic ions Na(+) and Ca(2+) on the sorption behavior of the monovalent organic cation metoprolol on a natural sandy sediment at pH=7. Isotherms for the beta-blocker metoprolol were obtained by sediment-water batch tests over a wide concentration range (1-100000 μg L(-1)). Concentrations of the competing inorganic ions were varied within freshwater relevant ranges. Data fitted well with the Freundlich sorption model and resulted in very similar Freundlich exponents (n=0.9), indicating slightly non-linear behavior. Results show that the influence of Ca(2+) compared to Na(+) is more pronounced. A logarithmic correlation between the Freundlich coefficient K(Fr) and the concentration or activity of the competing inorganic ions was found allowing the prediction of metoprolol sorption on the investigated sediment at different electrolyte concentrations. Additionally, the organic carbon of the sediment was completely removed for investigating the influence of organic matter on the sorption of metoprolol. The comparison between the experiments with and without organic carbon removal revealed no significant contribution of the organic carbon fraction (0.1%) to the sorption of metoprolol on the in this study investigated sediment. Results of this study will contribute to the development of predictive models for the transport of organic cations in the subsurface.

  19. Effect of various gelling cations on the physical properties of "wet" alginate films. (United States)

    Harper, B Allison; Barbut, Shai; Lim, Loong-Tak; Marcone, Massimo F


    In this study, the physical properties of "wet" alginate films gelled with various divalent cations (Ba(2+) , Ca(2+) , Mg(2+) , Sr(2+) , and Zn(2+) ) were explored. Additionally, the effect of adding NaCl to the alginate film-forming solution prior to gelling was evaluated. Aside from Mg(2+) , all of the divalent cations were able to produce workable "wet" alginate films. Films gelled with BaCl2 (without added NaCl) had the highest (P alginate and Sr-alginate films had the highest elongation at break values. Adding NaCl to the alginate film-forming solution increased the viscosity of the solution. Films with added NaCl were less transparent and had lower tensile strength, elongation, and puncture strength than films formed without NaCl in the film-forming solution. ATR-FTIR results showed a slight shift in the asymmetric COO(-) vibrational peak of the alginate when the "wet" alginate films were gelled with Zn(2+) .

  20. Efficient polymerization of acrylonitrile catalyzed by diValent lanthanide complex/sodium phenolate systems

    Institute of Scientific and Technical Information of China (English)


    Four divalent lanthanide complexes Sm(ArO)2(THF)4, Yb(ArO)2(THF)3, Eu(ArO)2(THF)3 (ArO = 2,6-ditert-butyl-4-methylphenolate) and (ButCp)2Sm(THF)2 were synthesized. Their catalytic activities on the polymerization of acrylonitrile were studied. The catalytic activities were influenced by the central metal ions involved. The catalytic activities of these divalent lanthanide complexes can be greatly increased by adding NaOC~H2-2,6-But2-4-Me,NaOC6H4-4-But, or NaOC10H6-2-Me. The amount of additive has apparent effect on the catalytic activity, but the additive has no effect on the tacticity of the resulting polyacrylonitrile

  1. Interactions of divalent calcium ions with head groups of zwitterionic phosphatidylcholine liposomal membranes. (United States)

    Santhosh, Poornima Budime; Velikonja, Aljaž; Gongadze, Ekaterina; Iglič, Aleš; Kralj-Iglič, Veronika; Ulrih, Nataša Poklar


    The interaction of the divalent calcium ions with the zwitterionic lipid membranes was studied by measuring the lipid order parameter which is inversely proportional to the membrane fluidity. Small unilamellar lipid vesicles were prepared from 1-palmitoyl-2-oleoyl-sn-glycero-3-phosphocholine and then treated with different concentrations of divalent calcium ions. An increase in the order parameter and decrease in the fluidity of the liposomal membranes were observed after treatment with the calcium ions. The presence of positively charged iron oxide nanoparticles in the suspension of liposomes negligibly changed the results. The results of experiments were discussed theoretically within modified Langevin-Poisson-Boltzmann (MLPB) model leading to the conclusion that the membrane fluidity and ordering of the membrane lipids are primarily altered by the accumulation of calcium ions in the region of negatively charged phosphate groups within the head groups of the membrane lipids.

  2. Aspartate buffer and divalent metal ions affect oxytocin in aqueous solution and protect it from degradation

    DEFF Research Database (Denmark)

    Avanti, Christina; Oktaviani, Nur Alia; Hinrichs, Wouther L.J.


    is improved by the addition of divalent metal ions (unpublished results). The stabilizing effect of Zn2+ was by far superior compared to that of Mg2+. In addition, it was found that stabilization correlated well with the ability of the divalent metal ions to interact with oxytocin in aspartate buffer...... favorable. These interactions may explain the protection of the disulfide bridge against intermolecular reactions that lead to dimerization.Mg or Zn, using 2D NOESY, TOCSY, H-C HSQC and H- N HSQC NMR spectroscopy. Almost all H, C and N resonances of oxytocin could be assigned using HSQC spectroscopy...... that the carboxylate group of aspartate neutralizes the positive charge of the N-terminus of Cys, allowing the interactions with Zn to become more favorable. These interactions may explain the protection of the disulfide bridge against intermolecular reactions that lead to dimerization....

  3. Electrochemical Studies of Eight New Divalent Transition Metal Benzenesulphonate Ternary Complexes with 1,10-Phenanthroline

    Institute of Scientific and Technical Information of China (English)

    LU Yao; GUO Li-ping; MA Jian-fang; YANG Jin; WU Dongmei


    The electrochemical properties of eight new divalent transition metal benzenesulphonate complexes with 1,10-phenanthroline in different solvents and supporting electrolytes were investigated by means of cyclic voltammetry(CV). Based on the CV data the influences of various coordination modes on the electrochemical behavior of the complexes were discussed. The diffusion coefficient Dc and rate constant ks of those complexes in DMF systems were estimated according to CV and the results show that these processes were all quasi-reversible.

  4. Green Luminescence of Divalent Europium in the Hydride Chloride EuHCl

    NARCIS (Netherlands)

    Kunkel, Nathalie; Rudolph, Daniel; Meijerink, A; Rommel, Stefan; Weihrich, Richard; Kohlmann, Holger; Schleid, Thomas


    Luminescence properties of divalent europium in the mixed-anion hydride chloride EuHCl were studied for the first time. Olive-green single crystals of EuHCl (PbFCl-type structure: tetragonal, P4/nmm, a = 406.58(3) pm, c = 693.12(5) pm, c/a = 1.705, Z = 2) resulted from the reaction of elemental euro

  5. Study the effects of divalent metallic ions on the combination of DNA and histones with fluorescence anisotropy assays

    Institute of Scientific and Technical Information of China (English)

    LIU YuYing; WANG PengYe; DOU ShuoXing; XIE Ping; XI XuGuang


    The effects of divalent ions (Mn2+, Mg2+, Ca2+) on the interaction between DNA and histone are studied using a fluorescence anisotropy assay. Fluorescence anisotropies of DNA and DNA-histone in the presence of divalent ions (Mn2+, Mg2+, Ca2+) are measured. The results indicate that histone reduces the fluorescence anisotropy of lambda DNA while the divalent ions (Mn2+, Mg2+, Ca2+) significantly enhance the fluorescence anisotropy. Compared to the case of DNA incubated with histone alone, there are more histones binding to DNA when divalent ion, histone and DNA are incubated together. We also find that Mn2+ makes the DNA-histone complexes more condensed than the other ions do.

  6. Influence of length and flexibility of spacers on the binding affinity of divalent ligands

    Directory of Open Access Journals (Sweden)

    Susanne Liese


    Full Text Available We present a quantitative model for the binding of divalent ligand–receptor systems. We study the influence of length and flexibility of the spacers on the overall binding affinity and derive general rules for the optimal ligand design. To this end, we first compare different polymeric models and determine the probability to simultaneously bind to two neighboring receptor binding pockets. In a second step the binding affinity of divalent ligands in terms of the IC50 value is derived. We find that a divalent ligand has the potential to bind more efficiently than its monovalent counterpart only, if the monovalent dissociation constant is lower than a critical value. This critical monovalent dissociation constant depends on the ligand-spacer length and flexibility as well as on the size of the receptor. Regarding the optimal ligand-spacer length and flexibility, we find that the average spacer length should be equal or slightly smaller than the distance between the receptor binding pockets and that the end-to-end spacer length fluctuations should be in the same range as the size of a receptor binding pocket.

  7. Influence of length and flexibility of spacers on the binding affinity of divalent ligands. (United States)

    Liese, Susanne; Netz, Roland R


    We present a quantitative model for the binding of divalent ligand-receptor systems. We study the influence of length and flexibility of the spacers on the overall binding affinity and derive general rules for the optimal ligand design. To this end, we first compare different polymeric models and determine the probability to simultaneously bind to two neighboring receptor binding pockets. In a second step the binding affinity of divalent ligands in terms of the IC50 value is derived. We find that a divalent ligand has the potential to bind more efficiently than its monovalent counterpart only, if the monovalent dissociation constant is lower than a critical value. This critical monovalent dissociation constant depends on the ligand-spacer length and flexibility as well as on the size of the receptor. Regarding the optimal ligand-spacer length and flexibility, we find that the average spacer length should be equal or slightly smaller than the distance between the receptor binding pockets and that the end-to-end spacer length fluctuations should be in the same range as the size of a receptor binding pocket.

  8. On the real performance of cation exchange resins in wastewater treatment under conditions of cation competition: the case of heavy metal pollution. (United States)

    Prelot, Benedicte; Ayed, Imen; Marchandeau, Franck; Zajac, Jerzy


    Sorption performance of cation-exchange resins Amberlite® IRN77 and Amberlite™ IRN9652 toward Cs(I) and Sr(II) has been tested in single-component aqueous solutions and simulated waste effluents containing other monovalent (Effluent 1) or divalent (Effluent 2) metal cations, as well as nitrate, borate, or carbonate anions. The individual sorption isotherms of each main component were measured by the solution depletion method. The differential molar enthalpy changes accompanying the ion-exchange between Cs+ or Sr2+ ions and protons at the resin surface from single-component nitrate solutions were measured by isothermal titration calorimetry and they showed a higher specificity of the two resins toward cesium. Compared to the retention limits of both resins under such idealized conditions, an important depression in the maximum adsorption capacity toward each main component was observed in multication systems. The overall effect of ion exchange process appeared to be an unpredictable outcome of the individual sorption capacities of the two resins toward various cations as a function of the cation charge, size, and concentration. The cesium retention capacity of the resins was diminished to about 25% of the "ideal" value in Effluent 1 and 50% in Effluent 2; a further decrease to about 15% was observed upon concomitant strontium addition. The uptake of strontium by the resins was found to be less sensitive to the addition of other metal components: the greatest decrease in the amount adsorbed was 60% of the ideal value in the two effluents for Amberlite® IRN77 and 75% for Amberlite™ IRN9652. It was therefore demonstrated that any performance tests carried out under idealized conditions should be exploited with much caution to predict the real performance of cation exchange resins under conditions of cation competition.

  9. Cation immobilization in pyrolyzed simulated spent ion exchange resins

    Energy Technology Data Exchange (ETDEWEB)

    Luca, Vittorio, E-mail: [Programa Nacional de Gestion de Residuos Radiactivos, Centro Atomico Constituyentes, Comision Nacional de Energia Atomica, Av. General, Paz 1499, 1650 San Martin, Provincia de Buenos Aires (Argentina); Bianchi, Hugo L. [Gerencia de Quimica, Centro Atomico Constituyentes, Comision Nacional de Energia Atomica, Av. General, Paz 1499, 1650 San Martin, Provincia de Buenos Aires (Argentina); ECyT, Universidad Nacional de General San Martin, Campus Miguelete, Ed. Tornavias, Martin de Irigoyen 3100, 1650 San Martin (Argentina); Conicet, Av. Rivadavia 1917, 1033 Buenos Aires (Argentina); Manzini, Alberto C. [Programa Nacional de Gestion de Residuos Radiactivos, Comision Nacional de Energia Atomica, Av. Del Libertador 8250, CP 1429, Ciudad Autonoma de Buenos Aires (Argentina)


    Significant quantities of spent ion exchange resins that are contaminated by an assortment of radioactive elements are produced by the nuclear industry each year. The baseline technology for the conditioning of these spent resins is encapsulation in ordinary Portland cement which has various shortcomings none the least of which is the relatively low loading of resin in the cement and the poor immobilization of highly mobile elements such as cesium. The present study was conducted with cationic resin samples (Lewatit S100) loaded with Cs{sup +}, Sr{sup 2+}, Co{sup 2+}, Ni{sup 2+} in roughly equimolar proportions at levels at or below 30% of the total cation exchange capacity. Low temperature thermal treatment of the resins was conducted in inert (Ar), or reducing (CH{sub 4}) gas atmospheres, or supercritical ethanol to convert the hydrated polymeric resin beads into carbonaceous materials that contained no water. This pyrolytic treatment resulted in at least a 50% volume reduction to give mechanically robust spherical materials. Scanning electron microscope investigations of cross-sections of the beads combined with energy dispersive analysis showed that initially all elements were uniformly distributed through the resin matrix but that at higher temperatures the distribution of Cs became inhomogeneous. Although Cs was found in the entire cross-section, a significant proportion of the Cs occurred within internal rings while a proportion migrated toward the outer surfaces to form a crustal deposit. Leaching experiments conducted in water at 25 Degree-Sign C showed that the divalent contaminant elements were very difficult to leach from the beads heated in inert atmospheres in the range 200-600 Degree-Sign C. Cumulative fractional loses of the order of 0.001 were observed for these divalent elements for temperatures below 500 Degree-Sign C. Regardless of the processing temperature, the cumulative fractional loss of Cs in water at 25 Degree-Sign C reached a plateau or

  10. Interaction of polyamines with proteins of photosystem II: Cation binding and photosynthetic oxygen evolution (United States)

    Beauchemin, R.; Harnois, J.; Rouillon, R.; Tajmir-Riahi, H. A.; Carpentier, R.


    Polyamines are organic cations that function in diverse physiological processes that share as a common thread a close relationship to cell proliferation and growth. Polyamines also affect photosynthetic oxygen evolution and therefore, this study was designed to investigate the interaction of 1,3-diaminopropane, 1,4-diaminobutane (putrescine), and 1,5-diaminopentane (cadaverine) cations with proteins of photosystem II (PSII) using PSII-enriched submembrane fractions with diamine concentrations between 0.01 and 20 mM. Fourier transformed infrared (FTIR) difference spectroscopy with its self-deconvolution and second derivative resolution enhancement, as well as curve-fitting procedures were applied in order to determine the diamine binding mode, the protein conformational changes, and the structural properties of diamine-protein complexes. Spectroscopic evidence showed that diamines interact with proteins (H-bonding) through polypeptide C dbnd O groups with no major perturbations of protein secondary structure. At very low diamine concentration (0.01 mM), no inhibition of oxygen-evolution occurred, while at higher diamine content (5-10 mM), 100% inhibition was observed. Chorophyll fluorescence measurements demonstrated that the inhibition mainly affects the oxygen evolving complex of PSII. Comparisons of the effects of these dipositive organic cations with divalent metal cations on one hand and with polyvalent spermine and spermidine on the other hand, show major alterations of the protein secondary structure as positive charge increases.

  11. Study of cation distribution of spinel zinc nano-ferrite by X-ray

    Energy Technology Data Exchange (ETDEWEB)

    Najafi Birgani, Azadeh, E-mail:; Niyaifar, Mohammad; Hasanpour, Ahmad


    A set of zinc ferrite samples with ZnFe{sub 2}O{sub 4} chemical composition were synthesized in 400, 500, and 1100 °C using conventional solid state synthesis method. The X-ray diffraction pattern of all the three samples was studied at room temperature. This diffraction pattern confirmed the existence of a single-phase cubic spinel structure with lattice parameters of 8.451, 8.448, and 8.437 Å, respectively. Oxygen position and cation distribution of the samples between the tetrahedral site, A and the octahedral site, B were examined using R-Factor method. The results showed that cation distribution of zinc ferrite samples changes from a normal spinel mode into a mixed spinel mode with the decrease of particle size. Moreover, the ratio of zinc divalent cations migrating from the tetrahedral site to the octahedral site was calculated. - Highlights: • The average crystallite size of a set of zinc ferrite samples compared. • The cation distribution of the samples were studied. • A fraction of zinc ions migrated to the octahedral site. • This migration due to reduced power of ligands. • Their spinel structure of samples change by this migration.

  12. Multi-scale simulation studies on interaction between anionic surfactants and cations

    Directory of Open Access Journals (Sweden)

    Siwei Meng


    Full Text Available In this paper, a dissipative particle dynamics (DPD simulation method was used to investigate the impact of cations on the rheological properties of dodecyl sulfonate surfactant solutions. In order to obtain reasonable interaction between head groups of the surfactant, the geometric structure and interaction between dodecyl sulfonate and cations are optimized using density function theory (DFT at the B3LYP/6-31G level. The DFT calculated results indicate that α-methylene nearest the head group can be classified as a part of the polar head. After binding, the charge on polar head decreases, thus greatly reduces the repulsion between the head groups. It is found that the presence of counterions is one of induction factors on the formation of wormlike micelles, thus greatly enhances the viscosity of surfactant solution. With the increasing in shear strengthen, the wormlike micelles are gradually oriented in the x direction and then broken up into small spherical micelles. This process is also shown by the decrease of viscosity, which decreases quickly at the low shear rates, then keeps almost a constant at the moderate shear rates and at last decreases again at the shear rates larger than a critical value. Compared with monovalent cations, divalent cations have a stronger effect on the rheological properties of dodecyl sulfonate solutions.

  13. Cations and hydration in catalytic RNA: molecular dynamics of the hepatitis delta virus ribozyme. (United States)

    Krasovska, Maryna V; Sefcikova, Jana; Réblová, Kamila; Schneider, Bohdan; Walter, Nils G; Sponer, Jirí


    The hepatitis delta virus (HDV) ribozyme is an RNA enzyme from the human pathogenic HDV. Cations play a crucial role in self-cleavage of the HDV ribozyme, by promoting both folding and chemistry. Experimental studies have revealed limited but intriguing details on the location and structural and catalytic functions of metal ions. Here, we analyze a total of approximately 200 ns of explicit-solvent molecular dynamics simulations to provide a complementary atomistic view of the binding of monovalent and divalent cations as well as water molecules to reaction precursor and product forms of the HDV ribozyme. Our simulations find that an Mg2+ cation binds stably, by both inner- and outer-sphere contacts, to the electronegative catalytic pocket of the reaction precursor, in a position to potentially support chemistry. In contrast, protonation of the catalytically involved C75 in the precursor or artificial placement of this Mg2+ into the product structure result in its swift expulsion from the active site. These findings are consistent with a concerted reaction mechanism in which C75 and hydrated Mg2+ act as general base and acid, respectively. Monovalent cations bind to the active site and elsewhere assisted by structurally bridging long-residency water molecules, but are generally delocalized.

  14. Evolutionary and structural perspectives of plant cyclic nucleotide-gated cation channels

    KAUST Repository

    Zelman, Alice K.


    Ligand-gated cation channels are a frequent component of signaling cascades in eukaryotes. Eukaryotes contain numerous diverse gene families encoding ion channels, some of which are shared and some of which are unique to particular kingdoms. Among the many different types are cyclic nucleotide-gated channels (CNGCs). CNGCs are cation channels with varying degrees of ion conduction selectivity. They are implicated in numerous signaling pathways and permit diffusion of divalent and monovalent cations, including Ca2+ and K+. CNGCs are present in both plant and animal cells, typically in the plasma membrane; recent studies have also documented their presence in prokaryotes. All eukaryote CNGC polypeptides have a cyclic nucleotide-binding domain and a calmodulin binding domain as well as a six transmembrane/one pore tertiary structure. This review summarizes existing knowledge about the functional domains present in these cation-conducting channels, and considers the evidence indicating that plant and animal CNGCs evolved separately. Additionally, an amino acid motif that is only found in the phosphate binding cassette and hinge regions of plant CNGCs, and is present in all experimentally confirmed CNGCs but no other channels was identified. This CNGC-specific amino acid motif provides an additional diagnostic tool to identify plant CNGCs, and can increase confidence in the annotation of open reading frames in newly sequenced genomes as putative CNGCs. Conversely, the absence of the motif in some plant sequences currently identified as probable CNGCs may suggest that they are misannotated or protein fragments. 2012 Zelman, Dawe, Gehring and Berkowitz.

  15. Synthetic cation-selective nanotube: Permeant cations chaperoned by anions (United States)

    Hilder, Tamsyn A.; Gordon, Dan; Chung, Shin-Ho


    The ability to design ion-selective, synthetic nanotubes which mimic biological ion channels may have significant implications for the future treatment of bacteria, diseases, and as ultrasensitive biosensors. We present the design of a synthetic nanotube made from carbon atoms that selectively allows monovalent cations to move across and rejects all anions. The cation-selective nanotube mimics some of the salient properties of biological ion channels. Before practical nanodevices are successfully fabricated it is vital that proof-of-concept computational studies are performed. With this in mind we use molecular and stochastic dynamics simulations to characterize the dynamics of ion permeation across a single-walled (10, 10), 36 Å long, carbon nanotube terminated with carboxylic acid with an effective radius of 5.08 Å. Although cations encounter a high energy barrier of 7 kT, its height is drastically reduced by a chloride ion in the nanotube. The presence of a chloride ion near the pore entrance thus enables a cation to enter the pore and, once in the pore, it is chaperoned by the resident counterion across the narrow pore. The moment the chaperoned cation transits the pore, the counterion moves back to the entrance to ferry another ion. The synthetic nanotube has a high sodium conductance of 124 pS and shows linear current-voltage and current-concentration profiles. The cation-anion selectivity ratio ranges from 8 to 25, depending on the ionic concentrations in the reservoirs.

  16. Stable divalent germanium, tin and lead amino(ether)-phenolate monomeric complexes: structural features, inclusion heterobimetallic complexes, and ROP catalysis. (United States)

    Wang, Lingfang; Roşca, Sorin-Claudiu; Poirier, Valentin; Sinbandhit, Sourisak; Dorcet, Vincent; Roisnel, Thierry; Carpentier, Jean-François; Sarazin, Yann


    Stable germanium(II) and lead(II) amido complexes {LO(i)}M(N(SiMe3)2) (M = Ge(II), Pb(II)) bearing amino(ether)phenolate ligands are readily available using the proteo-ligands {LO(i)}H of general formula 2-CH2NR2-4,6-tBu2-C6H2OH (i = 1, NR2 = N((CH2)2OCH3)2; i = 2, NR2 = NEt2; i = 3, NR2 = aza-15-crown-5) and M(N(SiMe3)2)2 precursors. The molecular structures of these germylenes and plumbylenes, as well as those of {LO(3)}GeCl, {LO(3)}SnCl and of the congeneric {LO(4)}Sn(II)(N(SiMe3)2) where NR2 = aza-12-crown-4, have been determined crystallographically. All complexes are monomeric, with 3-coordinate metal centres. The phenolate systematically acts as a N^O(phenolate) bidentate ligand, with no interactions between the metal and the O(side-arm) atoms in these cases (for {LO(1)}(-), {LO(3)}(-) and {LO(4)}(-)) where they could potentially arise. For each family, the lone pair of electrons essentially features ns(2) character, and there is little, if any, hybridization of the valence orbitals. Heterobimetallic complexes {LO(3)}M(N(SiMe3)2)·LiOTf, where the Li(+) cation sits inside the tethered crown-ether, were prepared by reaction of {LO(3)}M(N(SiMe3)2) and LiOTf (M = Ge(II), Sn(II)). The inclusion of Li(+) (featuring a close contact with the triflate anion) in the macrocycle bears no influence on the coordination sphere of the divalent tetrel element. In association with iPrOH, the amido germylenes, stannylenes and plumbylenes catalyse the controlled polymerisation of L- and racemic lactide. The activity increases linearly according to Ge(II) ≪ Sn(II) ≪ Pb(II). The simple germylenes generate very sluggish catalysts, but the activity is significantly boosted if the heterobimetallic complex {LO(3)}Ge(N(SiMe3)2)·LiOTf is used instead. On the other hand, with 10-25 equiv. of iPrOH, the plumbylenes afford highly active binary catalysts, converting 1000 or 5000 equiv. of monomer at 60 °C within 3 or 45 min, respectively, in a controlled fashion.

  17. Characterization of parvalbumin and polcalcin divalent ion binding by isothermal titration calorimetry. (United States)

    Henzl, Michael T


    The elucidation of structure-affinity relationships in EF-hand proteins requires a reliable assay of divalent ion affinity. In principle, isothermal titration calorimetry (ITC) should be capable of furnishing estimates for Ca2+- and Mg2+-binding constants in these systems. And because the method yields the binding enthalpy directly, ITC can provide a more detailed view of binding energetics than methods that rely on 45Ca2+ or fluorescent indicators. For several reasons, however, it is generally not possible to extract reliable binding parameters from single ITC experiments. Ca2+ affinity is often too high, and Mg2+ affinity is invariably too low. Moreover, least-squares minimization of multisite systems may not afford a unique fit because of strong parameter correlations. This chapter outlines a strategy for analyzing two-site systems that overcomes these obstacles. The method--which involves simultaneous, or global, least-squares analysis of direct and competitive ITC data--yields binding parameters for both Ca2+ and Mg2+. Application of the method is demonstrated for two systems. The S55D/E59D variant of rat alpha-parvalbumin, noteworthy for its elevated metal ion affinity, binds divalent ions noncooperatively and is amenable to analysis using an independent two-site model. On the other hand, Phl p 7, a pollen-specific EF-hand protein from timothy grass, binds Ca2+ with positive cooperativity. Divalent ion-binding data for the protein must be analyzed using a two-site Adair model.

  18. Asymmetric cation-binding catalysis

    DEFF Research Database (Denmark)

    Oliveira, Maria Teresa; Lee, Jiwoong


    and KCN, are selectively bound to the catalyst, providing exceptionally high enantioselectivities for kinetic resolutions, elimination reactions (fluoride base), and Strecker synthesis (cyanide nucleophile). Asymmetric cation-binding catalysis was recently expanded to silicon-based reagents, enabling...... solvents, thus increasing their applicability in synthesis. The expansion of this concept to chiral polyethers led to the emergence of asymmetric cation-binding catalysis, where chiral counter anions are generated from metal salts, particularly using BINOL-based polyethers. Alkali metal salts, namely KF...

  19. Higher cytotoxicity of divalent antibody-toxins than monovalent antibody-toxins

    Energy Technology Data Exchange (ETDEWEB)

    Won, JaeSeon; Nam, PilWon; Lee, YongChan [College of Life Sciences and Graduate School of Biotechnology, Korea University, 5-ga Anam-dong, Sungbuk-gu, Seoul 136-701 (Korea, Republic of); Choe, MuHyeon, E-mail: [College of Life Sciences and Graduate School of Biotechnology, Korea University, 5-ga Anam-dong, Sungbuk-gu, Seoul 136-701 (Korea, Republic of)


    Recombinant antibody-toxins are constructed via the fusion of a 'carcinoma-specific' antibody fragment to a toxin. Due to the high affinity and high selectivity of the antibody fragments, antibody-toxins can bind to surface antigens on cancer cells and kill them without harming normal cells [L.H. Pai, J.K. Batra, D.J. FitzGerald, M.C. Willingham, I. Pastan, Anti-tumor activities of immunotoxins made of monoclonal antibody B3 and various forms of Pseudomonas exotoxin, Proc. Natl. Acad. Sci. USA 88 (1991) 3358-3362]. In this study, we constructed the antibody-toxin, Fab-SWn-PE38, with SWn (n = 3, 6, 9) sequences containing n-time repeated (G{sub 4}S) between the Fab fragment and PE38 (38 kDa truncated form of Pseudomonas exotoxin A). The SWn sequence also harbored one cysteine residue that could form a disulfide bridge between two Fab-SWn-PE38 monomers. We assessed the cytotoxicity of the monovalent (Fab-SWn-PE38), and divalent ([Fab-SWn-PE38]{sub 2}) antibody-toxins. The cytotoxicity of the dimer against the CRL1739 cell line was approximately 18.8-fold higher than that of the monomer on the ng/ml scale, which was approximately 37.6-fold higher on the pM scale. These results strongly indicate that divalency provides higher cytotoxicity for an antibody-toxin.

  20. Photo-bleaching effect in divalent samarium-doped alkaline-earth fluorohalides

    Energy Technology Data Exchange (ETDEWEB)

    Qin, Weiping [Chinese Academy of Sciences, Changchun (China); Jang, Kiwan; Cho, Hyungab; Chung, Yonghwa; Park, Seongtae; Lee, Yongill [Changwon National University, Changwon (Korea, Republic of); Kim, Changdae [Mokpo National University, Mokpo (Korea, Republic of)


    When a CW laser was focused on a sample of divalent samarium-doped alkaline-earth fluorohalides (Mg{sub 0.5}Sr{sub 0.5}FCl{sub 0.5}Br{sub 0.5} : Sm{sup 2+} or BaFCl{sub 0.5}Br{sub 0.5} : Sm{sup 2+}), the fluorescence intensity of Sm{sup +2} ions decreased rapidly. Under irradiation from a 488-nm laser with a power density of 10 W/cm{sup 2}, the intensity of the {sup 5}D{sub 0} -> {sup 7}F{sub 0} (Sm{sup 2+}) emission decreased as much as 96 % of its initial intensity in 30 minutes (for an X-ray-reduced sample). The so-called photo-bleaching effect can be influenced by the processes used for sample synthesis, such as the reduction method, the grinding process or X-ray irradiation. The decreasing curves obtained in the photo-bleaching experiments were fitted, a biexponential decreasing mode was found, which included a fast decrease (time constant {approx}tens of seconds) and a slow decrease (time constant {approx}hundreds of seconds). There was no evidence to support the divalent samarium ions being photo-ionized into trivalent samarium ions in the photobleaching process. The most probable mechanism for the photo-bleaching effect involves structural defects and color centers in the samples.

  1. Kinetics studies with fruit bromelain (Ananas comosus) in the presence of cysteine and divalent ions. (United States)

    Kaur, Tajwinder; Kaur, Amandeep; Grewal, Ravneet K


    The kinetics of cysteine and divalent ion modulation viz. Ca(2+), Cu(2+), Hg(2+) of fruit bromelain (EC have been investigated in the present study. Kinetic studies revealed that at pH 4.5, cysteine induced V-type activation of bromelain catalyzed gelatin hydrolysis. At pH 3.5, Ca(2+) inhibited the enzyme noncompetitively, whereas, both K-and V-type activations of bromelain were observed in the presence of 0.5 mM Ca(2+) at pH 4.5 and 7.5. Bromelain was inhibited competitively at 0.6 mM Cu(2+) ions at pH 3.5, which changed to an uncompetitive inhibition at pH 4.5 and 7.5. An un-competitive inhibition of bromelain catalyzed gelatin hydrolysis was observed in the presence of 0.6 mM Hg(2+) at pH 3.5 and 4.5. These findings suggest that divalent ions modulation of fruit bromelain is pH dependent.

  2. Predicting 3D structure, flexibility and stability of RNA hairpins in monovalent and divalent ion solutions

    CERN Document Server

    Shi, Ya-Zhou; Wang, Feng-Hua; Zhu, Xiao-Long; Tan, Zhi-Jie


    A full understanding of RNA-mediated biology would require the knowledge of three-dimensional (3D) structures, structural flexibility and stability of RNAs. To predict RNA 3D structures and stability, we have previously proposed a three-bead coarse-grained predictive model with implicit salt/solvent potentials. In this study, we will further develop the model by improving the implicit-salt electrostatic potential and involving a sequence-dependent coaxial stacking potential to enable the model to simulate RNA 3D structure folding in divalent/monovalent ion solutions. As compared with the experimental data, the present model can predict 3D structures of RNA hairpins with bulge/internal loops (<77nt) from their sequences at the corresponding experimental ion conditions with an overall improved accuracy, and the model also makes reliable predictions for the flexibility of RNA hairpins with bulge loops of different length at extensive divalent/monovalent ion conditions. In addition, the model successfully pred...

  3. Full-potential KKR-calculations for MgO and divalent impurities in MgO


    Baranov, A. N.; Stepanyuk, V. S.; Hergert, W.; Katsnelson, A. A.; Settels, A.; Zeller, R.; Dederichs, P. H.


    We present a detailed investigation of bulk properties of MgO and lattice relaxations around divalent impurities in MgO by means of the full-potential Korringa-Kohn-Rostoker Green's function method. The local-density approximation and the perturbative generalized gradient corrections are used to calculate the lattice constant and bulk modulus of MgO. We obtain a very good description of the ground properties of MgO. Lattice relaxations around divalent impurities in MgO are determined using an...

  4. Effects of univalent cations on the activity of particulate starch synthetase. (United States)

    Nitsos, R E; Evans, H J


    An investigation was made to determine the univalent cation requirements of starch synthetase from a variety of plant species of economic importance. The particulate enzyme from sweet corn was shown to have an absolute requirement for potassium, with the optimum activation occurring at 0.05 M KCl. Rubidium, cesium, and ammonium were 80% as effective as potassium while sodium and lithium were respectively 21% and 8% as effective as potassium. The K(A) for potassium was determined to be 6 mM. In the case of the particulate starch synthetase from wheat, bush beans, field corn, soybeans, peas, or potatoes, considerable stimulation of enzyme activity was obtained by the addition of potassium to the reaction mixture. In these studies, low enzyme activity was observed in the absence of added potassium, but the content of endogenous univalent cations in the reactions may be sufficient to account for the activities observed. Anions of various types had no effect on starch synthetase activity. Divalent cations produced slight activation in the presence or absence of potassium. All efforts to show a potassium requirement for glycogen synthetase from rat liver have been negative.

  5. Divalent folate modification on PEG: an effective strategy for improving the cellular uptake and targetability of PEGylated polyamidoamine-polyethylenimine copolymer. (United States)

    Cao, Duanwen; Tian, Shouqin; Huang, Huan; Chen, Jianhai; Pan, Shirong


    -(PEG3.4k-FA2)1.72 complexes stronger penetrating ability and higher cellular uptake. With these advantages, PME-(PEG3.4k-FA2)1.72 may be a promising nonviral vector candidate for efficient gene delivery. This study also indicates that divalent folate modification on PEG can serve as an efficient strategy to improve the cellular uptake and targeting ability of PEGylated cationic polymers for gene delivery.

  6. Interaction of Divalent Metal Ions with the Adenosine Triphosphate Measured Using Nuclear Magnetic Resonance

    Institute of Scientific and Technical Information of China (English)


    The interaction of adenosine triphosphate with divalent metal ions is important in biochemical functions. The effects of pH and metal ions Mg2+, Ca2+, Zn2+, Mn2+, and Co2+ on the chemical shift of the phosphate group of ATP have been studied using Nuclear Magnetic Resonance. The chemical shift of the β-phosphate of ATP is the most sensitive to pH. Ca2+ and Mg2+ bind with the α- and β-phosphate groups of ATP. Zn2+ binds to the adenosine ring hydrogen as well as to phosphate. The paramagnetic ions Mn2+ and Co2+ do not cause chemical shifts of the phosphate or proton peak. Mn2+ and Co2+ broaden the resonance peak only.

  7. Polymerization of a divalent/tetravalent metal-storing atom-mimicking dendrimer. (United States)

    Albrecht, Ken; Hirabayashi, Yuki; Otake, Masaya; Mendori, Shin; Tobari, Yuta; Azuma, Yasuo; Majima, Yutaka; Yamamoto, Kimihisa


    The phenylazomethine dendrimer (DPA) has a layer-by-layer electron density gradient that is an analog of the Bohr atom (atom mimicry). In combination with electron pair mimicry, the polymerization of this atom-mimicking dendrimer was achieved. The valency of the mimicked atom was controlled by changing the chemical structure of the dendrimer. By mimicking a divalent atom, a one-dimensional (1D) polymer was obtained, and by using a planar tetravalent atom mimic, a 2D polymer was obtained. These poly(dendrimer) polymers could store Lewis acids (SnCl2) in their unoccupied orbitals, thus indicating that these poly(dendrimer) polymers consist of a series of nanocontainers.

  8. Research progress in cation-π interactions

    Institute of Scientific and Technical Information of China (English)


    Cation-π interaction is a potent intermolecular interaction between a cation and an aromatic system,which has been viewed as a new kind of binding force,as being compared with the classical interactions(e.g. hydrogen bonding,electrostatic and hydrophobic interactions). Cation-π interactions have been observed in a wide range of biological contexts. In this paper,we present an overview of the typical cation-π interactions in biological systems,the experimental and theoretical investigations on cation-π interactions,as well as the research results on cation-π interactions in our group.

  9. Research progress in cation-π interactions

    Institute of Scientific and Technical Information of China (English)

    CHENG JiaGao; LUO XiaoMin; YAN XiuHua; LI Zhong; TANG Yun; JIANG HuaLiang; ZHU WeiLiang


    Cation-π interaction is a potent intermolecular interaction between a cation and an aromatic system, which has been viewed as a new kind of binding force, as being compared with the classical interac-tions (e.g. hydrogen bonding, electrostatic and hydrophobic interactions). Cation-π interactions have been observed in a wide range of biological contexts. In this paper, we present an overview of the typi-cal cation-π interactions in biological systems, the experimental and theoretical investigations on cation-π interactions, as well as the research results on cation-π interactions in our group.

  10. Hypervalent Nonbonded Interactions of a Divalent Sulfur Atom. Implications in Protein Architecture and the Functions

    Directory of Open Access Journals (Sweden)

    Noriyoshi Isozumi


    Full Text Available In organic molecules a divalent sulfur atom sometimes adopts weak coordination to a proximate heteroatom (X. Such hypervalent nonbonded S···X interactions can control the molecular structure and chemical reactivity of organic molecules, as well as their assembly and packing in the solid state. In the last decade, similar hypervalent interactions have been demonstrated by statistical database analysis to be present in protein structures. In this review, weak interactions between a divalent sulfur atom and an oxygen or nitrogen atom in proteins are highlighted with several examples. S···O interactions in proteins showed obviously different structural features from those in organic molecules (i.e., πO → σS* versus nO → σS* directionality. The difference was ascribed to the HOMO of the amide group, which expands in the vertical direction (πO rather than in the plane (nO. S···X interactions in four model proteins, phospholipase A2 (PLA2, ribonuclease A (RNase A, insulin, and lysozyme, have also been analyzed. The results suggested that S···X interactions would be important factors that control not only the three-dimensional structure of proteins but also their functions to some extent. Thus, S···X interactions will be useful tools for protein engineering and the ligand design.

  11. H(+)-coupled divalent metal-ion transporter-1: functional properties, physiological roles and therapeutics. (United States)

    Shawki, Ali; Knight, Patrick B; Maliken, Bryan D; Niespodzany, Eric J; Mackenzie, Bryan


    Divalent metal-ion transporter-1 (DMT1) is a widely expressed, iron-preferring membrane transport protein. Animal models establish that DMT1 plays indispensable roles in intestinal nonheme-iron absorption and iron acquisition by erythroid precursor cells. Rare mutations in human DMT1 result in severe microcytic-hypochromic anemia. When we express DMT1 in RNA-injected Xenopus oocytes, we observe rheogenic Fe(2+) transport that is driven by the proton electrochemical potential gradient. In that same preparation, DMT1 also transports cadmium and manganese but not copper. Whether manganese metabolism relies upon DMT1 remains unclear but DMT1 contributes to the effects of overexposure to cadmium and manganese in some tissues. There exist at least four DMT1 isoforms that arise from variant transcription of the SLC11A2 gene. Whereas these isoforms display identical functional properties, N- and C-terminal variations contain cues that direct the cell-specific targeting of DMT1 isoforms to discrete subcellular compartments (plasma membrane, endosomes, and lysosomes). An iron-responsive element (IRE) in the mRNA 3'-untranslated region permits the regulation of some isoforms by iron status, and additional mechanisms by which DMT1 is regulated are emerging. Natural-resistance-associated macrophage protein-1 (NRAMP1)-the only other member of the mammalian SLC11 gene family-contributes to antimicrobial function by extruding from the phagolysosome divalent metal ions (e.g. Mn(2+)) that may be essential cofactors for bacteria-derived enzymes or required for bacterial growth. The principal or only intestinal nonheme-iron transporter, DMT1 is a validated therapeutic target in hereditary hemochromatosis (HHC) and other iron-overload disorders.

  12. A new strategy to stabilize oxytocin in aqueous solutions : I. The effects of divalent metal ions and citrate buffer

    NARCIS (Netherlands)

    Avanti, Christina; Amorij, Jean-Pierre; Setyaningsih, Dewi; Hawe, Andrea; Jiskoot, Wim; Visser, Jan; Kedrov, Alexej; Driessen, Arnold J. M.; Hinrichs, Wouter L. J.; Frijlink, Henderik W.


    In the current study, the effect of metal ions in combination with buffers (citrate, acetate, pH 4.5) on the stability of aqueous solutions of oxytocin was investigated. Both monovalent metal ions (Na+and K+) and divalent metal ions (Ca2+, Mg2+, and Zn2+) were tested all as chloride salts. The effec

  13. Divalent metals stabilize cellular prion proteins and alter the rate of proteinase-K dependent limited proteolysis (United States)

    Background: The key biochemical event in the pathogenesis of prion diseases is the conversion of normal cellular prion proteins (PrP**c) to the proteinase K (PK) resistant, abnormal form (PrP**sc); however, the cellular mechanisms underlying the conversion remain enigmatic. Binding of divalent ca...

  14. Divalent metal ion differentially regulates the sequential nicking reactions of the GIY-YIG homing endonuclease I-BmoI.

    Directory of Open Access Journals (Sweden)

    Benjamin P Kleinstiver

    Full Text Available Homing endonucleases are site-specific DNA endonucleases that function as mobile genetic elements by introducing double-strand breaks or nicks at defined locations. Of the major families of homing endonucleases, the modular GIY-YIG endonucleases are least understood in terms of mechanism. The GIY-YIG homing endonuclease I-BmoI generates a double-strand break by sequential nicking reactions during which the single active site of the GIY-YIG nuclease domain must undergo a substantial reorganization. Here, we show that divalent metal ion plays a significant role in regulating the two independent nicking reactions by I-BmoI. Rate constant determination for each nicking reaction revealed that limiting divalent metal ion has a greater impact on the second strand than the first strand nicking reaction. We also show that substrate mutations within the I-BmoI cleavage site can modulate the first strand nicking reaction over a 314-fold range. Additionally, in-gel DNA footprinting with mutant substrates and modeling of an I-BmoI-substrate complex suggest that amino acid contacts to a critical GC-2 base pair are required to induce a bottom-strand distortion that likely directs conformational changes for reaction progress. Collectively, our data implies mechanistic roles for divalent metal ion and substrate bases, suggesting that divalent metal ion facilitates the re-positioning of the GIY-YIG nuclease domain between sequential nicking reactions.

  15. A new strategy to stabilize oxytocin in aqueous solutions: I. The effects of divalent metal ions and citrate buffer. (United States)

    Avanti, Christina; Amorij, Jean-Pierre; Setyaningsih, Dewi; Hawe, Andrea; Jiskoot, Wim; Visser, Jan; Kedrov, Alexej; Driessen, Arnold J M; Hinrichs, Wouter L J; Frijlink, Henderik W


    In the current study, the effect of metal ions in combination with buffers (citrate, acetate, pH 4.5) on the stability of aqueous solutions of oxytocin was investigated. Both monovalent metal ions (Na(+) and K(+)) and divalent metal ions (Ca(2+), Mg(2+), and Zn(2+)) were tested all as chloride salts. The effect of combinations of buffers and metal ions on the stability of aqueous oxytocin solutions was determined by RP-HPLC and HP-SEC after 4 weeks of storage at either 4°C or 55°C. Addition of sodium or potassium ions to acetate- or citrate-buffered solutions did not increase stability, nor did the addition of divalent metal ions to acetate buffer. However, the stability of aqueous oxytocin in aqueous formulations was improved in the presence of 5 and 10 mM citrate buffer in combination with at least 2 mM CaCl(2), MgCl(2), or ZnCl(2) and depended on the divalent metal ion concentration. Isothermal titration calorimetric measurements were predictive for the stabilization effects observed during the stability study. Formulations in citrate buffer that had an improved stability displayed a strong interaction between oxytocin and Ca(2+), Mg(2+), or Zn(2+), while formulations in acetate buffer did not. In conclusion, our study shows that divalent metal ions in combination with citrate buffer strongly improved the stability of oxytocin in aqueous solutions.


    The divalent metal transporter-1 (DMT1) participates in the detoxification of metals that can damage lung epithelium. Elevated iron levels increase the expression of DMT1 in bronchial epithelial cells stimulating its uptake and storage in ferritin, thus making iron unavailable t...

  17. Changes in Specific Surface as observed by NMR, caused by saturation of Chalk with porewater bearing divalent Ions

    DEFF Research Database (Denmark)

    Katika, Konstantina; Addassi, Mouadh; Alam, Mohammad Monzurul


    depositional textures. We compared two cases. The first experiments on outcrop chalk with high salinity brines showed that saturation with divalent ions (Mg2+,Ca2+and SO42-) cause major shifts in the T2 distribution curve, probably due to precipitation in the pore space. In a second set of experiments, fluid...

  18. Influence of therapy with metformin on the concentration of certain divalent cations in patients with non-insulin-dependent diabetes mellitus. (United States)

    Doşa, Monica Daniela; Hangan, Laurentiu-Tony; Crauciuc, Eduard; Galeş, Cristina; Nechifor, Mihai


    Research was performed on a group of 30 patients with non-insulin-dependent diabetes mellitus (NIDDM), who never received antidiabetic medication before, and on a group of 17 healthy adults. The patients were administered treatment with metformin, 1,000 mg/day. Plasmatic and urinary concentration of magnesium have been measured, copper and zinc along with the concentrations of glucose, HDL, LDL, cholesterol, tryglicerides, HbA1c, and total erythrocyte magnesium, in advance and after 3 months of treatment. Data showed significant differences in the NIDDM group vs the control group: for plasma magnesium-1.95 ± 0.19 vs 2.20 ± 0.18 mg/dl, p zinc-67.56 ± 6.21 vs 98.41 ± 20.47 μg/dl, p zinc-1,347.54 ± 158.24 vs 851.65 ± 209.75 μg/24 h, p zinc was inversely correlated with glycemia (r = -0.399, p = 0.029). Our data show a significant action of metformin therapy, by increasing the total intraerythrocyte magnesium concentration and decreasing the urinary magnesium elimination, positively correlated with the decrease of glycemia and HbA1c in NIDDM patients.

  19. Redox-active on-surface polymerization of single-site divalent cations from pure metals by a ketone-functionalized phenanthroline

    Energy Technology Data Exchange (ETDEWEB)

    Skomski, Daniel; Tempas, Christopher D.; Bukowski, Gregory S.; Smith, Kevin A.; Tait, Steven L., E-mail: [Department of Chemistry, Indiana University, 800 E. Kirkwood Ave., Bloomington, Indiana 47405 (United States)


    Metallic iron, chromium, or platinum mixing with a ketone-functionalized phenanthroline ligand on a single crystal gold surface demonstrates redox activity to a well-defined oxidation state and assembly into thermally stable, one dimensional, polymeric chains. The diverging ligand geometry incorporates redox-active sub-units and bi-dentate binding sites. The gold surface provides a stable adsorption environment and directs growth of the polymeric chains, but is inert with regard to the redox chemistry. These systems are characterized by scanning tunnelling microscopy, non-contact atomic force microscopy, and X-ray photoelectron spectroscopy under ultra-high vacuum conditions. The relative propensity of the metals to interact with the ketone group is examined, and it is found that Fe and Cr more readily complex the ligand than Pt. The formation and stabilization of well-defined transition metal single-sites at surfaces may open new routes to achieve higher selectivity in heterogeneous catalysts.

  20. Comprehensive analysis of changes in clinically significant divalent serum cation levels during automated plateletpheresis in healthy donors in a tertiary care center in North India

    Directory of Open Access Journals (Sweden)

    Archana Solanki


    Full Text Available Background: Adverse effects due to apheresis are unusual. The most common apheresis-specific reaction is hypocalcemia due to citrate anticoagulation and induces ionized hypocalcemia and hypomagnesemia by chelating effect during the plateletpheresis; generally transient and self-limiting but has the potential of severely injuring donor. We have investigated total calcium (tCa ++ and magnesium (tMg ++ levels in sixty healthy plateletpheresis donors at different intervals during the procedure and 30 min post-procedure. Materials and Methods: A total of 60 procedures were performed on healthy donors. Blood samples were obtained from sterile diversion pouch placed on apheresis circuit. 5 ml sample in plain vials was obtained at different intervals during each procedure and 30 min after the end of the procedure. Samples were used for measurement of tCa ++ and tMg ++ levels. Results: There is continuous decrease in mean tCa ++ from baseline levels (9.83 ± 0.64 mg/dl till end of procedure (8.33 ± 0.78 mg/dl, but after 30 min, levels again reached near their respective baseline values (9.42 ± 0.54 mg/dl. Similarly, mean tMg ++ fell from baseline levels (2.36 ± 0.3 mg/dl till the end of procedure (1.39 ± 0.40 mg/dl. After 30 min, levels were again increased, their respective baseline values (2.25 ± 0.25 mg/dl. Conclusion: There is continuous, gradual, and significant fall (P < 0.05 in mean tCa ++ and mean tMg ++ from baseline levels to till the end of procedure but after 30 min of completion of procedure, levels again reached near their respective baseline values.

  1. Flexibility of the Zeolite RHO Framework in Situ X-Ray and Neutron Powder Structural Characterizations of Divalent Cation-Exchanged Zeolite RHO (United States)


    15 The equipment was designed for in situ structural studies of gas/liquid/solid and solid/solid interactions in the interval of 0 to 1 000C. The...defined constraints are used. These constraints are best obtained from experiemtnal observations such as those available over the wide range of zeolite

  2. Solubilization of immune complexes in complement factor deficient sera and the influence of temperature, ionic strength and divalent cations on the solubilization reaction

    DEFF Research Database (Denmark)

    Baatrup, Gunnar; Petersen, Ivan; Svehag, Svend-Erik;


    The complement-mediated solubilization (CMS) of immune complexes (IC) and the initial kinetics (IKS) of this reaction in human sera depleted of or deficient in C2, C3, C8, factors B, P and I were investigated. Sera depleted of B or P and those lacking native C3 or factor I showed virtually no CMS...... by a radioassay and kinetic data for the binding of C3b to preformed immune complexes. The CMS capacity reached maximum at 39-41 degrees C and at an ionic strength of approximately 0.20 mu. Selective chelation of Mg2+ completely abolished the CMS of IC. Maximal CMS was observed at Mg2+ concentration of about 2m...

  3. The adjuvant mechanism of cationic dimethyldioctadecylammonium liposomes

    DEFF Research Database (Denmark)

    Korsholm, Karen Smith; Agger, Else Marie; Foged, Camilla;


    Cationic liposomes are being used increasingly as efficient adjuvants for subunit vaccines but their precise mechanism of action is still unknown. Here, we investigated the adjuvant mechanism of cationic liposomes based on the synthetic amphiphile dimethyldioctadecylammonium (DDA). The liposomes ...

  4. Tripodal Receptors for Cation and Anion Sensors

    NARCIS (Netherlands)

    Kuswandi, Bambang; Nuriman,; Verboom, Willem; Reinhoudt, David N.


    This review discusses different types of artificial tripodal receptors for the selectiverecognition and sensing of cations and anions. Examples on the relationship between structure andselectivity towards cations and anions are described. Furthermore, their applications as potentiometricion sensing

  5. Prepared polymethacrylate-based monoliths for the separation of cations by non-suppressed capillary ion chromatography. (United States)

    Li, Jing; Zhu, Yan


    This paper describes a novel analytical system for non-suppressed capillary ion chromatography. Methacrylate monolithic columns were prepared from silanized fused-silica capillaries of 320 µm i.d. by in situ polymerization of glycidyl methacrylate and ethylene dimethacrylate in the presence of 1,4-butanediol, 1-propanol and water as the porogen solvents. The introduction of cation-exchange sites was achieved by sulfonating the matrix with sodium sulfite to produce total cation-exchange capacities in the range of 45-105 μequiv/mL for a 25 cm column. The conditions (concentrations of sodium sulfite solution, reacting time and modified flow rate) of sulfonation were optimized. The hydrodynamic and chromatographic performances were estimated. Coupled with a conductivity detector, a capillary ion chromatography system was set up with the prepared column. Finally, the resultant column was used for the separations of five common univalent cations (Li(+), Na(+), NH4(+), K(+) and Cs(+)) using methanesulfonic acid as the eluent and four divalent cations (Mg(2+), Ca(2+), Sr(2+) and Ba(2+)) by non-suppressed capillary ion chromatography; the chromatographic parameters were further researched.

  6. A Versatile Strategy for Production of Membrane Proteins with Diverse Topologies: Application to Investigation of Bacterial Homologues of Human Divalent Metal Ion and Nucleoside Transporters.

    Directory of Open Access Journals (Sweden)

    Cheng Ma

    Full Text Available Membrane proteins play key roles in many biological processes, from acquisition of nutrients to neurotransmission, and are targets for more than 50% of current therapeutic drugs. However, their investigation is hampered by difficulties in their production and purification on a scale suitable for structural studies. In particular, the nature and location of affinity tags introduced for the purification of recombinant membrane proteins can greatly influence their expression levels by affecting their membrane insertion. The extent of such effects typically depends on the transmembrane topologies of the proteins, which for proteins of unknown structure are usually uncertain. For example, attachment of oligohistidine tags to the periplasmic termini of membrane proteins often interferes with folding and drastically impairs expression in Escherichia coli. To circumvent this problem we have employed a novel strategy to enable the rapid production of constructs bearing a range of different affinity tags compatible with either cytoplasmic or periplasmic attachment. Tags include conventional oligohistidine tags compatible with cytoplasmic attachment and, for attachment to proteins with a periplasmic terminus, either tandem Strep-tag II sequences or oligohistidine tags fused to maltose binding protein and a signal sequence. Inclusion of cleavage sites for TEV or HRV-3C protease enables tag removal prior to crystallisation trials or a second step of purification. Together with the use of bioinformatic approaches to identify members of membrane protein families with topologies favourable to cytoplasmic tagging, this has enabled us to express and purify multiple bacterial membrane transporters. To illustrate this strategy, we describe here its use to purify bacterial homologues of human membrane proteins from the Nramp and ZIP families of divalent metal cation transporters and from the concentrative nucleoside transporter family. The proteins are expressed in

  7. Evaluation of effects of bivalent cations on the formation of purine-rich triple-helix DNA by ESI-FT-MS. (United States)

    Wan, Cuihong; Cui, Meng; Song, Fengrui; Liu, Zhiqiang; Liu, Shuying


    The GGA triplet repeats are widely dispersed throughout eukaryotic genomes. (GGA)n or (GGT)n oligonucleotides can interact with double-stranded DNA containing (GGA:CCT)n to form triple-stranded DNA. The effects of 8 divalent metal ions (3 alkaline-earth metals and 5 transition metals) on formation of these purine-rich triple-helix DNA were investigated by electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry (ESI-FT-MS). In the absence of metal ions, no triplex but single-strand, duplex, and purine homodimer ions were observed in mass spectra. The triple-helix DNA complexes were observed only in the presence of certain divalent ions. The effects of different divalent cations on the formation of purine-rich triplexes were compared. Transition-metal ions, especially Co(2+) and Ni(2+), significantly boost the formation of triple-helix DNA, whereas alkaline-earth metal ions have no positive effects on triplex formation. In addition, Ba(2+) is notably beneficial to the formation of homodimer instead of triplex.

  8. Highly Tunable Colloidal Perovskite Nanoplatelets through Variable Cation, Metal, and Halide Composition. (United States)

    Weidman, Mark C; Seitz, Michael; Stranks, Samuel D; Tisdale, William A


    Colloidal perovskite nanoplatelets are a promising class of semiconductor nanomaterials-exhibiting bright luminescence, tunable and spectrally narrow absorption and emission features, strongly confined excitonic states, and facile colloidal synthesis. Here, we demonstrate the high degree of spectral tunability achievable through variation of the cation, metal, and halide composition as well as nanoplatelet thickness. We synthesize nanoplatelets of the form L2[ABX3]n-1BX4, where L is an organic ligand (octylammonium, butylammonium), A is a monovalent metal or organic molecular cation (cesium, methylammonium, formamidinium), B is a divalent metal cation (lead, tin), X is a halide anion (chloride, bromide, iodide), and n-1 is the number of unit cells in thickness. We show that variation of n, B, and X leads to large changes in the absorption and emission energy, while variation of the A cation leads to only subtle changes but can significantly impact the nanoplatelet stability and photoluminescence quantum yield (with values over 20%). Furthermore, mixed halide nanoplatelets exhibit continuous spectral tunability over a 1.5 eV spectral range, from 2.2 to 3.7 eV. The nanoplatelets have relatively large lateral dimensions (100 nm to 1 μm), which promote self-assembly into stacked superlattice structures-the periodicity of which can be adjusted based on the nanoplatelet surface ligand length. These results demonstrate the versatility of colloidal perovskite nanoplatelets as a material platform, with tunability extending from the deep-UV, across the visible, into the near-IR. In particular, the tin-containing nanoplatelets represent a significant addition to the small but increasingly important family of lead- and cadmium-free colloidal semiconductors.

  9. Using Mössbauer spectroscopy to choose the sites that can be occupied by divalent tin (United States)

    Dénès, Georges; Merazig, Hocine; Muntasar, Abdualhafed


    Mössbauer spectroscopy can be a useful structural tool to assist crystallographic methods for site assignment when the compound under investigation contains divalent tin. The goal of this work was to show that the structure of tin(II) fluoride, also know as stannous fluoride, SnF2, could have been solved 14 years earlier if Mössbauer spectroscopic results, already known, had been used. A first attempt to solve the crystal structure, carried out by Bergerhoff in 1962 seemed to find the tin positions, however, it failed to find the positions of fluorine. Further extensive studies by Dénès et al. in the mid 1970s yielded the same results as those of Bergerhoff, despite the use of a Nonius CAD-4 automatic diffractometer, in contrast with Bergerhoff's film work. The tin positions yielded a residual of 0.23, and Fourier difference maps showed significant electron density that could be fluorine atoms, however, their number did not match the number of fluorine atoms expected and several F-F distances were way too short. In addition, refinement using these possible fluorine positions led to no improvement of the residual factor. Finally, the crystal structure was published by McDonald et al. in 1976. It was found that the tin sublattice determined by Bergerhoff was basically correct, except that half of the tin atoms found by Bergerhoff to be on the (4b) and (4e) special Wyckoff sites were actually on the (8f) general site. A translation of the origin of the unit-cell by the [1/8, 0, 3/16] vector allows to change the tin Wyckoff sites from (4b), (4e) and (8f) to two (8f) sites, while keeping the basic spatial distribution of tin. A method has now been designed, using 119Sn Mössbauer spectroscopy, to test the suitability of some Wyckoff sites for divalent tin, using the Mössbauer spectrum. The tin(II) doublet ( δ = 3.430(3) mm/s, Δ = 1.532(3) mm/s) shows that the lone pair is on a hybrid orbital, therefore, it is stereoactive, and it results that tin cannot be on

  10. Crystal Structure and Conformational Change Mechanism of a Bacterial Nramp-Family Divalent Metal Transporter. (United States)

    Bozzi, Aaron T; Bane, Lukas B; Weihofen, Wilhelm A; Singharoy, Abhishek; Guillen, Eduardo R; Ploegh, Hidde L; Schulten, Klaus; Gaudet, Rachelle


    The widely conserved natural resistance-associated macrophage protein (Nramp) family of divalent metal transporters enables manganese import in bacteria and dietary iron uptake in mammals. We determined the crystal structure of the Deinococcus radiodurans Nramp homolog (DraNramp) in an inward-facing apo state, including the complete transmembrane (TM) segment 1a (absent from a previous Nramp structure). Mapping our cysteine accessibility scanning results onto this structure, we identified the metal-permeation pathway in the alternate outward-open conformation. We investigated the functional impact of two natural anemia-causing glycine-to-arginine mutations that impaired transition metal transport in both human Nramp2 and DraNramp. The TM4 G153R mutation perturbs the closing of the outward metal-permeation pathway and alters the selectivity of the conserved metal-binding site. In contrast, the TM1a G45R mutation prevents conformational change by sterically blocking the essential movement of that helix, thus locking the transporter in an inward-facing state.

  11. Syntheses and structures of dinuclear double-stranded helicates of divalent manganese, iron, cobalt, and zinc. (United States)

    Reid, Stuart D; Blake, Alexander J; Wilson, Claire; Love, Jason B


    The syntheses and solid-state and solution structures of a series of unusually volatile, charge neutral, [4 + 4] double-stranded helical complexes of divalent manganese, iron, cobalt, and zinc are described. Deprotonation of the N4-donor iminopyrrole ligand H2L by KH cleanly generates the salt K2(THF)2L, which displays both sigma and pi interactions between K and iminopyrrolyl fragments in the X-ray crystal structure. Transamination, salt elimination, and protonolysis reactions were found to be versatile and, in general, high-yielding routes to the dinuclear double helicates [M2(L)2] (M = Mn, Fe, Co, and Zn). These compounds are isomorphous in the solid state by X-ray crystallography and adopt dinuclear cleft motifs as a result of pi stacking between opposing iminopyrrolyl fragments. This motif was also observed in the solution structures of [Fe2(L)2] and [Zn2(L)2] below 230 and 200 K, respectively (DeltaG++ = approximately 46 and 39.0 kJ mol(-1), respectively).

  12. Photochemical reactions of divalent mercury with thioglycolic acid: formation of mercuric sulfide particles. (United States)

    Si, Lin; Ariya, Parisa A


    Mercury (Hg) is a key toxic global pollutant. Studies in aquatic environment have suggested that thiols could be important for mercury speciation. Thioglycolic acid has been detected in various natural water systems and used as a model compound to study the complicated interaction between mercury and polyfunctional dissolved organic matter (DOM). We herein presented the first evidence for mercury particle formation during kinetic and product studies on the photochemistry of divalent mercury (Hg(2+)) with thioglycolic acid at near environmental conditions. Mercuric sulfide (HgS) particles formed upon photolysis were identified by high-resolution transmission electron microscopy coupled with energy dispersive spectrometry and select area electron diffraction. Kinetic data were obtained using UV-visible spectrophotometry and cold vapour atomic fluorescent spectrometry. The apparent first-order reaction rate constant under our experimental conditions was calculated to be (2.3±0.4)×10(-5) s(-1) at T=296±2 K and pH 4.0. It was found that (89±3)% of the reactants undergo photoreduction to generate elemental mercury (Hg(0)). The effects of ionic strengths, pH and potassium ion were also investigated. The formation of HgS particles pointed to the possible involvement of heterogeneous processes. Our kinetic results indicated the importance of weak binding sites on DOM to Hg in photoreduction of Hg(2+) to Hg(0). The potential implications of our data on environmental mercury transformation were discussed.

  13. Thermodynamic perturbation theory for self-assembling mixtures of divalent single patch colloids. (United States)

    Marshall, Bennett D; Chapman, Walter G


    In this work we extend Wertheim's thermodynamic perturbation theory (TPT) to binary mixtures (species A and species B) of patchy colloids were each species has a single patch which can bond a maximum of twice (divalent). Colloids are treated as hard spheres with a directional conical association site. We restrict the system such that only patches between unlike species share attractions; meaning there are AB attractions but no AA or BB attractions. The theory is derived in Wertheim's two density formalism for one site associating fluids. Since the patches are doubly bondable, associated chains, of all chain lengths, as well as 4-mer rings consisting of two species A and two species B colloids are accounted for. With the restriction of only AB attractions, triatomic rings of doubly bonded colloids, which dominate in the corresponding pure component case, cannot form. The theory is shown to be in good agreement with Monte Carlo simulation data for the structure and thermodynamics of these patchy colloid mixtures as a function of temperature, density, patch size and composition. It is shown that 4-mer rings dominate at low temperature, inhibiting the polymerization of the mixture into long chains. Mixtures of this type have been recently synthesized by researchers. This work provides the first theory capable of accurately modeling these mixtures.

  14. New 14-membered octaazamacrocyclic complexes of divalent transition metal ions with their antimicrobial and spectral studies (United States)

    Singh, D. P.; Kumar, Krishan; Sharma, Chetan


    A novel series of macrocyclic complexes of the type [M(C 18H 14N 10S 2)X 2]; where M = Co(II), Ni(II), Cu(II), Zn(II) and Cd(II); X = Cl -, NO 3-, CH 3COO - has been synthesized by [2+2] condensation of thiocarbohydrazide and isatin in the presence of divalent metal salts in methanolic medium. The complexes have been characterized with the help of elemental analyses, conductance measurements, magnetic measurements, electronic, NMR and infrared spectral studies. The low value of molar conductance indicates them to be non-electrolytes. On the basis of various studies a distorted octahedral geometry may be proposed for all of these complexes. These metal complexes were also tested for their in vitro antimicrobial activities against some Gram-positive bacteria viz. Staphylococcus aureus, Bacillus subtilis, and some Gram-negative bacteria Escherichia coli, Pseudomonas aeruginosa and some fungal strains Aspergillus niger, Aspergillus flavus (molds), Candida albicans, Saccharomyces cerevisiae (yeasts). The results obtained were compared with standard antibiotic: Ciprofloxacin and the standard antifungal drug: Amphotericin-B.

  15. The characteristics of action potential and nonselective cation current of cardiomyocytes in rabbit superior vena cava

    Institute of Scientific and Technical Information of China (English)

    WANG Pan; YANG XinChun; LIU XiuLan; BAO RongFeng; LIU TaiFeng


    As s special focus in initiating and maintaining atrial fibrillation (AF), cardiomyocytes in superior vena cavs (SVC) have distinctive electrophysiological characters. In this study, we found that comparing with the right atrial (RA) cardiomyoctyes, the SVC cardiomyoctyes had longer APD90 at the different basic cycle lengths; the conduction block could be observed on both RA and SVC cardiomyoctyes. A few of SVC cardiomyoctyes showed slow response action potentials with automatic activity and some others showed early afterdepolarization (EAD) spontaneously. Further more, we found that there are nonselective cation current (INs) in both SVC and RA cardiomyocytes. The peak density of INs in SVC cardiomyocytes was smaller than that in RA cardiomyocytes. Removal of extracellular divalent cation and glucose could increase INs in SVC cardiomyocytes. The agonist or the antagonist of INs may increase or decrease APD. To sum up, some SVC cardiomyocytes possess the ability of spontaneous activity; the difference of transmembrane action potentials between SVC and RA cardiomyocytes is partly because of the different density of INs between them; the agonist or the antagonist of INs can increase or decrease APD leading to the enhancement or reduction of EAD genesis in SVC cardiomyocytes. INs in rabbit myocytes is fairly similar to TRPC3 current in electrophysiological property, which might play an important role in the mechanisms of AF.

  16. The Free Tricoordinated Silyl Cation Problem

    Directory of Open Access Journals (Sweden)

    Čičak, H.


    Full Text Available As the importance and abundance of silicon in our environment is large, it has been thought that silicon might take the place of carbon in forming a host of similar compounds and silicon-based life. However, until today there is no experimental evidence for such a hypothesis and carbon is still unique among the elements in the vast number and variety of compounds it can form. Also, the corresponding derivatives of the two elements show considerable differences in their chemical properties.The essential debate concerning organosilicon chemistry relates to the existence of the free planar tricoordinated silyl cations in condensed phase (R3Si+, in analogy to carbocations (R3C+ which have been known and characterized as free species. Although silyl cations are thermodynamically more stable than their carbon analogs, they are very reactive due to their high inherent electrophilicity and the ability of hypervalent coordination. On the other hand, stabilization by inductive and hyperconjugative effects and larger steric effects of carbocations make them less sensitive to solvation or other environmental effects than silyl cations. Hence, observation of free silyl cations in the condensed phase proved extremely difficult and the actual problem is the question of the degree of the (remaining silyl cation character.The first free silyl cation, trimesitylsilyl cation, and in analogy with it tridurylsilyl cation, were synthesized by Lambert et al. Free silyl cations based on analogy to aromatic ions (homocyclopropenylium and tropylium have also been prepared. However, in these silyl cations the cationic character is reduced by internal π -conjugation. Čičak et al. prepared some silyl-cationic intermediates (Me3Si--CH≡CR+in solid state. With the help of quantum-mechanical calculations it was concluded that these adducts have much more silyl cation than carbocation character.

  17. Biophysical studies of the interaction of squalamine and other cationic amphiphilic molecules with bacterial and eukaryotic membranes: importance of the distribution coefficient in membrane selectivity. (United States)

    Di Pasquale, Eric; Salmi-Smail, Chanaz; Brunel, Jean-Michel; Sanchez, Patrick; Fantini, Jacques; Maresca, Marc


    The interaction of squalamine (SQ) with eukaryotic and prokaryotic membranes was studied and compared with the interaction of two other cationic amphipathic antimicrobials (CAAs), i.e. the antibiotic polymyxin B (PMB) and the detergent hexadecyltrimethylammonium bromide (CTAB). Whole cell experiments showed that the three CAA have in common the ability to interact with lipopolysaccharide-containing membranes through a divalent cation sensitive process. Differences were found regarding their kinetics of membrane permeabilisation and their selectivity for bacteria, with a preferential permeabilisation of bacteria by PMB>SQ and no selectivity for CTAB. Experiments with lipid monolayers and bilayers showed that this selectivity did not correlate with a preferential interaction of the CAAs with lipids but rather relies on differences in their ability to penetrate lipid bilayers and to cause electrically active lesions. Incidentally, our results also suggest that the distribution coefficient of CAAs could be used to predict their selectivity for bacteria.

  18. Concentration of cations in different parts of male reproductive system and their influence on in vitro sperm motility in lizard, Mabuya carinata Schneider. (United States)

    Aranha, Ivan; Bhagya, M; Yajurvedi, H N


    Concentrations of mono- and divalent cations in the testis, three different regions of the epididymis and the vas deferens of lizard, M. carinata were determined. The concentrations of Na+, K+ and Ca2+ increased gradually from testis to vas deferens. However, no significant variation in the levels of Mg2+ was observed between testis and anterior epididymis, and between posterior epididymis and vas deferens. Further, in an in vitro sperm motility study, wherein different concentrations of the cations were tested, the maximum forward progressive motility of posterior epididymal spermatozoa was observed following treatment with 140 mMNaCl, 25 mM KCl, and 50 mM CaCl2 whereas, treatment with magnesium brought about a decrease in sperm motility. The results indicate that Na+, K+, and Ca2+ have stimulatory effect at an optimum dose, whereas Mg2+ has an inhibitory effect even at very low concentration, on sperm motility in the lizard M carinata.

  19. Interaction of selected divalent metal ions with human ataxin-3 Q36. (United States)

    Stawoska, Iwona; Wesełucha-Birczyńska, Aleksandra; Regonesi, Maria Elena; Riva, Matteo; Tortora, Paolo; Stochel, Grazyna


    The mode of interaction of ataxin-3 Q36 (AT-3 Q36) with selected endogenous and exogenous metal ions, namely, Zn(2+), Cu(2+), Ni(2+), and Cd(2+), was examined. Metal-ion-induced structural changes of the protein were monitored by fluorescence as well as Fourier transform Raman spectroscopy. We found that the cations tested lead to a decrease in alpha-helical content and a concurrent increase in beta-sheet as well as undefined (beta-turn and random-coil) structures. The most evident effect was observed for copper and nickel cations. After titration with these cations, the AT3 Q36 secondary structure content (27% alpha-helices in the presence of either ion, 31 and 27% beta-sheets for Cu(2+) and Ni(2+), respectively) was similar to that observed for the aggregated form of the protein (27% alpha-helices, 36% beta-sheets). Using the 1-anilinonaphthalene-8-sulfonate hydrophobic fluorescence probe, we showed that the presence of the metal ions tested led to the formation of solvent-exposed hydrophobic patches of AT-3 Q36, and that such an effect decreased with increasing ionic radius.

  20. The role of trivalent cations and interlayer anions on the formation of layered double hydroxides in an oxic-CO2 medium (United States)

    Paikaray, Susanta; Hendry, M. Jim


    Most common occurrences of magnesium (Mg2+), aluminum (Al3+), iron (Fe3+), carbonate (CO32-), and sulfate (SO42-) in environmental settings can lead to formation of layered double hydroxides. This study investigated the role of different trivalent cations and divalent interlayer anions on the physicochemical properties of hydrotalcite-like layered double hydroxides. Hydrotalcite-like compounds (HTLCs) were synthesized at ambient temperature by co-precipitation while maintaining Mg2+ as the primary divalent cation and varying Al3+ and Fe3+ as the trivalent cations and SO42- and CO32- as the interlayer anions. X-ray diffractograms, Raman and infrared spectra, and scanning electron microscopy images confirmed the precipitation of rounded fibrous HTLCs. BET analyses showed that the MgAlCO3-type HTLC had the greatest surface area (101.7 m2/g), followed by MgAlSO4 (93.9 m2/g), MgFeCO3 (81.3 m2/g), and MgFeSO4 (17.8 m2/g). Substitution of Fe3+ increased lattice parameters compared to Al3+ substitution. Incorporation of SO42- as an interlayer anion was favored during Fe3+ substitution but reduced the crystallinity of the HTLC. Carbonate was the preferred interlayer anion, but available SO42- occupied the interlayer spaces together with CO32- if a high charge deficiency was maintained during HTLC precipitation. Two major stages of mass loss occurred (≤250 and 250-450 °C) for all the samples with better thermal stability for SO42- vs. CO32- as interlayer anion and Al3+ vs. Fe3+ as trivalent cation.

  1. Characterization of divalent metal metavanadates by 51V magic-angle spinning NMR spectroscopy of the central and satellite transitions. (United States)

    Nielsen, U G; Jakobsen, H J; Skibsted, J


    51V quadrupole coupling and chemical shielding tensors have been determined from 51V magic-angle spinning (MAS) NMR spectra at a magnetic field of 14.1 T for nine divalent metal metavanadates: Mg(VO3)2, Ca(VO3)2, Ca(VO3)(2).4H2O, alpha-Sr(VO3)2, Zn(VO3)2, alpha- and beta-Cd(VO3)2. The manifold of spinning sidebands (ssbs) from the central and satellite transitions, observed in the 15V MAS NMR spectra, have been analyzed using least-squares fitting and numerical error analysis. This has led to a precise determination of the eight NMR parameters characterizing the magnitudes and relative orientations of the quadrupole coupling and chemical shielding tensors. The optimized data show strong similarities between the NMR parameters for the isostructural groups of divalent metal metavanadates. This demonstrates that different types of metavanadates can easily be distinguished by their anisotropic NMR parameters. The brannerite type of divalent metal metavanadates exhibits very strong 51V quadrupole couplings (i.e., CQ = 6.46-7.50 MHz), which reflect the highly distorted octahedral environments for the V5+ ion in these phases. Linear correlations between the principal tensor elements for the 51V quadrupole coupling tensors and electric field gradient tensor elements, estimated from point-monopole calculations, are reported for the divalent metal metavanadates. These correlations are used in the assignment of the NMR parameters for the different crystallographic 51V sites of Ca(VO3)(2).4H2O, Pb(VO3)2, and Ba(VO3)2. For alpha-Sr(VO3)2, with an unknown crystal structure, the 51V NMR data strongly suggest that this metavanadate is isostructural with Ba(VO3)2, for which the crystal structure has been reported. Finally, the chemical shielding parameters for orthovanadates and mono- and divalent metal metavanadates are compared.

  2. Paving the way for the synthesis of a series of divalent actinide complexes: a theoretical perspective. (United States)

    Wu, Q-Y; Lan, J-H; Wang, C-Z; Cheng, Z-P; Chai, Z-F; Gibson, J K; Shi, W-Q


    Recently, the +2 formal oxidation state in soluble molecular complexes for lanthanides (La-Nd, Sm-Lu) and actinides (Th and U) has been discovered [W. J. Evans, et al., J. Am. Chem. Soc., 2011, 133, 15914; J. Am. Chem. Soc., 2012, 134, 8420; J. Am. Chem. Soc., 2013, 135, 13310; Chem. Sci., 2015, 6, 517]. To explore the nature of the bonding and stabilities of the low-valent actinide complexes, a series of divalent actinide species, [AnCp'3](-) (An[double bond, length as m-dash]Th-Am, Cp' = [η(5)-C5H4(SiMe3)](-)) have been investigated in THF solution using scalar relativistic density functional theory. The electronic structures and electron affinity properties were systematically studied to identify the interactions between the +2 actinide ions and Cp' ligands. The ground state electron configurations for the [AnCp'3](-) species are [ThCp'3](-) 6d(2), [PaCp'3](-) 5f(2)6d(1), [UCp'3](-) 5f(3)6d(1), [NpCp'3](-) 5f(5), [PuCp'3](-) 5f(6), and [AmCp'3](-) 5f(7), respectively, according to the MO analysis. The total bonding energy decreases from the Th- to the Am-complex and the electrostatic interactions mainly dominate the bonding between the actinide atom and ligands. The electron affinity analysis suggests that the reduction reaction of AnCp'3→ [AnCp'3](-) should become increasingly facile across the actinide series from Th to Am, in accord with the known An(iii/ii) reduction potentials. This work expands the knowledge on the low oxidation state chemistry of actinides, and further motivates and guides the synthesis of related low oxidation state compounds of 5f elements.

  3. Deposition kinetics of extracellular polymeric substances (EPS) on silica in monovalent and divalent salts. (United States)

    Zhu, Pingting; Long, Guoyu; Ni, Jinren; Tong, Meiping


    The deposition kinetics of extracellular polymeric substances (EPS) on silica surfaces were examined in both monovalent and divalent solutions under a variety of environmentally relevant ionic strength and pH conditions by employing a quartz crystal microbalance with dissipation (DCM-D). Soluble EPS (SEPS) and bound EPS (BEPS) were extracted from four bacterial strains with different characteristics. Maximum favorable deposition rates (k(fa)) were observed for all EPS at low ionic strengths in both NaCl and CaCl2 solutions. With the increase of ionic strength, k(fa) decreased due to the simultaneous occurrence of EPS aggregation in solutions. Deposition efficiency (alpha; the ratio of deposition rates obtained under unfavorable versus corresponding favorable conditions) for all EPS increased with increasing ionic strength in both NaCl and CaCl2 solutions, which agreed with the trends of zeta potentials and was consistent with the classic Derjaguin-Landau-Verwey-Overbeek (DLVO) theory. Comparison of alpha for SEPS and BEPS extracted from the same strain showed that the trends of alpha did not totally agree with trends of zeta potentials, indicating the deposition kinetics of EPS on silica surfaces were not only controlled by DLVO interactions, but also non-DLVO forces. Close comparison of alpha for EPS extracted from different sources showed alpha increased with increasing proteins to polysaccharides ratio. Subsequent experiments for EPS extracted from the same strain but with different proteins to polysaccharides ratios and from activated sludge also showed that alpha were largest for EPS with greatest proteins to polysaccharides ratio. Additional experiments for pure protein and solutions with different pure proteins to pure saccharides ratios further corroborated that larger proteins to polysaccharides ratio resulted in greater EPS deposition.

  4. A Three-Photon Active Organic Fluorophore for Deep Tissue Ratiometric Imaging of Intracellular Divalent Zinc. (United States)

    Philips, Divya Susan; Sreejith, Sivaramapanicker; He, Tingchao; Menon, Nishanth Venugopal; Anees, Palapuravan; Mathew, Jomon; Sajikumar, Sreedharan; Kang, Yuejun; Stuparu, Mihaiela Corina; Sun, Handong; Zhao, Yanli; Ajayaghosh, Ayyappanpillai


    Deep tissue bioimaging with three-photon (3P) excitation using near-infrared (NIR) light in the second IR window (1.0-1.4 μm) could provide high resolution images with an improved signal-to-noise ratio. Herein, we report a photostable and nontoxic 3P excitable donor-π-acceptor system (GMP) having 3P cross-section (σ3 ) of 1.78×10(-80)  cm(6)  s(2)  photon(-2) and action cross-section (σ3 η3 ) of 2.31×10(-81)  cm(6)  s(2)  photon(-2) , which provides ratiometric fluorescence response with divalent zinc ions in aqueous conditions. The probe signals the Zn(2+) binding at 530 and 600 nm, respectively, upon 1150 nm excitation with enhanced σ3 of 1.85×10(-80)  cm(6)  s(2)  photon(-2) and σ3 η3 of 3.33×10(-81)  cm(6)  s(2)  photon(-2) . The application of this probe is demonstrated for ratiometric 3P imaging of Zn(2+) in vitro using HuH-7 cell lines. Furthermore, the Zn(2+) concentration in rat hippocampal slices was imaged at 1150 nm excitation after incubation with GMP, illustrating its potential as a 3P ratiometric probe for deep tissue Zn(2+) ion imaging.

  5. Afrikaans Syllabification Patterns

    Directory of Open Access Journals (Sweden)

    Tilla Fick


    Full Text Available In contrast to English, automatic hyphenation by computer of Afrikaans words is a problem that still needs to be addressed, since errors are still often encountered in printed text. An initial step in this task is the ability to automatically syllabify words. Since new words are created continuously by joining words, it is necessary to develop an “intelligent” technique for syllabification. As a first phase of the research, we consider only the orthographic information of words, and disregard both syntactic and morphological information. This approach allows us to use machine-learning techniques such as artificial neural networks and decision trees that are known for their pattern recognition abilities. Both these techniques are trained with isolated patterns consisting of input patterns and corresponding outputs (or targets that indicate whether the input pattern should be split at a certain position, or not. In the process of compiling a list of syllabified words from which to generate training data for the  syllabification problem, irregular patterns were identified. The same letter patterns are split differently in different words and complete words that are spelled identically are split differently due to meaning. We also identified irregularities in and between  the different dictionaries that we used. We examined the influence range of letters that are involved in irregularities. For example, for their in agter-ente and vaste-rente we have to consider three letters to the left of r to be certain where the hyphen should be inserted. The influence range of the k in verstek-waarde and kleinste-kwadrate is four to the left and three to the right. In an analysis of letter patterns in Afrikaans words we found that the letter e has the highest frequency overall (16,2% of all letters in the word list. The frequency of words starting with s is the highest, while the frequency of words ending with e is the highest. It is important to

  6. Ceruloplasmin ferroxidase activity stimulates cellular iron uptake by a trivalent cation-specific transport mechanism (United States)

    Attieh, Z. K.; Mukhopadhyay, C. K.; Seshadri, V.; Tripoulas, N. A.; Fox, P. L.


    The balance required to maintain appropriate cellular and tissue iron levels has led to the evolution of multiple mechanisms to precisely regulate iron uptake from transferrin and low molecular weight iron chelates. A role for ceruloplasmin (Cp) in vertebrate iron metabolism is suggested by its potent ferroxidase activity catalyzing conversion of Fe2+ to Fe3+, by identification of yeast copper oxidases homologous to Cp that facilitate high affinity iron uptake, and by studies of "aceruloplasminemic" patients who have extensive iron deposits in multiple tissues. We have recently shown that Cp increases iron uptake by cultured HepG2 cells. In this report, we investigated the mechanism by which Cp stimulates cellular iron uptake. Cp stimulated the rate of non-transferrin 55Fe uptake by iron-deficient K562 cells by 2-3-fold, using a transferrin receptor-independent pathway. Induction of Cp-stimulated iron uptake by iron deficiency was blocked by actinomycin D and cycloheximide, consistent with a transcriptionally induced or regulated transporter. Cp-stimulated iron uptake was completely blocked by unlabeled Fe3+ and by other trivalent cations including Al3+, Ga3+, and Cr3+, but not by divalent cations. These results indicate that Cp utilizes a trivalent cation-specific transporter. Cp ferroxidase activity was required for iron uptake as shown by the ineffectiveness of two ferroxidase-deficient Cp preparations, copper-deficient Cp and thiomolybdate-treated Cp. We propose a model in which iron reduction and subsequent re-oxidation by Cp are essential for an iron uptake pathway with high ion specificity.

  7. Localization versus delocalization in diamine radical cations

    DEFF Research Database (Denmark)

    Brouwer, A.M.; Wiering, P.G.; Zwier, J.M.;


    The optical absorption spectrum of the radical cation of 1,4-diphenylpiperazine 2a shows a strong transition in the near-IR, and only a weak band at 445 nm, in the region where aniline radical cations normally absorb strongly. This indicates that the charge and spin are delocalized over the two...

  8. Advancements in Anion Exchange Membrane Cations

    Energy Technology Data Exchange (ETDEWEB)

    Sturgeon, Matthew R. [National Renewable Energy Lab. (NREL), Golden, CO (United States); Long, Hai [National Renewable Energy Lab. (NREL), Golden, CO (United States); Park, Andrew M. [National Renewable Energy Lab. (NREL), Golden, CO (United States); Pivovar, Bryan S. [National Renewable Energy Lab. (NREL), Golden, CO (United States)


    Anion-exchange membrane fuel cells (AME-FCs) are of increasingly popular interest as they enable the use of non-Pt fuel cell catalysts, the primary cost limitation of proton exchange membrane fuel cells. Benzyltrimethyl ammonium (BTMA) is the standard cation that has historically been utilized as the hydroxide conductor in AEMs. Herein we approach AEMs from two directions. First and foremost we study the stability of several different cations in a hydroxide solution at elevated temperatures. We specifically targeted BTMA and methoxy and nitro substituted BTMA. We've also studied the effects of adding an akyl spacer units between the ammonium cation and the phenyl group. In the second approach we use computational studies to predict stable ammonium cations, which are then synthesized and tested for stability. Our unique method to study cation stability in caustic conditions at elevated temperatures utilizes Teflon Parr reactors suitable for use under various temperatures and cation concentrations. NMR analysis was used to determine remaining cation concentrations at specific time points with GCMS analysis verifying product distribution. We then compare the experimental results with calculated modeling stabilities. Our studies show that the electron donating methoxy groups slightly increase stability (compared to that of BTMA), while the electron withdrawing nitro groups greatly decrease stability in base. These results give insight into possible linking strategies to be employed when tethering a BTMA like ammonium cation to a polymeric backbone; thus synthesizing an anion exchange membrane.

  9. Cation diffusion in the natural zeolite clinoptilolite

    Energy Technology Data Exchange (ETDEWEB)

    Dyer, A.; White, K.J. [Science Research Institute, Chemistry Division, Cockcroft Building, University of Salford, Salford (United Kingdom)


    The natural zeolite clinoptilolite is mined commercially in many parts of the world. It is a selective exchanger for the ammonium cation and this has prompted its use in waste water treatment, swimming pools and in fish farming. It is also used to scavenge radioisotopes in nuclear waste clean-up. Further potential uses for clinoptilolite are in soil amendment and remediation. The work described herein provides thermodynamic data on cation exchange processes in clinoptilolite involving the NH{sub 4}, Na, K, Ca, and Mg cations. The data includes estimates of interdiffusion coefficients together with free energies, entropies and energies of activation for the cation exchanges studied. Suggestions are made as to the mechanisms of cation-exchanges involved.

  10. Silica gel modified with ethylenediamine and succinic acid-adsorption and calorimetry of cations in aqueous solution

    Energy Technology Data Exchange (ETDEWEB)

    Arakaki, L.N.H.; Filha, V.L.S. Augusto; Germano, A.F.S.; Santos, S.S.G. [Department of Chemistry, Federal University of Paraíba, 58051-900 João Pessoa, Paraíba (Brazil); Fonseca, M.G., E-mail: [Department of Chemistry, Federal University of Paraíba, 58051-900 João Pessoa, Paraíba (Brazil); Sousa, K.S.; Espínola, J.G.P. [Department of Chemistry, Federal University of Paraíba, 58051-900 João Pessoa, Paraíba (Brazil); Arakaki, T. [Department of Food Engineering, CT, Federal University of Paraíba, 58059-900 João Pessoa, Paraíba (Brazil)


    Highlights: ► Succinic acid-modified silica acted as an adsorbent for Cu (II), Ni (II), and Co (II) from aqueous solutions. ► Modified silica adsorbed metallic cations in the order Cu{sup 2+} > Co{sup 2+} > Ni{sup 2+}. ► Succinic acid-modified silica could be employed as low-cost material for the removal of cations from aqueous solution. ► Thermodynamic data for these systems are favorable at the solid/liquid interface. - Abstract: Ethylenediamine molecules were covalently immobilized onto silica gel previously functionalized with 3-chlorosilylpropyltrimethoxysilane (Sil–Cl), producing a Sil–N surface. The Sil–N surface reacted with succinic acid, yielding a Sil–NSuc surface. This new synthesized silica gel surface was used to adsorb divalent cations from aqueous solutions at room temperature. The adsorption isotherms were fit to a modified Langmuir equation using the data obtained by suspending the solid in MCl{sub 2} (M = Cu, Ni, and Co) aqueous solutions, yielding the maximum number of moles adsorbed as 1.04 ± 0.01, 1.89 ± 0.02 and 1.85 ± 0.02 mmol g{sup −1} for divalent copper, nickel and cobalt, respectively. The metal-basic center ratio for complexes on the surfaces varied with the nature of the metal. The spontaneity of these systems was reflected in the negative values of the Gibbs free energy calculated using calorimetric data. The net thermal effects obtained from the calorimetric titration measurements were adjusted to a modified Langmuir equation, and the calculation of the enthalpies of the interaction for the complexation with Sil–NSuc yielded the following exothermic values: 2.81 ± 0.08, 0.35 ± 0.04 ± and 0.69 ± 0.05 kJ mol{sup −1} for Cu{sup 2+}, Co{sup 2+} and Ni{sup 2+}, respectively. Based on these values, the metals are preferentially adsorbed in the order Cu{sup 2+} > Co{sup 2+} > Ni{sup 2+}. The other thermodynamic data for these systems are favorable at the solid/liquid interface, suggesting the efficacy of this

  11. Divalent metal transporter 1 regulates iron-mediated ROS and pancreatic ß cell fate in response to cytokines

    DEFF Research Database (Denmark)

    Hansen, Jakob Bondo; Tonnesen, Morten Fog; Madsen, Andreas Nygaard


    divalent metal transporter 1 (DMT1) expression correlating with increased ß cell iron content and ROS production. Iron chelation and siRNA and genetic knockdown of DMT1 expression reduce cytokine-induced ROS formation and cell death. Glucose-stimulated insulin secretion in the absence of cytokines in Dmt1...... knockout islets is defective, highlighting a physiological role of iron and ROS in the regulation of insulin secretion. Dmt1 knockout mice are protected against multiple low-dose streptozotocin and high-fat diet-induced glucose intolerance, models of type 1 and type 2 diabetes, respectively. Thus, ß cells...

  12. Cationic Bolaamphiphiles for Gene Delivery (United States)

    Tan, Amelia Li Min; Lim, Alisa Xue Ling; Zhu, Yiting; Yang, Yi Yan; Khan, Majad


    Advances in medical research have shed light on the genetic cause of many human diseases. Gene therapy is a promising approach which can be used to deliver therapeutic genes to treat genetic diseases at its most fundamental level. In general, nonviral vectors are preferred due to reduced risk of immune response, but they are also commonly associated with low transfection efficiency and high cytotoxicity. In contrast to viral vectors, nonviral vectors do not have a natural mechanism to overcome extra- and intracellular barriers when delivering the therapeutic gene into cell. Hence, its design has been increasingly complex to meet challenges faced in targeting of, penetration of and expression in a specific host cell in achieving more satisfactory transfection efficiency. Flexibility in design of the vector is desirable, to enable a careful and controlled manipulation of its properties and functions. This can be met by the use of bolaamphiphile, a special class of lipid. Unlike conventional lipids, bolaamphiphiles can form asymmetric complexes with the therapeutic gene. The advantage of having an asymmetric complex lies in the different purposes served by the interior and exterior of the complex. More effective gene encapsulation within the interior of the complex can be achieved without triggering greater aggregation of serum proteins with the exterior, potentially overcoming one of the great hurdles faced by conventional single-head cationic lipids. In this review, we will look into the physiochemical considerations as well as the biological aspects of a bolaamphiphile-based gene delivery system.

  13. Electroanalytical tools to investigate the divalent state of Eu(Ⅲ) and Nd(Ⅲ) ions in non-aqueous medium

    Institute of Scientific and Technical Information of China (English)

    Jignasu P Mehta; Himanshu M Pandya; Kahan I Pandya


    The divalent state of Ln(Ⅲ) ions has attracted much interest because of their ability to serve isomorphously in many biological system of divalent Ca(Ⅱ) ion.Therefore,present paper deals with the study of divalent state of Eu(Ⅲ) and Nd(Ⅲ) ions in non-aqueous medium.In present study,cyclic voltammetry and chronopotentiometry were utilized to establish the divalent state of Eu(Ⅲ) and Nd(Ⅲ) ions.The cyclic voltammetric technique showed two-step reduction process at cathode for both Ln(Ⅲ) ions under specified experimental conditions and chronopotentiomeuic method also showed two different transition times (τ).Looking to the shape of cyclic voltammogram we calculated heterogeneous forward rate constant (K0fh,cm/s) and diffusion coefficient (D,cm2/s) for both ions,which suggested that sweep rate had great effect on the shape of cyclic voltammogram of Eu(Ⅲ) and Nd(Ⅲ) ions.The result of chronopotentiometry also suggested that stable divalent states of Eu(Ⅲ) and Nd(Ⅲ) ions existed with chronopotenuogram with two distinct transition times.The diffusion coefficients (D,cm2/s)were calculated from Sand equation.The diffusion coefficients of both techniques were compared and the results suggested that the system at electrode surface was changing from being reversible to irreversible.

  14. Phase behavior of concentrated hydroxypropyl methylcellulose solution in the presence of mono and divalent salt. (United States)

    Almeida, Nalinda; Rakesh, Leela; Zhao, Jin


    Thermo reversible sol-gel transitions of hydroxypropylmethylcellulose (HPMC) are critical for many pharmaceutical, cosmetic, and food applications. This study examined the effects of salt (NaCl and CaCl₂) on the viscoelastic properties of concentrated low molecular weight HPMC solutions and found that the gelation temperature decreased linearly as a function of salt concentrations, independent of valency of cations and the mole concentration of anions. Thermal analysis showed that the depression of melting temperature can be fitted for both NaCl and CaCl₂ as a function of the total number of ions by a single linear curve, which was consistent with the melting point depression of pure water by NaCl and CaCl₂, but with a higher linear slope.

  15. Cation distributions on rapidly solidified cobalt ferrite (United States)

    De Guire, Mark R.; Kalonji, Gretchen; O'Handley, Robert C.


    The cation distributions in two rapidly solidified cobalt ferrites have been determined using Moessbauer spectroscopy at 4.2 K in an 8-T magnetic field. The samples were obtained by gas atomization of a Co0-Fe2O3-P2O5 melt. The degree of cation disorder in both cases was greater than is obtainable by cooling unmelted cobalt ferrite. The more rapidly cooled sample exhibited a smaller departure from the equilibrium cation distribution than did the more slowly cooled sample. This result is explained on the basis of two competing effects of rapid solidification: high cooling rate of the solid, and large undercooling.

  16. Mutational analysis of divalent metal ion binding in the active site of class II α-mannosidase from sulfolobus solfataricus

    DEFF Research Database (Denmark)

    Hansen, Dennis K.; Webb, Helen; Nielsen, Jonas Willum;


    Mutational analysis of Sulfolobus solfataricus class II α-mannosidase was focused on side chains that interact with the hydroxyls of the-1 mannosyl of the substrate (Asp-534) or form ligands to the active site divalent metal ion (His-228 and His-533) judged from crystal structures of homologous...... enzymes. D534A and D534N appeared to be completely inactive. When compared to the wild-type enzyme, the mutant enzymes in general showed only small changes in KM for the substrate, p-nitrophenyl-α-mannoside, but elevated activation constants, KA, for the divalent metal ion (Co2+, Zn2+, Mn2+, or Cd2......+). Some mutant enzyme forms displayed an altered preference for the metal ion compared to that of the wild type-enzyme. Furthermore, the H228Q, H533E, and H533Q enzymes were inhibited at increasing Zn2+ concentrations. The catalytic rate was reduced for all enzymes compared to that of the wild-type enzyme...

  17. The Influence of Divalent Anions on the Rectification Properties of Nanofluidic Diodes: Insights from Experiments and Theoretical Simulations. (United States)

    Pérez-Mitta, Gonzalo; Albesa, Alberto G; Toimil Molares, María Eugenia; Trautmann, Christina; Azzaroni, Omar


    During the last decade, the possibility of generating synthetic nanoarchitectures with functionalities comparable to biological entities has sparked the interest of the scientific community related to diverse research fields. In this context, gaining fundamental understanding of the central features that determine the rectifying characteristics of the conical nanopores is of mandatory importance. In this work, we analyze the influence of mono- and divalent salts in the ionic current transported by asymmetric nanopores and focus on the delicate interplay between ion exclusion and charge screening effects that govern the functional response of the nanofluidic device. Experiments were performed using KCl and K2 SO4 as representative species of singly and doubly charged species. Results showed that higher currents and rectification efficiencies are achieved by doubly charged salts. In order to understand the physicochemical processes underlying these effects simulations using the Poisson-Nernst-Planck formalism were performed. We consider that our theoretical and experimental account of the effect of divalent anions in the functional response of nanofluidic diodes provides further insights into the critical role of electrostatic interactions (ion exclusion versus charge screening effects) in presetting the ionic selectivity to anions as well as the observed rectification properties of these chemical nanodevices.

  18. The laws governing ionic liquid extraction of cations: partition of 1-ethylpyridinium monocation and paraquat dication in ionic liquid/water biphasic systems. (United States)

    Hamamoto, Takuya; Okai, Miho; Katsuta, Shoichi


    To find the laws governing the extraction of cations from aqueous solutions into hydrophobic ionic liquids (ILs), we investigated the partition of 1-ethylpyridinium monocation and paraquat (1,1'-dimethyl-4,4'-bipyridinium) dication in various IL/water biphasic systems. Ten different ILs of 1-butyl-3-methylimidazolium-based or bis(trifluoromethanesulfonyl)amide-based salts were used. The distribution ratio of the target cations (T(n+)) was dependent on the initial concentration in the aqueous phase and also very sensitive to the kind of IL. The behavior was quantitatively explained on the basis of a model in which the extraction goes through both the ion exchange and ion pair transfer processes, while keeping the product of the aqueous concentrations of the IL constituent ions a constant value (solubility product, Ksp). The distribution ratio of T(n+) is expressed as a function of the difference between the initial and equilibrium concentrations of T(n+) in the aqueous phase (Δ[T(n+)]W), the aqueous solubility of IL (Ksp(1/2)), and the cation valence n. The distribution ratio is a nearly constant value (D0) when Δ[T(n+)]W ≪ Ksp(1/2)/n and decreases inversely proportional to the nth power of Δ[T(n+)]W when Δ[T(n+)]W ≫ Ksp(1/2)/n. The log D0 versus log Ksp(1/2) plot gives a linear relationship with a slope of +n for the ILs with the same anion but different cations and that with a slope of nearly -n for the ILs with the same cation but different anions. This means that the extractability dependence on the kinds of IL constituent ions is greater for the divalent cation than for the monovalent one.

  19. Cationic ruthenium alkylidene catalysts bearing phosphine ligands. (United States)

    Endo, Koji; Grubbs, Robert H


    The discovery of highly active catalysts and the success of ionic liquid immobilized systems have accelerated attention to a new class of cationic metathesis catalysts. We herein report the facile syntheses of cationic ruthenium catalysts bearing bulky phosphine ligands. Simple ligand exchange using silver(i) salts of non-coordinating or weakly coordinating anions provided either PPh3 or chelating Ph2P(CH2)nPPh2 (n = 2 or 3) ligated cationic catalysts. The structures of these newly reported catalysts feature unique geometries caused by ligation of the bulky phosphine ligands. Their activities and selectivities in standard metathesis reactions were also investigated. These cationic ruthenium alkylidene catalysts reported here showed moderate activity and very similar stereoselectivity when compared to the second generation ruthenium dichloride catalyst in ring-closing metathesis, cross metathesis, and ring-opening metathesis polymerization assays.

  20. Cation locations and dislocations in zeolites (United States)

    Smith, Luis James

    The focus of this dissertation is the extra-framework cation sites in a particular structural family of zeolites, chabazite. Cation sites play a particularly important role in the application of these sieves for ion exchange, gas separation, catalysis, and, when the cation is a proton, acid catalysis. Structural characterization is commonly performed through the use of powder diffraction and Rietveld analysis of powder diffraction data. Use of high-resolution nuclear magnetic resonance, in the study of the local order of the various constituent nuclei of zeolites, complements well the long-range order information produced by diffraction. Recent developments in solid state NMR techniques allow for increased study of disorder in zeolites particularly when such phenomena test the detection limits of diffraction. These two powerful characterization techniques, powder diffraction and NMR, offer many insights into the complex interaction of cations with the zeolite framework. The acids site locations in SSZ-13, a high silica chabazite, and SAPO-34, a silicoaluminophosphate with the chabazite structure, were determined. The structure of SAPO-34 upon selective hydration was also determined. The insensitivity of X-rays to hydrogen was avoided through deuteration of the acid zeolites and neutron powder diffraction methods. Protons at inequivalent positions were found to have different acid strengths in both SSZ-13 and SAPO-34. Other light elements are incorporated into zeolites in the form of extra-framework cations, among these are lithium, sodium, and calcium. Not amenable by X-ray powder diffraction methods, the positions of such light cations in fully ion-exchanged versions of synthetic chabazite were determined through neutron powder diffraction methods. The study of more complex binary cation systems were conducted. Powder diffraction and solid state NMR methods (MAS, MQMAS) were used to examine cation site preferences and dislocations in these mixed-akali chabazites

  1. Cationized Carbohydrate Gas-Phase Fragmentation Chemistry (United States)

    Bythell, Benjamin J.; Abutokaikah, Maha T.; Wagoner, Ashley R.; Guan, Shanshan; Rabus, Jordan M.


    We investigate the fragmentation chemistry of cationized carbohydrates using a combination of tandem mass spectrometry, regioselective labeling, and computational methods. Our model system is D-lactose. Barriers to the fundamental glyosidic bond cleavage reactions, neutral loss pathways, and structurally informative cross-ring cleavages are investigated. The most energetically favorable conformations of cationized D-lactose were found to be similar. In agreement with the literature, larger group I cations result in structures with increased cation coordination number which require greater collision energy to dissociate. In contrast with earlier proposals, the B n -Y m fragmentation pathways of both protonated and sodium-cationized analytes proceed via protonation of the glycosidic oxygen with concerted glycosidic bond cleavage. Additionally, for the sodiated congeners our calculations support sodiated 1,6-anhydrogalactose B n ion structures, unlike the preceding literature. This affects the subsequent propensity of formation and prediction of B n /Y m branching ratio. The nature of the anomeric center (α/β) affects the relative energies of these processes, but not the overall ranking. Low-energy cross-ring cleavages are observed for the metal-cationized analytes with a retro-aldol mechanism producing the 0,2 A 2 ion from the sodiated forms. Theory and experiment support the importance of consecutive fragmentation processes, particularly for the protonated congeners at higher collision energies.

  2. Influence of both cation and alginate nature on the rheological behavior of transition metal alginate gels. (United States)

    Agulhon, Pierre; Robitzer, Mike; Habas, Jean-Pierre; Quignard, Françoise


    The rheological properties of several ionotropic alginate hydrogels were investigated according to the nature of the divalent cation (Mn(2+), Co(2+), Cu(2+)) and the guluronic fraction of the alginate (HG and LG for "high G-content" and "low G-content"). Six hydrogels (Mn-LG, Mn-HG, Co-LG, Co-HG, Cu-LG and Cu-HG) were synthesized and studied by spectromechanical analyses. On one hand, Cu-HG, Cu-LG and Co-HG behaved as viscoelastic solids: the elastic contribution was higher than the dissipative component in all the frequency range studied (G'>G"). No flow zone (G">G') was detected even at very low values of the shearing frequency. On the other, Mn-HG, Mn-LG and Co-LG presented a spectromechanical behavior that resembled that observed classically for entangled polymers. Indeed, at high frequency, these latter materials could be compared to a viscoelastic solid but at low frequency, the flow zone was described and the viscous character became prevalent with finite relaxation time. Very good correlations with the microscopic structurations of the network were evidenced (rubbery vs. flow zone and fibrillar vs. complex morphology respectively).

  3. The characteristics of action potential and nonselec-tive cation current of cardiomyocytes in rabbit superior vena cava

    Institute of Scientific and Technical Information of China (English)


    As a special focus in initiating and maintaining atrial fibrillation (AF), cardiomyocytes in superior vena cava (SVC) have distinctive electrophysiological characters. In this study, we found that comparing with the right atrial (RA) cardiomyoctyes, the SVC cardiomyoctyes had longer APD90 at the different basic cycle lengths; the conduction block could be observed on both RA and SVC cardiomyoctyes. A few of SVC cardiomyoctyes showed slow response action potentials with automatic activity and some others showed early afterdepolarization (EAD) spontaneously. Further more, we found that there are nonselective cation current (INs) in both SVC and RA cardiomyocytes. The peak density of INs in SVC cardiomyocytes was smaller than that in RA cardiomyocytes. Removal of extracellular divalent cation and glucose could increase INs in SVC cardiomyocytes. The agonist or the antagonist of INs may in-crease or decrease APD. To sum up, some SVC cardiomyocytes possess the ability of spontaneous activity; the difference of transmembrane action potentials between SVC and RA cardiomyocytes is partly because of the different density of INs between them; the agonist or the antagonist of INs can in-crease or decrease APD leading to the enhancement or reduction of EAD genesis in SVC cardiomyo-cytes. INs in rabbit myocytes is fairly similar to TRPC3 current in electrophysiological property, which might play an important role in the mechanisms of AF.

  4. [Inhibitory action of divalent copper compounds on cumene hydroperoxide oxidative demethylation of N,N-dimethylaniline by cytochrome P-450]. (United States)

    Kurchenko, V P; Usanov, S A; Metelitsa, D I


    The inhibitory action of divalent copper compounds on hydroperoxide-dependent oxidative demethylation of N,N-demethylaniline involving rabbit liver microsomes and highly purified cytochrome P-450 has been studied. CuCl2 is a non-competitive inhibitor, whereas copper tyrosine and lysine complexes are characterized by a mixed type inhibition. The inhibitory action of copper complexes is based on a decrease of cumene hydroperoxide concentration. The reaction results in formation of RO and RO2 radicals destroying cytochrome P-450 CuCl2 (0,001 M) also destroys cytochrome P-450 in the absence of cumene hydroperoxide; the destruction process is characterized by two phases with different rate constants. The nature of the inhibitory action of CuCl2 on N,N-demethylaniline oxidation by hydroperoxides is discussed.

  5. Synthesis and characterization of divalent metal complexes with ligand derived from the reaction of 3-aminopyridine and biacetyl

    Directory of Open Access Journals (Sweden)



    Full Text Available Divalent cobalt, nickel and copper salts reacted in situ with 3-aminopyridine and biacetyl to form complexes of the type: [M(Ap2biac2X2], where Ap2biac is the ligand and X=Cl, Br, NO3 or NCS. The complexes were analysed and characterized as distorted octahedral by conductance, molecular weight, magnetic, electronic and IR spectral studies. The electronic spectra were interpreted and tentative aassignments made. The infrared spectral studies revealed that two molecules of 3-aminopyridine were joined by molecules of biacetyl through a two carbon atom bridge and that the ligand coordinated through azomethine nitrogen atoms, whereas the pyridine nitrogen does not participate in the coordination. In the far infrared spectra, various metal–ligand vibrations were observed and are discussed.

  6. Synthesis and characterization of divalent manganese, iron, and cobalt complexes in tripodal phenolate/N-heterocyclic carbene ligand environments. (United States)

    Käß, Martina; Hohenberger, Johannes; Adelhardt, Mario; Zolnhofer, Eva M; Mossin, Susanne; Heinemann, Frank W; Sutter, Jörg; Meyer, Karsten


    Two novel tripodal ligands, (BIMPN(Mes,Ad,Me))(-) and (MIMPN(Mes,Ad,Me))(2-), combining two types of donor atoms, namely, NHC and phenolate donors, were synthesized to complete the series of N-anchored ligands, ranging from chelating species with tris(carbene) to tris(phenolate) chelating arms. The complete ligand series offers a convenient way of tuning the electronic and steric environment around the metal center, thus, allowing for control of the complex's reactivity. This series of divalent complexes of Mn, Fe, and Co was synthesized and characterized by (1)H NMR, IR, and UV/vis spectroscopy as well as by single-crystal X-ray diffraction studies. Variable-temperature SQUID magnetization measurements in the range from 2 to 300 K confirmed high-spin ground states for all divalent complexes and revealed a trend of increasing zero-field splitting |D| from Mn(II), to Fe(II), to Co(II) complexes. Zero-field (57)Fe Mössbauer spectroscopy of the Fe(II) complexes 3, 4, 8, and 11 shows isomer shifts δ that increase gradually as carbenes are substituted for phenolates in the series of ligands. From the single-crystal structure determinations of the complexes, the different steric demand of the ligands is evident. Particularly, the molecular structure of 1-in which a pyridine molecule is situated next to the Mn-Cl bond-and those of azide complexes 2, 4, and 6 demonstrate the flexibility of these mixed-ligand derivatives, which, in contrast to the corresponding symmetrical TIMEN(R) ligands, allow for side access of, e.g., organic substrates, to the reactive metal center.

  7. Studies on the effect of divalent metal ions on exfoliative toxins from Staphylococcus hyicus: indications of ExhA and ExhB being metalloproteins

    DEFF Research Database (Denmark)

    Andresen, Lars Ole


    The exfoliative toxins ExhA and ExhB produced by Staphylococcus hyicus strains NCTC10350 and 1289D-88, respectively, were investigated with regard to the effect of divalent metal ions on toxin production as measured in indirect enzyme-linked immunosorbent assay (ELISA) using monoclonal antibodies...

  8. Investigation of the encapsulation of metal cations (Cu(2+), Zn(2+), Ca(2+) and Ba(2+)) by the dipeptide Phe-Phe using natural bond orbital theory and molecular dynamics simulation. (United States)

    Bhunia, Snehasis; Singh, Ajeet; Ojha, Animesh K


    Complexes of the dipeptide phenylalanine-phenylalanine (Phe-Phe) with divalent metal cations (Cu(2+), Zn(2+), Ca(2+) and Ba(2+)) were studied at the B3LYP and MP2 levels of theory with the basis sets 6-311++G(d,p) and 6-31 + G(d) in the gas phase. The relative energies of these complexes indicated that cation-π bidentate/tridentate conformations are more favourable than other conformations with uncoordinated rings. These findings were confirmed by the calculated values of thermodynamic parameters such as the Gibbs free energy. Natural bond orbital (NBO) analysis was carried out to explore the metal-ligand coordination in Phe-Phe-Cu(2+)/Zn(2+) complexes. Possible orbital transitions, types of orbitals and their occupancies were determined for a range of Phe-Phe-Cu(2+)/Zn(2+) complexes. The charge transfer involved in various orbital transitions was explored by considering the second-order perturbation energy. NBO analysis revealed that the change transfer is stronger when the metal cation uses both the 4s + 4p subshells rather than just its 4p subshell. We also performed molecular dynamics (MD) simulations to check the stability and consistency of the most favourable binding motifs of Cu(2+), Zn(2+), Ca(2+) and Ba(2+) with Phe-Phe over time. The structures of the Phe-Phe-Cu(2+)/Zn(2+)/Ca(2+)/Ba(2+) complexes obtained using MD simulation were found to be in good agreement with those obtained in the DFT-based calculations. Graphical Abstract Conformational search on encapsulation of divalent metal cations (Ca(2+), Zn(2+), Ca(2+), Ba(2+)) by the Phe-Phe dipeptide.

  9. Disease-Homologous Mutation in the Cation Diffusion Facilitator Protein MamM Causes Single-Domain Structural Loss and Signifies Its Importance. (United States)

    Barber-Zucker, Shiran; Uebe, René; Davidov, Geula; Navon, Yotam; Sherf, Dror; Chill, Jordan H; Kass, Itamar; Bitton, Ronit; Schüler, Dirk; Zarivach, Raz


    Cation diffusion facilitators (CDF) are highly conserved, metal ion efflux transporters that maintain divalent transition metal cation homeostasis. Most CDF proteins contain two domains, the cation transporting transmembrane domain and the regulatory cytoplasmic C-terminal domain (CTD). MamM is a magnetosome-associated CDF protein essential for the biomineralization of magnetic iron-oxide particles in magnetotactic bacteria. To investigate the structure-function relationship of CDF cytoplasmic domains, we characterized a MamM M250P mutation that is synonymous with the disease-related mutation L349P of the human CDF protein ZnT-10. Our results show that the M250P exchange in MamM causes severe structural changes in its CTD resulting in abnormal reduced function. Our in vivo, in vitro and in silico studies indicate that the CTD fold is critical for CDF proteins' proper function and support the previously suggested role of the CDF cytoplasmic domain as a CDF regulatory element. Based on our results, we also suggest a mechanism for the effects of the ZnT-10 L349P mutation in human.

  10. Cation Effect on Copper Chemical Mechanical Polishing

    Institute of Scientific and Technical Information of China (English)

    WANG Liang-Yong; LIU Bo; SONG Zhi-Tang; FENG Song-Lin


    We examine the effect of cations in solutions containing benzotriazole (BTA) and H2O2 on copper chemical mechanical polishing (CMP). On the base of atomic force microscopy (AFM) and material removal rate (MRR) results, it is found that ammonia shows the highest MRR as well as good surface after CMP, while KOH demon-strates the worst performance. These results reveal a mechanism that sma//molecules with lone-pairs rather than molecules with steric effect and common inorganic cations are better for copper CMP process, which is indirectly confirmed by open circuit potential (OCP).

  11. Cation Effect on Copper Chemical Mechanical Polishing (United States)

    Wang, Liang-Yong; Liu, Bo; Song, Zhi-Tang; Feng, Song-Lin


    We examine the effect of cations in solutions containing benzotriazole (BTA) and H2O2 on copper chemical mechanical polishing (CMP). On the base of atomic force microscopy (AFM) and material removal rate (MRR) results, it is found that ammonia shows the highest MRR as well as good surface after CMP, while KOH demonstrates the worst performance. These results reveal a mechanism that small molecules with lone-pairs rather than molecules with steric effect and common inorganic cations are better for copper CMP process, which is indirectly confirmed by open circuit potential (OCP).

  12. Cationically polymerizable monomers derived from renewable sources

    Energy Technology Data Exchange (ETDEWEB)

    Crivello, J.V.


    The objectives of this project are to design and synthesize novel monomers which orginate from renewable biological sources and to carry out their rapid, efficient, pollution-free and energy efficient cationic polymerization to useful products under the influence of ultraviolet light or heat. A summary of the results of the past year's research on cationically polymerizable monomers derived from renewable sources is presented. Three major areas of investigation corresponding to the different classes of naturally occurring starting materials were investigated; epoxidized terpenes and natural rubber and vinyl ethers from alcohols and carbohydrates.

  13. Layered inorganic-organic hybrid with talc-like structure for cation removal at the solid/liquid interface

    Energy Technology Data Exchange (ETDEWEB)

    Badshah, Syed [Institute of Chemistry, University of Campinas, UNICAMP, P.O. Box 6154, 13084-971 Campinas, SP (Brazil); Airoldi, Claudio, E-mail: [Institute of Chemistry, University of Campinas, UNICAMP, P.O. Box 6154, 13084-971 Campinas, SP (Brazil)


    Graphical abstract: A lamellar inorganic-organic hybrid with talc-like structure has been synthesized through a single sol-gel step. Highlights: Black-Right-Pointing-Pointer New silylating agent isolated from acrylamide includes basic centers attached to enlarged chain. Black-Right-Pointing-Pointer Lamellar inorganic-organic talc-like structure has been synthesized through a single sol-gel step. Black-Right-Pointing-Pointer High basal distance accommodates the pendant chain in the cavities only in inclined disposition. Black-Right-Pointing-Pointer The pendant chain sorbs spontaneously and favorable cations as demonstrated by thermodynamic data. - Abstract: A new silylating agent N-((3-(3-(trimethoxysilyl)propylthio)propanamido)methyl)acrylamide synthesized from the reaction of N,N-methylenebisacrylamide and 3-mercaptopropyltrimethoxysilane yielded layered inorganic-organic talc-like magnesium phyllosilicate through the sol-gel process. Elemental analysis data based on sulfur demonstrated incorporation of 2.70 mmol g{sup -1} of organic moiety inside the lamellar cavities and the X-ray diffraction patterns confirmed the talc-like structure with a basal distance of 2.11 nm. Infrared spectroscopy, {sup 13}C and {sup 29}Si NMR in the solid state are in agreement with the presence of organic chains covalently bonded to the inorganic lamellar framework, as also supported by the presence of T{sup n} silicon species. Nitrogen, oxygen and sulfur basic centers sorb divalent lead, copper and cobalt cations with maximum capacity of 5.30, 3.82 and 1.60 mmol g{sup -1}. The thermodynamic data for cation/basic center interactions at the solid/liquid interface were determined through calorimetric titration with exothermic enthalpy, negative Gibbs energy and positive entropy, as expected for spontaneous and favorable reaction conditions.

  14. Cationic dialkylarylphosphates: a new family of bio-inspired cationic lipids for gene delivery. (United States)

    Le Corre, Stéphanie S; Belmadi, Nawal; Berchel, Mathieu; Le Gall, Tony; Haelters, Jean-Pierre; Lehn, Pierre; Montier, Tristan; Jaffrès, Paul-Alain


    In this work that aims to synthesize and evaluate new cationic lipids as vectors for gene delivery, we report the synthesis of a series of cationic lipids in which a phosphate functional group acts as a linker to assemble on a molecular scale, two lipid chains and one cationic polar head. The mono or dicationic moiety is connected to the phosphate group by an aryl spacer. In this work, two synthesis strategies were evaluated. The first used the Atherton-Todd coupling reaction to introduce a phenolic derivative to dioleylphosphite. The second strategy used a sequential addition of lipid alcohol and a phenolic derivative on POCl3. The two methods are efficient, but the latter allows larger yields. Different polar head groups were introduced, thus producing amphiphilic compounds possessing either one permanent (N-methyl-imidazolium, pyridinium, trimethylammonium) or two permanent cationic charges. All these cationic lipids were formulated as liposomal solutions and characterized (size and zeta potential). They formed stable liposomal solutions both in water (at pH 7.0) and in a weakly acidic medium (at pH 5.5). Finally, this new generation of cationic lipids was used to deliver DNA into various human-derived epithelial cells cultured in vitro. Compared with Lipofectamine used as a reference commercial lipofection reagent, some cationic dialkylarylphosphates were able to demonstrate potent gene transfer abilities, and noteworthily, monocationic derivatives were much more efficient than dicationic analogues.

  15. Effects of monovalent and divalent salts on the phospholipid and fatty acid compositions of a halotolerant Planococcus sp. (United States)

    Miller, K J


    The phospholipid headgroup and fatty acid compositions of a halotolerant Planococcus sp. (strain A4a) were examined when cells were grown in the presence of high concentrations of a variety of salts. The fatty acid composition of Planococcus sp. strain A4a was altered primarily as a function of the osmolality of the growth medium. The phospholipid headgroup composition was influenced by both the osmolality of the growth medium and the nature of the cation species present. An increase in the cardiolipin/phosphatidylglycerol molar ratio was detected when cells were grown in the presence of high concentrations of monovalent cations.

  16. Cation Selectivity in Biological Cation Channels Using Experimental Structural Information and Statistical Mechanical Simulation. (United States)

    Finnerty, Justin John; Peyser, Alexander; Carloni, Paolo


    Cation selective channels constitute the gate for ion currents through the cell membrane. Here we present an improved statistical mechanical model based on atomistic structural information, cation hydration state and without tuned parameters that reproduces the selectivity of biological Na+ and Ca2+ ion channels. The importance of the inclusion of step-wise cation hydration in these results confirms the essential role partial dehydration plays in the bacterial Na+ channels. The model, proven reliable against experimental data, could be straightforwardly used for designing Na+ and Ca2+ selective nanopores.

  17. Mixed cation effect in sodium aluminosilicate glasses

    DEFF Research Database (Denmark)

    Kjeldsen, Jonas; Smedskjær, Morten Mattrup; Mauro, John C.

    , network structure, and the resistances associated with the deformation processes in mixed cation glasses by partially substituting magnesium for calcium and calcium for lithium in sodium aluminosilicate glasses. We use Raman and 27Al NMR spectroscopies to obtain insights into the structural...

  18. Resonance raman studies of phenylcyclopropane radical cations

    NARCIS (Netherlands)

    Godbout, J.T.; Zuilhof, H.; Heim, G.; Gould, I.R.; Goodman, J.L.; Dinnocenzo, J.P.; Myers Kelley, A.


    Resonance Raman spectra of the radical cations of phenylcyclopropane and trans-1-phenyl-2-methylcyclopropane are reported. A near-UV pump pulse excites a photosensitizer which oxidizes the species of interest, and a visible probe pulse delayed by 35 ns obtains the spectrum of the radical ion. The tr

  19. Simultaneous anion and cation mobility in polypyrrole

    DEFF Research Database (Denmark)

    Skaarup, Steen; Bay, Lasse; Vidanapathirana, K.;


    Polypyrrole (PPy) polymer films permanently doped with large, immobile anion dodecyl benzene sulfonate (DBS) have been characterized by cyclic voltammetry in order to clarify the roles of cations and anions in the aqueous electrolyte as mobile ions in the film. Aqueous solutions of 0.05-0.1 M...... alkali metal chlorides as well as BaCl2, NaBr and (CH3CH2CH2)(4)NBr were used to investigate the effects of both the ionic charge, size and shape. In 1: 1 electrolytes using small ions only three peaks are present: a sharp cathodic peak at ca. - 0.6 V vs, SCE representing both the insertion of cations...... complicating reproducibility when employing PPy(DBS) polymers as actuators. When the cation is doubly charged, it enters the film less readily, and anions dominate the mobility. Using a large and bulky cation switches the mechanism to apparently total anion motion. The changes in area of the three peaks...

  20. Anionic/cationic complexes in hair care. (United States)

    O'Lenick, Tony


    The formulation of cosmetic products is always more complicated than studying the individual components in aqueous solution. This is because there are numerous interactions between the components, which make the formulation truly more than the sum of the parts. This article will look at interactions between anionic and cationic surfactants and offer insights into how to use these interactions advantageously in making formulations.

  1. Controlled Cationic Polymerization of N-Vinylcarbazol

    NARCIS (Netherlands)

    Nuyken, O.; Rieß, G.; Loontjens, J.A.


    Cationic polymerization of N-Vinylcarbazol (NVC) was initiated with 1-iodo-1-(2-methylpropyloxy)ethane in the presence of N(n-Bu)4ClO4 and without addition of this activator. Furthermore, 1-chloro-1-(2-methylpropyloxy) ethane, with and without activator has been applied as initiator for NVC. These i

  2. Cationic lipids and cationic ligands induce DNA helix denaturation: detection of single stranded regions by KMnO4 probing. (United States)

    Prasad, T K; Gopal, Vijaya; Rao, N Madhusudhana


    Cationic lipids and cationic polymers are widely used in gene delivery. Using 1,2-dioleoyl-3-trimethylammonium-propane (DOTAP) as a cationic lipid, we have investigated the stability of the DNA in DOTAP:DNA complexes by probing with potassium permanganate (KMnO4). Interestingly, thymidines followed by a purine showed higher susceptibility to cationic ligand-mediated melting. Similar studies performed with other water-soluble cationic ligands such as polylysine, protamine sulfate and polyethyleneimine also demonstrated melting of the DNA but with variations. Small cations such as spermine and spermidine and a cationic detergent, cetyl trimethylammonium bromide, also rendered the DNA susceptible to modification by KMnO4. The data presented here provide direct proof for melting of DNA upon interaction with cationic lipids. Structural changes subsequent to binding of cationic lipids/ligands to DNA may lead to instability and formation of DNA bubbles in double-stranded DNA.

  3. Dendritic Cells Stimulated by Cationic Liposomes. (United States)

    Vitor, Micaela Tamara; Bergami-Santos, Patrícia Cruz; Cruz, Karen Steponavicius Piedade; Pinho, Mariana Pereira; Barbuto, José Alexandre Marzagão; De La Torre, Lucimara Gaziola


    Immunotherapy of cancer aims to harness the immune system to detect and destroy cancer cells. To induce an immune response against cancer, activated dendritic cells (DCs) must present tumor antigens to T lymphocytes of patients. However, cancer patients' DCs are frequently defective, therefore, they are prone to induce rather tolerance than immune responses. In this context, loading tumor antigens into DCs and, at the same time, activating these cells, is a tempting goal within the field. Thus, we investigated the effects of cationic liposomes on the DCs differentiation/maturation, evaluating their surface phenotype and ability to stimulate T lymphocytes proliferation in vitro. The cationic liposomes composed by egg phosphatidylcholine, 1,2-dioleoyl-3-trimethylammonium propane and 1,2-dioleoylphosphatidylethanolamine (50/25/25% molar) were prepared by the thin film method followed by extrusion (65 nm, polydispersity of 0.13) and by the dehydration-rehydration method (95% of the population 107 nm, polydispersity of 0.52). The phenotypic analysis of dendritic cells and the analysis of T lymphocyte proliferation were performed by flow cytometry and showed that both cationic liposomes were incorporated and activated dendritic cells. Extruded liposomes were better incorporated and induced higher CD86 expression for dendritic cells than dehydrated-rehydrated vesicles. Furthermore, dendritic cells which internalized extruded liposomes also provided stronger T lymphocyte stimulation. Thus, cationic liposomes with a smaller size and polydispersity seem to be better incorporated by dendritic cells. Hence, these cationic liposomes could be used as a potential tool in further cancer immunotherapy strategies and contribute to new strategies in immunotherapy.

  4. Bithiophene radical cation: Resonance Raman spectroscopy and molecular orbital calculations

    DEFF Research Database (Denmark)

    Grage, M.M.-L.; Keszthelyi, T.; Offersgaard, J.F.


    The resonance Raman spectrum of the photogenerated radical cation of bithiophene is reported. The bithiophene radical cation was produced via a photoinduced electron transfer reaction between excited bithiophene and the electron acceptor fumaronitrile in a room temperature acetonitrile solution a...


    Institute of Scientific and Technical Information of China (English)

    Dongmei Yu; Chuanshan Zhao; Kefu Chen


    This study investigated the effects of several different cationic additives on the viscosity 、zeta potential and printing properties of the ink-jet coating. The cationic additives have greatly improved sheet's gloss and printabilities.

  6. Ion dynamics in cationic lipid bilayer systems in saline solutions

    DEFF Research Database (Denmark)

    Miettinen, Markus S; Gurtovenko, Andrey A; Vattulainen, Ilpo


    mixture of cationic dimyristoyltrimethylammoniumpropane (DMTAP) and zwitterionic (neutral) dimyristoylphosphatidylcholine (DMPC) lipids. Using atomistic molecular dynamics simulations, we address the effects of bilayer composition (cationic to zwitterionic lipid fraction) and of NaCl electrolyte...

  7. The effect of divalent ions on the elasticity and pore collapse of chalk evaluated from compressional wave velocity and low-field Nuclear Magnetic Resonance (NMR)

    DEFF Research Database (Denmark)

    Katika, Konstantina; Addassi, Mouadh; Alam, Mohammad Monzurul


    electron microscopy of the materials were conducted prior to the experiments. The iso-frame model was used to predict the bulk moduli in dry and saturated conditions from the compressional modulus of water-saturated rocks. The effective stress coefficient, as introduced by Biot, was also determined from......The effects of divalent ions on the elasticity and the pore collapse of chalk were studied through rock-mechanical testing and low-field Nuclear Magnetic Resonance (NMR) measurements. Chalk samples saturated with deionized water and brines containing sodium, magnesium, calcium and sulfate ions were...... and effects on the elasticity after the saturation since none of the other plugs saturated with divalent ions (Ca2+ and SO42+) experienced it....

  8. Interpretation with a Donnan-based concept of the influence of simple salt concentration on the apparent binding of divalent ions to the polyelectrolytes polystyrenesulfonate and dextran sulfate (United States)

    Marinsky, J.A.; Baldwin, Robert F.; Reddy, M.M.


    It has been shown that the apparent enhancement of divalent metal ion binding to polyions such as polystyrenesulfonate (PSS) and dextran sulfate (DS) by decreasing the ionic strength of these mixed counterion systems (M2+, M+, X-, polyion) can be anticipated with the Donnan-based model developed by one of us (J.A.M.). Ion-exchange distribution methods have been employed to measure the removal by the polyion of trace divalent metal ion from simple salt (NaClO4)-polyion (NaPSS) mixtures. These data and polyion interaction data published earlier by Mattai and Kwak for the mixed counterion systems MgCl2-LiCl-DS and MgCl2-CsCl-DS have been shown to be amenable to rather precise analysis by this model. ?? 1985 American Chemical Society.

  9. Novel kinetic model of the removal of divalent heavy metal ions from aqueous solutions by natural clinoptilolite. (United States)

    Jovanovic, Mina; Rajic, Nevenka; Obradovic, Bojana


    Removal of heavy metal ions from aqueous solutions using zeolites is widely described by pseudo-second order kinetics although this model may not be valid under all conditions. In this work, we have extended approaches used for derivation of this model in order to develop a novel kinetic model that is related to the ion exchange mechanism underlying sorption of metal ions in zeolites. The novel model assumed two reversible steps, i.e. release of sodium ions from the zeolite lattice followed by bonding of the metal ion. The model was applied to experimental results of Cu(II) sorption by natural clinoptilolite-rich zeolitic tuff at different initial concentrations and temperatures and then validated by predictions of ion exchange kinetics of other divalent heavy metal ions (i.e. Mn(II), Zn(II) and Pb(II)). Model predictions were in excellent agreements with experimental data for all investigated systems. In regard to the proposed mechanism, modeling results implied that the sodium ion release rate was constant for all investigated metals while the overall rate was mainly determined by the rate of heavy metal ion bonding to the lattice. In addition, prediction capabilities of the novel model were demonstrated requiring one experimentally determined parameter, only.

  10. Headgroup interactions and ion flotation efficiency in mixtures of a chelating surfactant, different foaming agents, and divalent metal ions. (United States)

    Svanedal, Ida; Boija, Susanne; Norgren, Magnus; Edlund, Håkan


    The correlation between interaction parameters and ion flotation efficiency in mixtures of chelating surfactant metal complexes and different foaming agents was investigated. We have recently shown that chelating surfactant 2-dodecyldiethylenetriaminepentaacetic acid (4-C12-DTPA) forms strong coordination complexes with divalent metal ions, and this can be utilized in ion flotation. Interaction parameters for mixed micelles and mixed monolayer formation for Mg(2+) and Ni(2+) complexes with the chelating surfactant 4-C12-DTPA and different foaming agents were calculated by Rubingh's regular solution theory. Parameters for the calculations were extracted from surface tension measurements and NMR diffusometry. The effects of metal ion coordination on the interactions between 4-C12-DTPA and the foaming agents could be linked to a previously established difference in coordination chemistry between the examined metal ions. As can be expected from mixtures of amphoteric surfactants, the interactions were strongly pH-dependent. Strong correlation was found between interaction parameter β(σ) for mixed monolayer formation and the phase-transfer efficiency of Ni(2+) complexes with 4-C12-DTPA during flotation in a customized flotation cell. In a mixture of Cu(2+) and Zn(2+), the significant difference in conditional stability constants (log K) between the metal complexes was utilized to selectively recover the metal complex with the highest log K (Cu(2+)) by ion flotation. Flotation experiments in an excess concentration of metal ions confirmed the coordination of more than one metal ion to the headgroup of 4-C12-DTPA.

  11. Removal of divalent nickel from aqueous solutions using Carissa carandas and Syzygium aromaticum: isothermal studies and kinetic modelling (United States)

    Sharma, Sanjay K.; Mahiya, Suresh; Lofrano, Giusy


    Biosorptive removal of divalent nickel from aqueous solution using Carissa Carandas and Syzygium aromaticum was investigated in batch mode and the observations were correlated with the pH variation, agitation time, dose of the adsorbent and initial metal ion concentration in the solution. In the course of this study Sorption efficiency of C. carandas leaf powder found higher than that of S. aromaticum under identical experimental conditions. The maximum adsorption capacities estimated for Ni(II) through Freundlich isotherm model were 3.76 and 2.96 mg/g for C. carandas and S. aromaticum, respectively. In kinetic studies the correlation coefficient (R 2 = 0.99) for the pseudo-second order kinetics modal was higher than that of pseudo-first order kinetics model and the calculated value of q e for the pseudo-second order kinetic model resulted very close to the experimental value, which indicates that it fits well with the equilibrium data for Ni(II) sorption from aqueous solutions on biosorbents.

  12. Design, Synthesis, and Structural Analysis of Divalent N(I) Compounds and Identification of a New Electron-Donating Ligand. (United States)

    Bharatam, Prasad V; Arfeen, Minhajul; Patel, Neha; Jain, Priyanka; Bhatia, Sonam; Chakraborti, Asit K; Khullar, Sadhika; Gupta, Vijay; Mandal, Sanjay K


    The dative-bond representation (L→E) in compounds with main group elements (E) has triggered extensive debate in the recent past. The scope and limits of this nonclassical coordination bond warrant comprehensive exploration. Particularly compounds with (L→N←L')(+) arrangement are of special interest because of their therapeutic importance. This work reports the design and synthesis of novel chemical species with the general structural formula (L→N←L')(+) carrying the unusual ligand cyclohexa-2,5-diene-4-(diaminomethynyl)-1-ylidene. Four species belonging to the (L→N←L')(+) class carrying this unconventional ligand were synthesized. Quantum chemical and X-ray diffraction analyses showed that the electronic and geometric parameters are consistent with those of already reported divalent N(I) compounds. The molecular orbital analysis, geometric parameters, and spectral data clearly support the L→N and N←L' interactions in these species. The newly identified ligand has the properties of a reactive carbene and high nucleophilicity.

  13. Influence of the ADP/ATP ratio, 2-oxoglutarate and divalent ions on Azospirillum brasilense PII protein signalling. (United States)

    Gerhardt, Edileusa C M; Araújo, Luíza M; Ribeiro, Ronny R; Chubatsu, Leda S; Scarduelli, Marcelo; Rodrigues, Thiago E; Monteiro, Rose A; Pedrosa, Fábio O; Souza, Emanuel M; Huergo, Luciano F


    Proteins belonging to the P(II) family coordinate cellular nitrogen metabolism by direct interaction with a variety of enzymes, transcriptional regulators and transporters. The sensing function of P(II) relies on its ability to bind the nitrogen/carbon signalling molecule 2-oxoglutarate (2-OG). In Proteobacteria, P(II) is further subject to reversible uridylylation according to the intracellular levels of glutamine, which reflect the cellular nitrogen status. A number of P(II) proteins have been shown to bind ADP and ATP in a competitive manner, suggesting that P(II) might act as an energy sensor. Here, we analyse the influence of the ADP/ATP ratio, 2-OG levels and divalent metal ions on in vitro uridylylation of the Azospirillum brasilense P(II) proteins GlnB and GlnZ, and on interaction with their targets AmtB, DraG and DraT. The results support the notion that the cellular concentration of 2-OG is a key factor governing occupation of the GlnB and GlnZ nucleotide binding sites by ATP or ADP, with high 2-OG levels favouring the occupation of P(II) by ATP. Both P(II) uridylylation and interaction with target proteins responded to the ADP/ATP ratio within the expected physiological range, supporting the concept that P(II) proteins might act as cellular energy sensors.

  14. Production of sulfonated cation-exchangers from petroleum asphaltites

    Energy Technology Data Exchange (ETDEWEB)

    Pokonova, Yu.V.; Pol' kin, G.B.; Proskuryakov, V.A.; Vinogradov, M.V.


    Continuing our studies of the preparation of products of practical value from asphaltite, a new by-product of oil refining, we obtained sulfonated cation-exchangers from a mixture of asphaltite and acid tar. It is shown that these cation-exchangers have good kinetic properties and are superior in thermal and thermohydrolytic stability to the commercial cation-exchange resin KU-2.

  15. Cation Permeability in Soybean Aleurone Layer


    Noda, Hiroko; Fukuda, Mitsuru


    The permeation of water and ions into bean seeds is essential for processing and cooking of beans. The permeability of cations, K, Na, Ca, and Mg ions, into soybean seed tissue, especially aleurone layer, during water uptake was investigated to characterize the ion permeation into soybeans. Aleurone layers and seed coats contained relatively high concentration of endogenous K and Ca ions, and endogenous Ca ion, respectively. The amounts of Ca ion entered seed coats and aleurone layers were gr...

  16. Limited data speaker identification

    Indian Academy of Sciences (India)

    H S Jayanna; S R Mahadeva Prasanna


    In this paper, the task of identifying the speaker using limited training and testing data is addressed. Speaker identification system is viewed as four stages namely, analysis, feature extraction, modelling and testing. The speaker identification performance depends on the techniques employed in these stages. As demonstrated by different experiments, in case of limited training and testing data condition, owing to less data, existing techniques in each stage will not provide good performance. This work demonstrates the following: multiple frame size and rate (MFSR) analysis provides improvement in the analysis stage, combination of mel frequency cepstral coefficients (MFCC), its temporal derivatives $(\\Delta,\\Delta \\Delta)$, linear prediction residual (LPR) and linear prediction residual phase (LPRP) features provides improvement in the feature extraction stage and combination of learning vector quantization (LVQ) and gaussian mixture model – universal background model (GMM–UBM) provides improvement in the modelling stage. The performance is further improved by integrating the proposed techniques at the respective stages and combining the evidences from them at the testing stage. To achieve this, we propose strength voting (SV), weighted borda count (WBC) and supporting systems (SS) as combining methods at the abstract, rank and measurement levels, respectively. Finally, the proposed hierarchical combination (HC) method integrating these three methods provides significant improvement in the performance. Based on these explorations, this work proposes a scheme for speaker identification under limited training and testing data.

  17. Controlling chemistry with cations: photochemistry within zeolites. (United States)

    Ramamurthy, V; Shailaja, J; Kaanumalle, Lakshmi S; Sunoj, R B; Chandrasekhar, J


    The alkali ions present in the supercages of zeolites X and Y interact with included guest molecules through quadrupolar (cation-pi), and dipolar (cation-carbonyl) interactions. The presence of such interactions can be inferred through solid-state NMR spectra of the guest molecules. Alkali ions, as illustrated in this article, can be exploited to control the photochemical and photophysical behaviors of the guest molecules. For example, molecules that rarely phosphoresce can be induced to do so within heavy cation-exchanged zeolites. The nature (electronic configuration) of the lowest triplet state of carbonyl compounds can be altered with the help of light alkali metal ions. This state switch (n pi*-pi pi*) helps to bring out reactivity that normally remains dormant. Selectivity obtained during the singlet oxygen oxidation of olefins within zeolites illustrates the remarkable control that can be exerted on photoreactions with the help of a confined medium that also has active sites. The reaction cavities of zeolites, like enzymes, are not only well-defined and confined, but also have active sites that closely guide the reactant molecule from start to finish. The examples provided here illustrate that zeolites are far more useful than simple shape-selective catalysts.

  18. Cell volume-regulated cation channels. (United States)

    Wehner, Frank


    Considering the enormous turnover rates of ion channels when compared to carriers it is quite obvious that channel-mediated ion transport may serve as a rapid and efficient mechanism of cell volume regulation. Whenever studied in a quantitative fashion the hypertonic activation of non-selective cation channels is found to be the main mechanism of regulatory volume increase (RVI). Some channels are inhibited by amiloride (and may be related to the ENaC), others are blocked by Gd(3) and flufenamate (and possibly linked to the group of transient receptor potential (TRP) channels). Nevertheless, the actual architecture of hypertonicity-induced cation channels remains to be defined. In some preparations, hypertonic stress decreases K(+) channel activity so reducing the continuous K(+) leak out of the cell; this is equivalent to a net gain of cell osmolytes facilitating RVI. The hypotonic activation of K(+) selective channels appears to be one of the most common principles of regulatory volume decrease (RVD) and, in most instances, the actual channels involved could be identified on the molecular level. These are BKCa (or maxi K(+)) channels, IK(Ca) and SK(Ca) channels (of intermediate and small conductance, respectively), the group of voltage-gated (Kv) channels including their Beta (or Kv ancilliary) subunits, two-pore K(2P) channels, as well as inwardly rectifying K(+) (Kir) channels (also contributing to K(ATP) channels). In some cells, hypotonicity activates non-selective cation channels. This is surprising, at first sight, because of the inside negative membrane voltage and the sum of driving forces for Na(+) and K(+) diffusion across the cell membrane rather favouring net cation uptake. Some of these channels, however, exhibit a P(K)/P(Na) significantly higher than 1, whereas others are Ca(++) permeable linking hypotonic stress to the activation of Ca(++) dependent ion channels. In particular, the latter holds for the group of TRPs which are specialised in the

  19. [Antioxidant activity of cationic whey protein isolate]. (United States)

    titova, M E; Komolov, S A; Tikhomirova, N A


    The process of lipid peroxidation (LPO) in biological membranes of cells is carried out by free radical mechanism, a feature of which is the interaction of radicals with other molecules. In this work we investigated the antioxidant activity of cationic whey protein isolate, obtained by the cation-exchange chromatography on KM-cellulose from raw cow's milk, in vitro and in vivo. In biological liquids, which are milk, blood serum, fetal fluids, contains a complex of biologically active substances with a unique multifunctional properties, and which are carrying out a protective, antimicrobial, regenerating, antioxidant, immunomodulatory, regulatory and others functions. Contents of the isolate were determined electrophoretically and by its biological activity. Cationic whey protein isolate included lactoperoxidase, lactoferrin, pancreatic RNase, lysozyme and angeogenin. The given isolate significantly has an antioxidant effect in model experimental systems in vitro and therefore may be considered as a factor that can adjust the intensity of lipid oxidation. In model solutions products of lipid oxidation were obtained by oxidation of phosphatidylcholine by hydrogen peroxide in the presence of a source of iron. The composition of the reaction mixture: 0,4 mM H2O2; 50 mcM of hemin; 2 mg/ml L-alpha-phosphatidylcholine from soybean (Sigma, German). Lipid peroxidation products were formed during the incubation of the reaction mixture for two hours at 37 degrees C. In our studies rats in the adaptation period immediately after isolation from the nest obtained from food given orally native cationic whey protein isolate at the concentration three times higher than in fresh cow's milk. On the manifestation of the antioxidant activity of cationic whey protein isolate in vivo evidence decrease of lipid peroxidation products concentration in the blood of rats from the experimental group receipt whey protein isolate in dos 0,6 mg/g for more than 20% (pwhey protein isolate has an

  20. Alkali cation specific adsorption onto fcc(111) transition metal electrodes. (United States)

    Mills, J N; McCrum, I T; Janik, M J


    The presence of alkali cations in electrolyte solutions is known to impact the rate of electrocatalytic reactions, though the mechanism of such impact is not conclusively determined. We use density functional theory (DFT) to examine the specific adsorption of alkali cations to fcc(111) electrode surfaces, as specific adsorption may block catalyst sites or otherwise impact surface catalytic chemistry. Solvation of the cation-metal surface structure was investigated using explicit water models. Computed equilibrium potentials for alkali cation adsorption suggest that alkali and alkaline earth cations will specifically adsorb onto Pt(111) and Pd(111) surfaces in the potential range of hydrogen oxidation and hydrogen evolution catalysis in alkaline solutions.

  1. The effect of cations on the aggregation of commercial ZnO nanoparticle suspension (United States)

    Liu, Wei-Szu; Peng, Yu-Huei; Shiung, Chia-En; Shih, Yang-hsin


    Nanoscale ZnO materials have been largely used in many products due to their distinct properties. However, ZnO nanoparticles (NPs) are hazardous to human health and the ecosystem. The characteristics and the stability of ZnO NPs are relevant to their fate in the environment and their potential toxicities. In this study, a stable commercial ZnO NP suspension was chosen to investigate its aggregation under various salt additions. Different concentrations of NaCl, KCl and CaCl2 were chosen to represent various environmental conditions. Under pH 8-9, the surface charge of commercial ZnO NPs was negative. The behavior of the stabilized ZnO NPs in water was affected by ionic combinations and ionic strength; that is, divalent cations were more effective than monovalent ones in promoting aggregation formation. The attachment efficiencies of ZnO aggregates were calculated based upon the aggregation kinetics. The critical coagulation concentration values for this commercial ZnO NPs were higher than previous reported for ZnO NPs, indicating this ZnO NP could be stable in the aquatic environment and might have increased hazardous potentials. Based upon the Derjaguin-Landau-Verwey-Overbeek theory, interactions between ZnO NPs in the presence of different ions were evaluated to illustrate the aggregation mechanism. Our results indicated that critical ionic type and concentration promote the aggregation of stable ZnO NPs. These understandings also can facilitate the design of the precipitation treatment to remove NPs from water.

  2. Interaction between alginates and manganese cations: identification of preferred cation binding sites. (United States)

    Emmerichs, N; Wingender, J; Flemming, H-C; Mayer, C


    Algal and bacterial alginates have been studied by means of 13C NMR spectroscopy in presence of paramagnetic manganese ions in order to reveal the nature of their interaction with bivalent cations. It is found that the mannuronate blocks bind manganese cations externally near their carboxylate groups, while guluronate blocks show the capability to integrate Mn2+ into pocket-like structures formed by adjacent guluronate residues. In alternating mannuronate-guluronate blocks, manganese ions preferentially locate in a concave structure formed by guluronate-mannuronate pairs. Partial acetylation of the alginate generally reduces its capability to interact with bivalent cations, however, the selectivity of the binding geometry is conserved. The results may serve as a hint for the better understanding of the alginate gelation in presence of calcium ions.

  3. Development of an optical thermal history coating sensor based on the oxidation of a divalent rare earth ion phosphor (United States)

    Yáñez-González, Álvaro; Ruiz-Trejo, Enrique; van Wachem, Berend; Skinner, Stephen; Beyrau, Frank; Heyes, Andrew


    The measurement of temperatures in gas turbines, boilers, heat exchangers and other components exposed to hot gases is essential to design energy efficient systems and improve maintenance procedures. When on-line measurements, such as those performed with thermocouples and pyrometers, are not possible or inconvenient, the maximum temperatures of operation can be recorded and measured off-line after operation. Although thermal paints have been used for many years for this purpose, a novel technique based on irreversible changes in the optical properties of thermographic phosphors, can overcome some of the disadvantages of previous methods. In particular, oxidation of the divalent rare earth ion phosphor BaMgAl10O17:Eu (BAM:Eu) has shown great potential for temperature sensing between 700 °C and 1200 °C. The emission spectra of this phosphor change with temperature, which permits to define an intensity ratio between different lines in the spectra that can be used as a measurand of the temperature. In this paper, the study of the sensing capabilities of a sensor coating based on BAM:Eu phosphor material is addressed for the first time. The sensitivity of the intensity ratio is investigated in the temperature range from 800 °C to 1100 °C, and is proved to be affected by ionic diffusion of transition metals from the substrate. The use of an interlayer made of zirconia proves efficient in reducing ionic diffusion and coatings with this diffusion barrier present sensitivity comparable to that of the powder material.

  4. Radical bonding: structure and stability of bis(phenalenyl) complexes of divalent metals from across the periodic table. (United States)

    Craciun, Smaranda; Donald, Kelling J


    We examine the bonding possibilities of the bis(phenalenyl) MP(2) sandwich complexes of the divalent metals M = Be, Mg, Ca, Sr, Ba, Zn, Cd, and Hg, at the B3LYP level of theory. The outcome is an extraordinarily diverse class of low symmetry bis(phenalenyl)metal complexes in which bonding preferences and binding enthalpies differ dramatically. The lowest energy group 2 metal MP(2) complexes include an intriguing eta(1),eta(3) BeP(2) structure, and bent eta(6),eta(6) systems for M = Ca, Sr, and Ba. The group 12 bis(phenalenyl) complexes are thermodynamically unstable eta(1),eta(1) slip-sandwich structures. To better understand changes in the structural preferences going from the (eta(6),eta(6)) group 2 to the (eta(1),eta(1)) group 12 complexes, we explored the bonding in the bis(phenalenyl) complexes of transition metals with stable +2 oxidations states between Ca and Zn in period 4. The computed binding enthalpies are large and negative for nearly all of the minimum energy bis(phenalenyl) complexes of the group 2 and the transition metals; they are tiny for MgP(2), and are quite positive for the group 12 systems. The structural preferences and stability of the complexes is a subtle negotiation of several influences: the (un)availability of (n - 1)d and np, orbitals for bonding, the cost of the rehybridization at carbon sites in the phenalenyl rings in preparation for bonding to the metals, and the (P---P) interaction between the phenalenyl radicals.

  5. On-line coupling of an ion chromatograph to the ICP-MS: Separations with a cation exchange chromatography column

    Energy Technology Data Exchange (ETDEWEB)

    Roellin, Stefan [Studsvik Nuclear AB, Nykoeping (Sweden)


    An ion chromatography system was coupled on-line to the ICP-MS. All separations were made with a cation exchange chromatography column. Fundamental laws about elution parameters affecting individual retention times and elution forms are explained by applying a proper ion exchange mechanism for the isocratic elution (separations with constant eluent concentration) of mono-, di-, tri-, and tetravalent cations and the actinide species MO{sub 2}{sup +} and MO{sub 2}{sup 2+}. A separation method with two eluents has been investigated to separate mono- from divalent ions in order to separate isobaric overlaps of Rb/Sr and Cs/Ba. The ions normally formed by actinides in aqueous solutions in the oxidation states III to VI are M{sup 3+}, M{sup 4+}, MO{sub 2}{sup +} and MO{sub 2}{sup 2+} respectively. Elution parameters were investigated to separate all four actinide species from each other in order to separate isobaric overlaps of the actinides Np, Pu, U and Am. A major question of concern over the possible release of actinides to the environment is the speciation of actinides within their four possible oxidation states. To check the possibility of speciation analysis with ion chromatography, a separation method was investigated to separate U{sup 4+} and UO{sub 2}{sup 2+} without changing the redox species composition during the separation. First results of Pu speciation analysis showed that Pu could be eluted as three different species. Pu(VI) was always eluting at the same time as Np(V). This was surprising as Pu(VI) is expected to have the same chemical characteristics as U(VI) and thus was expected to elute at the same time as U(VI)

  6. DNA-poly(vinyl alcohol) gel matrices: release properties are strongly dependent on electrolytes and cationic surfactants. (United States)

    Valente, Artur J M; Cruz, Sandra M A; Murtinho, Dina M B; Miguel, M Graça; Muniz, Edvani C


    The release of DNA from cryogel PVA-DNA gel matrices to different electrolyte aqueous solutions was investigated. The rate of release and the distribution coefficient of DNA have been quantified by using a first order kinetic law equation, developed in the frame of a partition-based model. The release of DNA from gels to 1:1 sodium and nitrate salts shows that the transport properties are dependent on the ability of anions/cations to solubilise the DNA in the aqueous phase which, with the exception of bromide, can be related to the Hofmeister series; in the presence of multivalent electrolytes, or increasing the ionic strength, the condensation of DNA inside the gel, followed by a phase separation as seen by scanning electron microscopy, induces the retention of DNA inside the polymer matrix. The DNA condensation and/or phase separation, which contribute to a decrease in the water volume fraction inside the gel, determined by swelling degree experiments, also lead to a decrease in the rate constant of DNA release; such decrease can be justified by the difficulty of the molecular aggregate to move through out the polymeric structure. The DNA release is also dependent on the pH of the bulk solution. The effect of uni- and di-valent cationic surfactants on the release properties of DNA was also evaluated. Our findings suggest that the kinetics of DNA release depends on a complex balance between different structural properties of the surfactants, namely charge, bulkiness of the headgroup and alkyl chain length.

  7. Acid decomposition and thiourea leaching of silver from hazardous jarosite residues: Effect of some cations on the stability of the thiourea system. (United States)

    Calla-Choque, D; Nava-Alonso, F; Fuentes-Aceituno, J C


    The recovery of silver from hazardous jarosite residues was studied employing thiourea as leaching agent at acid pH and 90°C. The stability of the thiourea in synthetic solutions was evaluated in the presence of some cations that can be present in this leaching system: cupric and ferric ions as oxidant species, and zinc, lead and iron as divalent ions. Two silver leaching methods were studied: the simultaneous jarosite decomposition-silver leaching, and the jarosite decomposition followed by the silver leaching. The study with synthetic solutions demonstrated that cupric and ferric ions have a negative effect on thiourea stability due to their oxidant properties. The effect of cupric ions is more significant than the effect of ferric ions; other studied cations (Fe(2+), Zn(2+), Pb(2+)) had no effect on the stability of thiourea. When the decomposition of jarosite and the silver leaching are carried out simultaneously, 70% of the silver can be recovered. When the acid decomposition was performed at pH 0.5 followed by the leaching step at pH 1, total silver recovery increased up to 90%. The zinc is completely dissolved with any of these processes while the lead is practically insoluble with these systems producing a lead-rich residue.

  8. Aggregate Formed by a Cationic Fluorescence Probe

    Institute of Scientific and Technical Information of China (English)

    TIAN, Juan; SANG, Da-Yong; JI, Guo-Zhen


    The aggregation behavior of a cationic fluorescence probe 10-(4,7,10,13,16-pentaoxa-1-azacyclooctadecyl-methyl)anthracen-9-ylmethyl dodecanoate (1) was observed and studied by a fluorescence methodology in acidic and neutral conditions. By using the Py scale, differences between simple aggregates and micelles have been discussed. The stability of simple aggregates was discussed in terms of hydrophobic interaction and electrostatic repulsion. The absence of excimer emission of the anthrancene moiety of probe 1 in neutral condition was attributed to the photoinduced electron transfer mechanism instead of photodimerization.

  9. Complex Macromolecular Architectures by Living Cationic Polymerization

    KAUST Repository

    Alghamdi, Reem D.


    Poly (vinyl ether)-based graft polymers have been synthesized by the combination of living cationic polymerization of vinyl ethers with other living or controlled/ living polymerization techniques (anionic and ATRP). The process involves the synthesis of well-defined homopolymers (PnBVE) and co/terpolymers [PnBVE-b-PCEVE-b-PSiDEGVE (ABC type) and PSiDEGVE-b-PnBVE-b-PSiDEGVE (CAC type)] by sequential living cationic polymerization of n-butyl vinyl ether (nBVE), 2-chloroethyl vinyl ether (CEVE) and tert-butyldimethylsilyl ethylene glycol vinyl ether (SiDEGVE), using mono-functional {[n-butoxyethyl acetate (nBEA)], [1-(2-chloroethoxy) ethyl acetate (CEEA)], [1-(2-(2-(t-butyldimethylsilyloxy)ethoxy) ethoxy) ethyl acetate (SiDEGEA)]} or di-functional [1,4-cyclohexanedimethanol di(1-ethyl acetate) (cHMDEA), (VEMOA)] initiators. The living cationic polymerizations of those monomers were conducted in hexane at -20 0C using Et3Al2Cl3 (catalyst) in the presence of 1 M AcOEt base.[1] The PCEVE segments of the synthesized block terpolymers were then used to react with living macroanions (PS-DPE-Li; poly styrene diphenyl ethylene lithium) to afford graft polymers. The quantitative desilylation of PSiDEGVE segments by n-Bu4N+F- in THF at 0 °C led to graft co- and terpolymers in which the polyalcohol is the outer block. These co-/terpolymers were subsequently subjected to “grafting-from” reactions by atom transfer radical polymerization (ATRP) of styrene to afford more complex macromolecular architectures. The base assisted living cationic polymerization of vinyl ethers were also used to synthesize well-defined α-hydroxyl polyvinylether (PnBVE-OH). The resulting polymers were then modified into an ATRP macro-initiator for the synthesis of well-defined block copolymers (PnBVE-b-PS). Bifunctional PnBVE with terminal malonate groups was also synthesized and used as a precursor for more complex architectures such as H-shaped block copolymer by “grafting-from” or

  10. Heart imaging with cationic complexes of technetium

    Energy Technology Data Exchange (ETDEWEB)

    Deutsch, E.; Bushong, W.; Glavan, K.A.; Elder, R.C.; Sodd, V.J.; Scholz, K.L.; Fortman, D.L.; Lukes, S.J.


    The cationic technetium-99 complex trans-(99TC(dmpe)2Cl2)+, where dmpe is bis(1,2-dimethylphosphino)ethane or (CH3)2P-CH2-P(CH3)2, has been prepared and characterized by single-crystal, x-ray structural analysis. The technetium-99m analog, trans-(99mTc(dmpe) 2Cl2)+, has also been prepared and shown to yield excellent gamma-ray images of the heart. The purposeful design, characterization, and synthesis of this technetium-99m radiopharmaceutical represents a striking application of fundamental inorganic chemistry to a problem in applied nuclear medicine.

  11. Phosphate absorption and efflux of three ectomycorrhizal fungi as affected by external phosphate, cation and carbohydrate concentrations. (United States)

    Bücking, Heike


    A prerequisite for symbiotic phosphate transfer in an ectomycorrhizal (ECM) association is hypothesized to be conditions in the interface between both symbiotic partners, that either promote the release of inorganic phosphate (P) from the Hartig net into the interfacial apoplast and/or decrease the fungal reabsorption from this location. To get more information about conditions, which might be involved in the regulation of P efflux or P reabsorption, the effect of various external conditions on 33P-orthophosphate (33P) uptake or efflux by axenic cultures of the ECM basidiomycetes Hebeloma crustliniforme, Amanita muscaria and Laccaria laccata was analysed. In short-time experiments the following external conditions were analysed: an external supply of (1) P in the preculture, (2) cations (0.1-100 mM K, 0.1-50 mM Na, Mg and Ca), and (3) carbohydrates (0.5-50 mM glucose, fructose or sucrose). The P absorption was generally reduced in cultures previously supplied with an abundant P supply and with increased P concentrations in their tissues. The P uptake was also affected by an external supply of cations, whereas carbohydrates had only a slight effect. Compared to Na, Mg and Ca, the P absorption by H. crustuliniforme and L. laccata was increased by 0.1 mM K in the labelling solution but decreased after a supply of 100 mM K and then did not differ from the other cation treatments. Compared to other cations, an addition of 50 mM Ca led to a decrease of P absorption by A. muscaria, whereas 50 mM Mg increased the P uptake by H. crustuliniforme. The P efflux from the fungi was affected by both the cation and carbohydrate concentration of the bathing solution. High concentrations of the monovalent cations K and Na (5 mM or 50 mM) in the bathing solution increased the P efflux by H. crustuliniforme (only Na) and L. laccata (K and Na), but had little effects on A. muscaria. By contrast, the same concentrations of the divalent cation Mg reduced the P efflux from all fungal

  12. Antibacterial Activity of Geminized Amphiphilic Cationic Homopolymers. (United States)

    Wang, Hui; Shi, Xuefeng; Yu, Danfeng; Zhang, Jian; Yang, Guang; Cui, Yingxian; Sun, Keji; Wang, Jinben; Yan, Haike


    The current study is aimed at investigating the effect of cationic charge density and hydrophobicity on the antibacterial and hemolytic activities. Two kinds of cationic surfmers, containing single or double hydrophobic tails (octyl chains or benzyl groups), and the corresponding homopolymers were synthesized. The antimicrobial activity of these candidate antibacterials was studied by microbial growth inhibition assays against Escherichia coli, and hemolysis activity was carried out using human red blood cells. It was interestingly found that the homopolymers were much more effective in antibacterial property than their corresponding monomers. Furthermore, the geminized homopolymers had significantly higher antibacterial activity than that of their counterparts but with single amphiphilic side chains in each repeated unit. Geminized homopolymers, with high positive charge density and moderate hydrophobicity (such as benzyl groups), combine both advantages of efficient antibacterial property and prominently high selectivity. To further explain the antibacterial performance of the novel polymer series, the molecular interaction mechanism is proposed according to experimental data which shows that these specimens are likely to kill microbes by disrupting bacterial membranes, leading them unlikely to induce resistance.

  13. Photodissociation of Cerium Oxide Nanocluster Cations. (United States)

    Akin, S T; Ard, S G; Dye, B E; Schaefer, H F; Duncan, M A


    Cerium oxide cluster cations, CexOy(+), are produced via laser vaporization in a pulsed nozzle source and detected with time-of-flight mass spectrometry. The mass spectrum displays a strongly preferred oxide stoichiometry for each cluster with a specific number of metal atoms x, with x ≤ y. Specifically, the most prominent clusters correspond to the formula CeO(CeO2)n(+). The cluster cations are mass selected and photodissociated with a Nd:YAG laser at either 532 or 355 nm. The prominent clusters dissociate to produce smaller species also having a similar CeO(CeO2)n(+) formula, always with apparent leaving groups of (CeO2). The production of CeO(CeO2)n(+) from the dissociation of many cluster sizes establishes the relative stability of these clusters. Furthermore, the consistent loss of neutral CeO2 shows that the smallest neutral clusters adopt the same oxidation state (IV) as the most common form of bulk cerium oxide. Clusters with higher oxygen content than the CeO(CeO2)n(+) masses are present with much lower abundance. These species dissociate by the loss of O2, leaving surviving clusters with the CeO(CeO2)n(+) formula. Density functional theory calculations on these clusters suggest structures composed of stable CeO(CeO2)n(+) cores with excess oxygen bound to the surface as a superoxide unit (O2(-)).

  14. Electronic absorptions of the benzylium cation (United States)

    Dryza, Viktoras; Chalyavi, Nahid; Sanelli, Julian A.; Bieske, Evan J.


    The electronic transitions of the benzylium cation (Bz+) are investigated over the 250-550 nm range by monitoring the photodissociation of mass-selected C7H7+-Arn (n = 1, 2) complexes in a tandem mass spectrometer. The Bz+-Ar spectrum displays two distinct band systems, the S1←S0 band system extending from 370 to 530 nm with an origin at 19 067 ± 15 cm-1, and a much stronger S3←S0 band system extending from 270 to 320 nm with an origin at 32 035 ± 15 cm-1. Whereas the S1←S0 absorption exhibits well resolved vibrational progressions, the S3←S0 absorption is broad and relatively structureless. Vibronic structure of the S1←S0 system, which is interpreted with the aid of time-dependent density functional theory and Franck-Condon simulations, reflects the activity of four totally symmetric ring deformation modes (ν5, ν6, ν9, ν13). We find no evidence for the ultraviolet absorption of the tropylium cation, which according to the neon matrix spectrum should occur over the 260 - 275 nm range [A. Nagy, J. Fulara, I. Garkusha, and J. Maier, Angew. Chem., Int. Ed. 50, 3022 (2011)], 10.1002/anie.201008036.

  15. Transition-Metal Hydride Radical Cations. (United States)

    Hu, Yue; Shaw, Anthony P; Estes, Deven P; Norton, Jack R


    Transition-metal hydride radical cations (TMHRCs) are involved in a variety of chemical and biochemical reactions, making a more thorough understanding of their properties essential for explaining observed reactivity and for the eventual development of new applications. Generally, these species may be treated as the ones formed by one-electron oxidation of diamagnetic analogues that are neutral or cationic. Despite the importance of TMHRCs, the generally sensitive nature of these complexes has hindered their development. However, over the last four decades, many more TMHRCs have been synthesized, characterized, isolated, or hypothesized as reaction intermediates. This comprehensive review focuses on experimental studies of TMHRCs reported through the year 2014, with an emphasis on isolated and observed species. The methods used for the generation or synthesis of TMHRCs are surveyed, followed by a discussion about the stability of these complexes. The fundamental properties of TMHRCs, especially those pertaining to the M-H bond, are described, followed by a detailed treatment of decomposition pathways. Finally, reactions involving TMHRCs as intermediates are described.

  16. Cationic Antimicrobial Polymers and Their Assemblies

    Directory of Open Access Journals (Sweden)

    Ana Maria Carmona-Ribeiro


    Full Text Available Cationic compounds are promising candidates for development of antimicrobial agents. Positive charges attached to surfaces, particles, polymers, peptides or bilayers have been used as antimicrobial agents by themselves or in sophisticated formulations. The main positively charged moieties in these natural or synthetic structures are quaternary ammonium groups, resulting in quaternary ammonium compounds (QACs. The advantage of amphiphilic cationic polymers when compared to small amphiphilic molecules is their enhanced microbicidal activity. Besides, many of these polymeric structures also show low toxicity to human cells; a major requirement for biomedical applications. Determination of the specific elements in polymers, which affect their antimicrobial activity, has been previously difficult due to broad molecular weight distributions and random sequences characteristic of radical polymerization. With the advances in polymerization control, selection of well defined polymers and structures are allowing greater insight into their structure-antimicrobial activity relationship. On the other hand, antimicrobial polymers grafted or self-assembled to inert or non inert vehicles can yield hybrid antimicrobial nanostructures or films, which can act as antimicrobials by themselves or deliver bioactive molecules for a variety of applications, such as wound dressing, photodynamic antimicrobial therapy, food packing and preservation and antifouling applications.

  17. Nature as a source of inspiration for cationic lipid synthesis. (United States)

    Labas, Romain; Beilvert, Fanny; Barteau, Benoit; David, Stéphanie; Chèvre, Raphaël; Pitard, Bruno


    Synthetic gene delivery systems represent an attractive alternative to viral vectors for DNA transfection. Cationic lipids are one of the most widely used non-viral vectors for the delivery of DNA into cultured cells and are easily synthesized, leading to a large variety of well-characterized molecules. This review discusses strategies for the design of efficient cationic lipids that overcome the critical barriers of in vitro transfection. A particular focus is placed on natural hydrophilic headgroups and lipophilic tails that have been used to synthesize biocompatible and non-toxic cationic lipids. We also present chemical features that have been investigated to enhance the transfection efficiency of cationic lipids by promoting the escape of lipoplexes from the endosomal compartment and DNA release from DNA-liposome complexes. Transfection efficiency studies using these strategies are likely to improve the understanding of the mechanism of cationic lipid-mediated gene delivery and to help the rational design of novel cationic lipids.

  18. Structural Studies of Divalent Transition Metal Cobalt With Bis-(2,6-Diacetyl Pyridine Monoxime 1,2-Di-Iminobenzene.

    Directory of Open Access Journals (Sweden)

    Shamshad Ahmad Khan


    Full Text Available The complexes of divalent Cobalt with bis(2,6-diacetyl pyridine monoxime1,2-di-iminobenzene have been prepared separately in presence of respective salts. The general molecular formula of the complexes have been found to be [Co(L]X2 where L=Bis(2,6-diacetyl pyridine monoxime1,2-di-iminobenzene, X=chloride, bromide, sulphate, perchlorate, nitrate, acetate ions, On the characterisation of the complexes by usual physico-chemical method, all the complexes have been found to be monomeric and octahedral in geometry.

  19. Solvent Extraction of Some Divalent Metal Cations into Nitrobenzene by Using a Synergistic Mixture of Strontium Dicarbollylcobaltate and p-tert-Butylcalix[4]arene-tetrakis (N,N-Diethylacetamide). (United States)

    Makrlík, Emanuel; Budka, Jan; Vaňura, Petr; Selucký, Pavel


    From extraction experiments and g-activity measurements, the exchange extraction constants corresponding to the general equilibrium M2+(aq) + 1•Sr2+(nb) 1•M2+(nb) + Sr2+(aq) taking place in the two-phase water-nitrobenzene system (M2+ = Ca2+, Ba2+, Cu2+, Zn2+, Cd2+, Pb2+, UO22+, Mn2+, Co2+, Ni2+; 1 = p-tert-butylcalix[4]arene-tetrakis(N,N-diethylacetamide); aq = aqueous phase, nb = nitrobenzene phase) were determined. Further, the stability constants of the 1•M2+ complexes in water-saturated nitrobenzene were calculated; they were found to increase in the series of Cu2+ < Ba2+ < Zn2+ < Ni2+ < UO22+ < Co2+ < Mn2+ < Cd2+ < Ca2+ < Pb2+.

  20. Cation-π interaction of the univalent silver cation with meso-octamethylcalix[4]pyrrole: Experimental and theoretical study (United States)

    Polášek, Miroslav; Kvíčala, Jaroslav; Makrlík, Emanuel; Křížová, Věra; Vaňura, Petr


    By using electrospray ionization mass spectrometry (ESI-MS), it was proven experimentally that the univalent silver cation Ag+ forms with meso-octamethylcalix[4]pyrrole (abbrev. 1) the cationic complex species 1·Ag+. Further, applying quantum chemical DFT calculations, four different conformations of the resulting complex 1·Ag+ were derived. It means that under the present experimental conditions, this ligand 1 can be considered as a macrocyclic receptor for the silver cation.

  1. Capturing dynamic cation hopping in cubic pyrochlores (United States)

    Brooks Hinojosa, Beverly; Asthagiri, Aravind; Nino, Juan C.


    In direct contrast to recent reports, density functional theory predicts that the most stable structure of Bi2Ti2O7 pyrochlore is a cubic Fd3¯m space group by accounting for atomic displacements. The displaced Bi occupies the 96g(x,x,z) Wyckoff position with six equivalent sites, which create multiple local minima. Using nudged elastic band method, the transition states of Bi cation hopping between equivalent minima were investigated and an energy barrier between 0.11 and 0.21 eV was determined. Energy barriers associated with the motion of Bi between equivalent sites within the 96g Wyckoff position suggest the presence of dielectric relaxation in Bi2Ti2O7.

  2. Retention of Cationic Starch onto Cellulose Fibres (United States)

    Missaoui, Mohamed; Mauret, Evelyne; Belgacem, Mohamed Naceur


    Three methods of cationic starch titration were used to quantify its retention on cellulose fibres, namely: (i) the complexation of CS with iodine and measurement of the absorbency of the ensuing blue solution by UV-vis spectroscopy; (ii) hydrolysis of the starch macromolecules followed by the conversion of the resulting sugars to furan-based molecules and quantifying the ensuing mixture by measuring their absorbance at a Ι of 490 nm, using the same technique as previous one and; finally (iii) hydrolysis of starch macromolecules by trifluoro-acetic acid and quantification of the sugars in the resulting hydrolysates by high performance liquid chromatography. The three methods were found to give similar results within the range of CS addition from 0 to 50 mg per g of cellulose fibres.

  3. Repurposing Cationic Amphiphilic Antihistamines for Cancer Treatment

    DEFF Research Database (Denmark)

    Ellegaard, Anne-Marie; Dehlendorff, Christian; Vind, Anna C.;


    Non-small cell lung cancer (NSCLC) is one of the deadliest cancers worldwide. In search for new NSCLC treatment options, we screened a cationic amphiphilic drug (CAD) library for cytotoxicity against NSCLC cells and identified several CAD antihistamines as inducers of lysosomal cell death. We...... then performed a cohort study on the effect of CAD antihistamine use on mortality of patients diagnosed with non-localized cancer in Denmark between 1995 and 2011. The use of the most commonly prescribed CAD antihistamine, loratadine, was associated with significantly reduced all-cause mortality among patients...... with non-localized NSCLC or any non-localized cancer when compared with use of non-CAD antihistamines and adjusted for potential confounders. Of the less frequently described CAD antihistamines, astemizole showed a similar significant association with reduced mortality as loratadine among patients with any...

  4. Heart imaging with cationic complexes of technetium

    Energy Technology Data Exchange (ETDEWEB)

    Deutsch, E. (Univ. of Cincinnati, Cincinnati, OH); Bushong, W.; Glavan, K.A.; Elder, R.C.; Sodd, V.J.; Scholz, K.L.; Fortman, D.L.; Lukes, S.J.


    The cationic technetium-99 complex trans-(/sup 99/Tc(dmpe)/sub 2/Cl/sub 2/)/sup +/, where dmpe is bis(1,2-dimethylphosphino)ethane or (CH/sub 3/)/sub 2/P-CH/sub 2/CH/sub 2/-P(CH/sub 3/)/sub 2/, has been prepared and characterized by single-crystal, x-ray structural analysis. The technetium-99m analog, trans-(/sup 99m/Tc (dmpe)/sub 2/Cl/sub 2/)/sup +/, has also been prepared and shown to yield excellent gamma-ray images of the heart. The purposeful design, characterization, and synthesis of this technetium-99m radiopharmaceutical represents a striking application of fundamental inorganic chemistry to a problem in applied nuclear medicine.

  5. Electron spectra of radical cations of heteroanalogs

    Energy Technology Data Exchange (ETDEWEB)

    Petrushenko, K.B.; Turchaninov, V.K.; Vokin, A.I.; Ermikov, A.F.; Frolov, Yu.L.


    Radical cation spectra of indazole and benzothiophene in the visible region were obtained by laser photolysis during the reaction of photoexcited quinones with these compounds in acetonitrile. The charge transfer bands of the complexes of the test compounds with p-chloranil and 7,7,8,8-tetracyanoquinodimethane in dioxane were recorded on a Specord M-40. Photoelectron spectra were obtained on a ES-3201 electron spectrometer. The He(I) resonance band (21.21 eV) was used for excitation. Measurements were carried out in the 60-120/sup 0/C range. The energy scale was calibrated form the first ionization potentials of Ar (15.76 eV) and chlorobenzene (9.06 eV). The error in the determination of the ionization potentials for the first four photoelectron bands was 0.05 eV.

  6. Hydration Structure of the Quaternary Ammonium Cations

    KAUST Repository

    Babiaczyk, Wojtek Iwo


    Two indicators of the hydropathicity of small solutes are introduced and tested by molecular dynamics simulations. These indicators are defined as probabilities of the orientation of water molecules\\' dipoles and hydrogen bond vectors, conditional on a generalized distance from the solute suitable for arbitrarily shaped molecules. Using conditional probabilities, it is possible to distinguish features of the distributions in close proximity of the solute. These regions contain the most significant information on the hydration structure but cannot be adequately represented by using, as is usually done, joint distance-angle probability densities. Our calculations show that using our indicators a relative hydropathicity scale for the interesting test set of the quaternary ammonium cations can be roughly determined. © 2010 American Chemical Society.

  7. Antiviral effect of cationic compounds on bacteriophages

    Directory of Open Access Journals (Sweden)

    Mai Huong eChatain-Ly


    Full Text Available The antiviral activity of several cationic compounds - cetytrimethylammonium (CTAB, chitosan, nisin and lysozyme - was investigated on the bacteriophage c2 (DNA head and non-contractile tail infecting Lactococcus strains and the bacteriophage MS2 (F-specific RNA infecting E.coli. Firstly, these activities were evaluated in a phosphate buffer pH 7- 10 mM. The CTAB had a virucidal effect on the Lactococcus bacteriophages, but not on the MS2. After 1 min of contact with 0.125 mM CTAB, the c2 population was reduced from 6 log(pfu/mL to 1,5 log(pfu/mL and completely deactivated at 1 mM. On the contrary, chitosan inhibited the MS2 more than it did the bacteriophages c2. No antiviral effect was observed for the nisin or the lysozyme on bacteriophages after 1 min of treatment. A 1 and 2.5 log reduction was respectively observed for nisin and lysozyme when the treatment time increased (5 or 10 min. These results showed that the antiviral effect depended both on the virus and structure of the antimicrobial compounds. The antiviral activity of these compounds was also evaluated in different physico-chemical conditions and in complex matrices. The antiviral activity of CTAB was impaired in acid pH and with an increase of the ionic strength. These results might be explained by the electrostatic interactions between cationic compounds and negatively charged particles such as bacteriophages or other compounds in a matrix. Milk proved to be protective suggesting the components of food could interfere with antimicrobial compounds.

  8. Role of extracellular cations in cell motility, polarity, and chemotaxis

    Directory of Open Access Journals (Sweden)

    Soll D


    Full Text Available David R Soll1, Deborah Wessels1, Daniel F Lusche1, Spencer Kuhl1, Amanda Scherer1, Shawna Grimm1,21Monoclonal Antibody Research Institute, Developmental Studies, Hybridoma Bank, Department of Biology, University of Iowa, Iowa City; 2Mercy Medical Center, Surgical Residency Program, Des Moines, Iowa, USAAbstract: The concentration of cations in the aqueous environment of free living organisms and cells within the human body influence motility, shape, and chemotaxis. The role of extracellular cations is usually perceived to be the source for intracellular cations in the process of homeostasis. The role of surface molecules that interact with extracellular cations is believed to be that of channels, transporters, and exchangers. However, the role of Ca2+ as a signal and chemoattractant and the discovery of the Ca2+ receptor have demonstrated that extracellular cations can function as signals at the cell surface, and the plasma membrane molecules they interact with can function as bona fide receptors that activate coupled signal transduction pathways, associated molecules in the plasma membrane, or the cytoskeleton. With this perspective in mind, we have reviewed the cationic composition of aqueous environments of free living cells and cells that move in multicellular organisms, most notably humans, the range of molecules interacting with cations at the cell surface, the concept of a cell surface cation receptor, and the roles extracellular cations and plasma membrane proteins that interact with them play in the regulation of motility, shape, and chemotaxis. Hopefully, the perspective of this review will increase awareness of the roles extracellular cations play and the possibility that many of the plasma membrane proteins that interact with them could also play roles as receptors.Keywords: extracellular cations, chemotaxis, transporters, calcium, receptors

  9. The Effect of Hydration on the Cation-π Interaction Between Benzene and Various Cations

    Indian Academy of Sciences (India)



    The effect of hydration on cation-π interaction in Mq+ BmWn (B = benzene; W = water; Mq+ =Na⁺, K⁺, Mg²⁺, Ca²⁺, Al³⁺, 0 ≤ n,m ≤ 4, 1≤ m + n ≤ 4) complexes has been investigated using ab initio quantum chemical methods. Interaction energy values computed at the MP2 level of theory using the 6-31G(d,p) basis set reveal a qualitative trend in the relative affinity of different cations for benzene and water in these complexes. The π–cloud thickness values for benzene have also been estimated for these systems.

  10. In vivo toxicity of cationic micelles and liposomes

    DEFF Research Database (Denmark)

    Knudsen, Kristina Bram; Northeved, Helle; Ek, Pramod Kumar


    This study investigated toxicity of nanocarriers comprised of cationic polymer and lipid components often used in gene and drug delivery, formulated as cationic micelles and liposomes. Rats were injected intravenously with 10, 25 or 100 mg/kg and sacrificed after 24 or 48 h, or 24 h after the last...

  11. How mobile are sorbed cations in clays and clay rocks? (United States)

    Gimmi, T; Kosakowski, G


    Diffusion of cations and other contaminants through clays is of central interest, because clays and clay rocks are widely considered as barrier materials for waste disposal sites. An intriguing experimental observation has been made in this context: Often, the diffusive flux of cations at trace concentrations is much larger and the retardation smaller than expected based on their sorption coefficients. So-called surface diffusion of sorbed cations has been invoked to explain the observations but remains a controversial issue. Moreover, the corresponding surface diffusion coefficients are largely unknown. Here we show that, by an appropriate scaling, published diffusion data covering a broad range of cations, clays, and chemical conditions can all be modeled satisfactorily by a surface diffusion model. The average mobility of sorbed cations seems to be primarily an intrinsic property of each cation that follows inversely its sorption affinity. With these surface mobilities, cation diffusion coefficients can now be estimated from those of water tracers. In pure clays at low salinities, surface diffusion can reduce the cation retardation by a factor of more than 1000.

  12. Interactions between cationic liposomes and drugs or biomolecules

    Directory of Open Access Journals (Sweden)



    Full Text Available Multiple uses for synthetic cationic liposomes composed of dioctadecyldimethylammonium bromide (DODAB bilayer vesicles are presented. Drugs or biomolecules can be solubilized or incorporated in the cationic bilayers. The cationic liposomes themselves can act as antimicrobial agents causing death of bacteria and fungi at concentrations that barely affect mammalian cells in culture. Silica particles or polystyrene microspheres can be functionalized by coverage with DODAB bilayers or phospholipid monolayers. Negatively charged antigenic proteins can be carried by the cationic liposomes which generate a remarkable immunoadjuvant action. Nucleotides or DNA can be physically adsorbed to the cationic liposomes to be transferred to mammalian cells for gene therapy. An overview of the interactions between DODAB vesicles and some biomolecules or drugs clearly points out their versatility for useful applications in a near future.

  13. Interactions between cationic liposomes and drugs or biomolecules. (United States)

    Carmona-Ribeiro, A M


    Multiple uses for synthetic cationic liposomes composed of dioctadecyldimethylammonium bromide (DODAB) bilayer vesicles are presented. Drugs or biomolecules can be solubilized or incorporated in the cationic bilayers. The cationic liposomes themselves can act as antimicrobial agents causing death of bacteria and fungi at concentrations that barely affect mammalian cells in culture. Silica particles or polystyrene microspheres can be functionalized by coverage with DODAB bilayers or phospholipid monolayers. Negatively charged antigenic proteins can be carried by the cationic liposomes which generate a remarkable immunoadjuvant action. Nucleotides or DNA can be physically adsorbed to the cationic liposomes to be transferred to mammalian cells for gene therapy. An overview of the interactions between DODAB vesicles and some biomolecules or drugs clearly points out their versatility for useful applications in a near future.

  14. Do Cation-π Interactions Exist in Bacteriorhodopsin

    Institute of Scientific and Technical Information of China (English)

    HU Kun-Sheng; WANG Guang-Yu; HE Jin-An


    Metal ions are essential to the structure and physiological functions of bacteriorhodopsin. Experimental evidence suggests the existence of specific cation binding to the negatively charged groups of Asp85 and Asp212 via an electrostatic interaction. However, only using electrostatic force is not enough to explain the role of the metal cations because the carboxylate of Asp85 is well known to be protonated in the M intermediate. Considering the presence of some aromatic amino acid residues in the vicinity of the retinal pocket, the existence of cation-π interactions between the metal cation and aromatic amino acid residues is suggested. Obviously, introduction of this kind of interaction is conducive to understanding the effects of the metal cations and aromatic amino acid residues inside the protein on the structural stability and proton pumping of bacteriorhodopsin.

  15. Synthesis, characterization, and ligand exchange reactivity of a series of first row divalent metal 3-hydroxyflavonolate complexes. (United States)

    Grubel, Katarzyna; Rudzka, Katarzyna; Arif, Atta M; Klotz, Katie L; Halfen, Jason A; Berreau, Lisa M


    A series of divalent metal flavonolate complexes of the general formula [(6-Ph(2)TPA)M(3-Hfl)]X (1-5-X; X = OTf(-) or ClO(4)(-); 6-Ph(2)TPA = N,N-bis((6-phenyl-2-pyridyl)methyl)-N-((2-pyridyl)methyl)amine; M = Mn(II), Co(II), Ni(II), Cu(II), Zn(II); 3-Hfl = 3-hydroxyflavonolate) were prepared and characterized by X-ray crystallography, elemental analysis, FTIR, UV-vis, (1)H NMR or EPR, and cyclic voltammetry. All of the complexes have a bidentate coordinated flavonolate ligand. The difference in M-O distances (Delta(M-O)) involving this ligand varies through the series, with the asymmetry of flavonolate coordination increasing in the order Mn(II) approximately Ni(II) pi*) of the coordinated flavonolate ligand in 1-5-OTf (relative to that in free anion) increases in the order Ni(II) metals fit well with this ordering. (1)H NMR studies indicate that the 3-Hfl complexes of Co(II), Ni(II), and Zn(II) exhibit a pseudo-octahedral geometry in solution. EPR studies suggest that the Mn(II) complex 1-OTf may form binuclear structures in solution. The mononuclear Cu(II) complex 4-OTf has a distorted square pyramidal geometry. The oxidation potential of the flavonolate ligand depends on the metal ion present and/or the solution structure of the complex, with the Mn(II) complex 1-OTf exhibiting the lowest potential, followed by the pseudo-octahedral Ni(II) and Zn(II) 3-Hfl complexes, and the distorted square pyramidal Cu(II) complex 4-OTf. The Mn(II) complex [(6-Ph(2)TPA)Mn(3-Hfl)]OTf (1-OTf) is unique in the series in undergoing ligand exchange reactions in the presence of M(ClO(4))(2).6H(2)O (M = Co, Ni, Zn) in CD(3)CN to produce [(6-Ph(2)TPA)M(CD(3)CN)(n)](X)(2), [Mn(3-Hfl)(2).0.5H(2)O], and MnX(2) (X = OTf(-) or ClO(4)(-)). Under similar conditions, the 3-Hfl complexes of Co(II), Ni(II), and Cu(II) undergo flavonolate ligand exchange to produce [(6-Ph(2)TPA)M(CD(3)CN)(n)](X)(2) (M = Co, Ni, Cu; n = 1 or 2) and [Zn(3-Hfl)(2).2H(2)O]. An Fe(II) complex of 3-Hfl, [(6-Ph(2)TPA

  16. Trace Metals in Groundwater and Vadose Zone Calcite: In Situ Containment and Stabilization of Stronthium-90 and Other Divalent Metals and Radionuclides at Arid Western DOE Sites: Final Report for Award Number DE-FG07-02ER63486 to the University of Idaho (RW Smith) Environmental Management Science Program Project Number 87016

    Energy Technology Data Exchange (ETDEWEB)

    Smith, Robert W.; Fujita, Yoshiko


    Radionuclide and metal contaminants are present in the vadose zone and groundwater throughout the U.S. Department of Energy (DOE) energy research and weapons complex. In situ containment and stabilization of these contaminants represents a cost-effective treatment strategy that minimizes workers’ exposure to hazardous substances, does not require removal or transport of contaminants, and generally does not generate a secondary waste stream. We have investigated an in situ bioremediation approach that immobilizes radionuclides or contaminant metals (e.g., strontium-90) by their microbially facilitated co-precipitation with calcium carbonate in groundwater and vadose zone systems. Calcite, a common mineral in many aquifers and vadose zones in the arid west, can incorporate divalent metals such as strontium, cadmium, lead, and cobalt into its crystal structure by the formation of a solid solution. Collaborative research undertaken by the Idaho National Laboratory (INL), University of Idaho, and University of Toronto as part of this Environmental Management Science Program project has focused on in situ microbially-catalyzed urea hydrolysis, which results in an increase in pH, carbonate alkalinity, ammonium, calcite precipitation, and co-precipitation of divalent cations. In calcite-saturated aquifers, microbially facilitated co-precipitation with calcium carbonate represents a potential long-term contaminant sequestration mechanism. Key results of the project include: **Demonstrating the linkage between urea hydrolysis and calcite precipitation in field and laboratory experiments **Observing strontium incorporation into calcite precipitate by urea hydrolyzers with higher distribution coefficient than in abiotic **Developing and applying molecular methods for characterizing microbial urease activity in groundwater including a quantitative PCR method for enumerating ureolytic bacteria **Applying the suite of developed molecular methods to assess the feasibility of the

  17. Anaerobic toxicity of cationic silver nanoparticles

    Energy Technology Data Exchange (ETDEWEB)

    Gitipour, Alireza; Thiel, Stephen W. [Biomedical, Chemical, and Environmental Engineering, University of Cincinnati, Cincinnati, OH (United States); Scheckel, Kirk G. [USEPA, Office of Research and Development, Cincinnati, OH (United States); Tolaymat, Thabet, E-mail: [USEPA, Office of Research and Development, Cincinnati, OH (United States)


    The microbial toxicity of silver nanoparticles (AgNPs) stabilized with different capping agents was compared to that of Ag{sup +} under anaerobic conditions. Three AgNPs were investigated: (1) negatively charged citrate-coated AgNPs (citrate-AgNPs), (2) minimally charged polyvinylpyrrolidone coated AgNPs (PVP-AgNPs) and (3) positively charged branched polyethyleneimine coated AgNPs (BPEI-AgNPs). The AgNPs investigated in this experiment were similar in size (10–15 nm), spherical in shape, but varied in surface charge which ranged from highly negative to highly positive. While, at AgNPs concentrations lower than 5 mg L{sup −1}, the anaerobic decomposition process was not influenced by the presence of the nanoparticles, there was an observed impact on the diversity of the microbial community. At elevated concentrations (100 mg L{sup −1} as silver), only the cationic BPEI-AgNPs demonstrated toxicity similar in magnitude to that of Ag{sup +}. Both citrate and PVP-AgNPs did not exhibit toxicity at the 100 mg L{sup −1} as measured by biogas evolution. These findings further indicate the varying modes of action for nanoparticle toxicity and represent one of the few studies that evaluate end-of-life management concerns with regards to the increasing use of nanomaterials in our everyday life. These findings also highlight some of the concerns with a one size fits all approach to the evaluation of environmental health and safety concerns associated with the use of nanoparticles. - Highlights: • At concentrations -1 the anaerobic decomposition process was not impacted. • An impact on the microbial community at concentrations -1 were observed. • At high concentrations (100 mg L{sup −1}), the cationic BPEI-AgNPs demonstrated toxicity. • Toxicity was demonstrated without the presence of oxidative dissolution of silver. • A one size fits all approach for the evaluation of NPs may not be accurate.

  18. IRMPD Action Spectroscopy of Alkali Metal Cation-Cytosine Complexes: Effects of Alkali Metal Cation Size on Gas Phase Conformation

    NARCIS (Netherlands)

    Yang, B.; Wu, R.R.; Polfer, N.C.; Berden, G.; Oomens, J.; Rodgers, M.T.


    The gas-phase structures of alkali metal cation-cytosine complexes generated by electrospray ionization are probed via infrared multiple photon dissociation (IRMPD) action spectroscopy and theoretical calculations. IRMPD action spectra of five alkali metal cation-cytosine complexes exhibit both simi

  19. The role of trivalent cations and interlayer anions on the formation of layered double hydroxides in an oxic-CO{sub 2} medium

    Energy Technology Data Exchange (ETDEWEB)

    Paikaray, Susanta, E-mail: [Department of Geological Sciences, University of Saskatchewan, Saskatoon, SK, S7N 5E2 (Canada); Hendry, M. Jim [Department of Geological Sciences, University of Saskatchewan, Saskatoon, SK, S7N 5E2 (Canada)


    Highlights: Black-Right-Pointing-Pointer Strong agglomeration of nano particles. Black-Right-Pointing-Pointer Atmospheric CO{sub 2} easily incorporates as interlayer anion even in presence of dissolved SO{sub 4}{sup 2-}. Black-Right-Pointing-Pointer Fe{sup 3+} substitution attracts excess anion vs. Al{sup 3+}, both SO{sub 4}{sup 2-} and CO{sub 3}{sup 2-}, due to high charge deficiency. Black-Right-Pointing-Pointer Iron (Fe{sup 3+}) causes increase in lattice parameters compared to Al{sup 3+}. Black-Right-Pointing-Pointer MgAlCO{sub 3}/SO{sub 4}-type LDHs have better cation ordering compared to MgFeCO{sub 3}/SO{sub 4}-type LDHs. - Abstract: Most common occurrences of magnesium (Mg{sup 2+}), aluminum (Al{sup 3+}), iron (Fe{sup 3+}), carbonate (CO{sub 3}{sup 2-}), and sulfate (SO{sub 4}{sup 2-}) in environmental settings can lead to formation of layered double hydroxides. This study investigated the role of different trivalent cations and divalent interlayer anions on the physicochemical properties of hydrotalcite-like layered double hydroxides. Hydrotalcite-like compounds (HTLCs) were synthesized at ambient temperature by co-precipitation while maintaining Mg{sup 2+} as the primary divalent cation and varying Al{sup 3+} and Fe{sup 3+} as the trivalent cations and SO{sub 4}{sup 2-} and CO{sub 3}{sup 2-} as the interlayer anions. X-ray diffractograms, Raman and infrared spectra, and scanning electron microscopy images confirmed the precipitation of rounded fibrous HTLCs. BET analyses showed that the MgAlCO{sub 3}-type HTLC had the greatest surface area (101.7 m{sup 2}/g), followed by MgAlSO{sub 4} (93.9 m{sup 2}/g), MgFeCO{sub 3} (81.3 m{sup 2}/g), and MgFeSO{sub 4} (17.8 m{sup 2}/g). Substitution of Fe{sup 3+} increased lattice parameters compared to Al{sup 3+} substitution. Incorporation of SO{sub 4}{sup 2-} as an interlayer anion was favored during Fe{sup 3+} substitution but reduced the crystallinity of the HTLC. Carbonate was the preferred interlayer anion, but

  20. Cation Defects and Conductivity in Transparent Oxides

    Energy Technology Data Exchange (ETDEWEB)

    Exarhos, Gregory J.; Windisch, Charles F.; Ferris, Kim F.; Owings, Robert R.


    High quality doped zinc oxide and mixed transition metal spinel oxide films have been deposited by means of sputter deposition from metal and metal oxide targets, and by spin casting from aqueous or alcoholic precursor solutions. Deposition conditions and post-deposition processing are found to alter cation oxidation states and their distributions in both oxide materials resulting in marked changes to both optical transmission and electrical response. For ZnO, partial reduction of the neat or doped material by hydrogen treatment of the heated film or by electrochemical processing renders the oxide n-type conducting. Continued reduction was found to diminish conductivity. In contrast, oxidation of the infrared transparent p-type spinel conductors typified by NiCo2O4 was found to increase conductivity. The disparate behavior of these two materials is caused in part by the sign of the charge carrier and by the existence of two different charge transport mechanisms that are identified as free carrier conduction and polaron hopping. While much work has been reported concerning structure/property relationships in the free carrier conducting oxides, there is a significantly smaller body of information on transparent polaron conductors. In this paper, we identify key parameters that promote conductivity in mixed metal spinel oxides and compare their behavior with that of the free carrier TCO’s.


    Directory of Open Access Journals (Sweden)

    Elina Orblin


    Full Text Available Papermaking pulps are a mixture of fibres, fibre fragments, and small cells (parenchyma or ray cells, usually called pulp fines. The interactions between pulp fines and a cationic copolymer of acrylamide and acryloxyethyltrimethyl ammonium chloride were investigated based on solid-liquid isotherms prepared under different turbulence, and subsequent advanced surface characterization using X-ray photoelectron spectroscopy (XPS and time-of-flight secondary ion mass spectrometry (ToF-SIMS. The surface charge and surface area of pulp fine substrates were measured by methylene blue sorption-XPS analysis and nitrogen adsorption combined with mercury porosimetry, respectively. The driving force behind polyelectrolyte adsorption was the amount of the surface anionic charge, whereas surface area appeared to be of less importance. Based on a comparison of solid-liquid and XPS sorption isotherms, different polyelectrolyte conformations were suggested, depending on the types of fines: A flatter conformation and partial cell-wall penetration of polyelectrolytes on kraft fines from freshly prepared pulp, and a more free conformation with extended loops and tails on lignocellulosic fines from recycled pulp. Additionally, ToF-SIMS imaging proved that recycled pulp fines contained residual de-inking chemicals (primarily palmitic acid salts that possibly hinder the electrostatic interactions with polyelectrolytes.

  2. Cationic Noncovalent Interactions: Energetics and Periodic Trends. (United States)

    Rodgers, M T; Armentrout, P B


    In this review, noncovalent interactions of ions with neutral molecules are discussed. After defining the scope of the article, which excludes anionic and most protonated systems, methods associated with measuring thermodynamic information for such systems are briefly recounted. An extensive set of tables detailing available thermodynamic information for the noncovalent interactions of metal cations with a host of ligands is provided. Ligands include small molecules (H2, NH3, CO, CS, H2O, CH3CN, and others), organic ligands (O- and N-donors, crown ethers and related molecules, MALDI matrix molecules), π-ligands (alkenes, alkynes, benzene, and substituted benzenes), miscellaneous inorganic ligands, and biological systems (amino acids, peptides, sugars, nucleobases, nucleosides, and nucleotides). Hydration of metalated biological systems is also included along with selected proton-based systems: 18-crown-6 polyether with protonated peptides and base-pairing energies of nucleobases. In all cases, the literature thermochemistry is evaluated and, in many cases, reanchored or adjusted to 0 K bond dissociation energies. Trends in these values are discussed and related to a variety of simple molecular concepts.

  3. Repurposing Cationic Amphiphilic Antihistamines for Cancer Treatment

    Directory of Open Access Journals (Sweden)

    Anne-Marie Ellegaard


    Full Text Available Non-small cell lung cancer (NSCLC is one of the deadliest cancers worldwide. In search for new NSCLC treatment options, we screened a cationic amphiphilic drug (CAD library for cytotoxicity against NSCLC cells and identified several CAD antihistamines as inducers of lysosomal cell death. We then performed a cohort study on the effect of CAD antihistamine use on mortality of patients diagnosed with non-localized cancer in Denmark between 1995 and 2011. The use of the most commonly prescribed CAD antihistamine, loratadine, was associated with significantly reduced all-cause mortality among patients with non-localized NSCLC or any non-localized cancer when compared with use of non-CAD antihistamines and adjusted for potential confounders. Of the less frequently described CAD antihistamines, astemizole showed a similar significant association with reduced mortality as loratadine among patients with any non-localized cancer, and ebastine use showed a similar tendency. The association between CAD antihistamine use and reduced mortality was stronger among patients with records of concurrent chemotherapy than among those without such records. In line with this, sub-micromolar concentrations of loratadine, astemizole and ebastine sensitized NSCLC cells to chemotherapy and reverted multidrug resistance in NSCLC, breast and prostate cancer cells. Thus, CAD antihistamines may improve the efficacy of cancer chemotherapy.

  4. Cation exchange properties of zeolites in hyper alkaline aqueous media. (United States)

    Van Tendeloo, Leen; de Blochouse, Benny; Dom, Dirk; Vancluysen, Jacqueline; Snellings, Ruben; Martens, Johan A; Kirschhock, Christine E A; Maes, André; Breynaert, Eric


    Construction of multibarrier concrete based waste disposal sites and management of alkaline mine drainage water requires cation exchangers combining excellent sorption properties with a high stability and predictable performance in hyper alkaline media. Though highly selective organic cation exchange resins have been developed for most pollutants, they can serve as a growth medium for bacterial proliferation, impairing their long-term stability and introducing unpredictable parameters into the evolution of the system. Zeolites represent a family of inorganic cation exchangers, which naturally occur in hyper alkaline conditions and cannot serve as an electron donor or carbon source for microbial proliferation. Despite their successful application as industrial cation exchangers under near neutral conditions, their performance in hyper alkaline, saline water remains highly undocumented. Using Cs(+) as a benchmark element, this study aims to assess the long-term cation exchange performance of zeolites in concrete derived aqueous solutions. Comparison of their exchange properties in alkaline media with data obtained in near neutral solutions demonstrated that the cation exchange selectivity remains unaffected by the increased hydroxyl concentration; the cation exchange capacity did however show an unexpected increase in hyper alkaline media.

  5. Lipopolysaccharide Neutralization by Cationic-Amphiphilic Polymers through Pseudoaggregate Formation. (United States)

    Uppu, Divakara S S M; Haldar, Jayanta


    Synthetic polymers incorporating the cationic charge and hydrophobicity to mimic the function of antimicrobial peptides (AMPs) have been developed. These cationic-amphiphilic polymers bind to bacterial membranes that generally contain negatively charged phospholipids and cause membrane disintegration resulting in cell death; however, cationic-amphiphilic antibacterial polymers with endotoxin neutralization properties, to the best of our knowledge, have not been reported. Bacterial endotoxins such as lipopolysaccharide (LPS) cause sepsis that is responsible for a great amount of mortality worldwide. These cationic-amphiphilic polymers can also bind to negatively charged and hydrophobic LPS and cause detoxification. Hence, we envisaged that cationic-amphiphilic polymers can have both antibacterial as well as LPS binding properties. Here we report synthetic amphiphilic polymers with both antibacterial as well as endotoxin neutralizing properties. Levels of proinflammatory cytokines in human monocytes caused by LPS stimulation were inhibited by >80% when coincubated with these polymers. These reductions were found to be dependent on concentration and, more importantly, on the side-chain chemical structure due to variations in the hydrophobicity profiles of these polymers. These cationic-amphiphilic polymers bind and cause LPS neutralization and detoxification. Investigations of polymer interaction with LPS using fluorescence spectroscopy and dynamic light scattering (DLS) showed that these polymers bind but neither dissociate nor promote LPS aggregation. We show that polymer binding to LPS leads to sort of a pseudoaggregate formation resulting in LPS neutralization/detoxification. These findings provide an unusual mechanism of LPS neutralization using novel synthetic cationic-amphiphilic polymers.

  6. Neutron diffraction investigations of kesterites: cation order and disorder

    Energy Technology Data Exchange (ETDEWEB)

    Schorr, Susan [Free University Berlin, Institute of Geological Sciences (Germany); Tovar, Michael [Helmholtz Zentrum Berlin fuer Materialien und Energie (Germany); Levcenco, Sergej; Napetrov, Alexander; Arushanov, Ernest [Academy of Sciences of Moldova Republic, Institute of Applied Physics, Chisinau (Moldova)


    The quaternary chalcogenides Cu{sub 2}ZnSnS{sub 4} and Cu{sub 2}ZnSnSe{sub 4} have newly attracted attention as possible absorber materials in thin film solar cells. They crystallize in the kesterite type (space group I anti 4) or stannite type structure (space group I anti 42m), which are described as an ordered distribution of the cations on different structural sites. Cation disorder may cause site defects and hence influences the electronic properties of the material. Thus the degree of cation order/disorder plays a crucial role and was therefor in the focus of the presented investigations. A differentiation between the isoelectronic cations Cu{sup +} and Zn{sup 2+} is not possible using X-ray diffraction due to their similar scattering power. But their neutron scattering lengths are different, thus neutron diffraction opens the possibility to determine the cation distribution in these compounds. A simultaneous Rietveld analysis of neutron and X-ray powder diffraction data revealed that in dependence on the thermal history of the samples cation disorder appears. The correlation trend between cation order/disorder and the sample growth method (solid state synthesis, Bridgman method) are discussed.

  7. Atmospheric CO2 enrichment facilitates cation release from soil. (United States)

    Cheng, L; Zhu, J; Chen, G; Zheng, X; Oh, N-H; Rufty, T W; Richter, D deB; Hu, S


    Atmospheric CO(2) enrichment generally stimulates plant photosynthesis and nutrient uptake, modifying the local and global cycling of bioactive elements. Although nutrient cations affect the long-term productivity and carbon balance of terrestrial ecosystems, little is known about the effect of CO(2) enrichment on cation availability in soil. In this study, we present evidence for a novel mechanism of CO(2)-enhancement of cation release from soil in rice agricultural systems. Elevated CO(2) increased organic C allocation belowground and net H(+) excretion from roots, and stimulated root and microbial respiration, reducing soil redox potential and increasing Fe(2+) and Mn(2+) in soil solutions. Increased H(+), Fe(2+), and Mn(2+) promoted Ca(2+) and Mg(2+) release from soil cation exchange sites. These results indicate that over the short term, elevated CO(2) may stimulate cation release from soil and enhance plant growth. Over the long-term, however, CO(2)-induced cation release may facilitate cation losses and soil acidification, negatively feeding back to the productivity of terrestrial ecosystems.

  8. Cations bind only weakly to amides in aqueous solutions. (United States)

    Okur, Halil I; Kherb, Jaibir; Cremer, Paul S


    We investigated salt interactions with butyramide as a simple mimic of cation interactions with protein backbones. The experiments were performed in aqueous metal chloride solutions using two spectroscopic techniques. In the first, which provided information about contact pair formation, the response of the amide I band to the nature and concentration of salt was monitored in bulk aqueous solutions via attenuated total reflection Fourier transform infrared spectroscopy. It was found that molar concentrations of well-hydrated metal cations (Ca(2+), Mg(2+), Li(+)) led to the rise of a peak assigned to metal cation-bound amides (1645 cm(-1)) and a decrease in the peak associated with purely water-bound amides (1620 cm(-1)). In a complementary set of experiments, the effect of cation identity and concentration was investigated at the air/butyramide/water interface via vibrational sum frequency spectroscopy. In these studies, metal ion-amide binding led to the ordering of the adjacent water layer. Such experiments were sensitive to the interfacial partitioning of cations in either a contact pair with the amide or as a solvent separated pair. In both experiments, the ordering of the interactions of the cations was: Ca(2+) > Mg(2+) > Li(+) > Na(+) ≈ K(+). This is a direct cationic Hofmeister series. Even for Ca(2+), however, the apparent equilibrium dissociation constant of the cation with the amide carbonyl oxygen was no tighter than ∼8.5 M. For Na(+) and K(+), no evidence was found for any binding. As such, the interactions of metal cations with amides are far weaker than the analogous binding of weakly hydrated anions.

  9. Cationic starches on cellulose surfaces. A study of polyelectrolyte adsorption.


    Steeg, van der, P.A.H.


    Cationic starches are used on a large scale in paper industry as wet-end additives. They improve dry strength. retention of fines and fillers, and drainage. Closure of the white water systems in the paper mills hase increased the concentration of detrimental substances. This might be the reason for the poor retention of cationic starches observed in the last few years.The purpose of the research described in this thesis was to obtain a better understanding of the adsorption of cationic starch...

  10. Electrostatic charge confinement using bulky tetraoctylammonium cation and four anions (United States)

    Andreeva, Nadezhda A.; Chaban, Vitaly V.


    Thanks to large opposite electrostatic charges, cations and anions establish strong ionic bonds. However, applications of ionic systems - electrolytes, gas capture, solubilization, etc. - benefit from weaker non-covalent bonds. The common approaches are addition of cosolvents and delocalization of electron charge density via functionalization of ions. We report fine tuning of closest-approach distances, effective radii, and cation geometry by different anions using the semi-empirical molecular dynamics simulations. We found that long fatty acid chains employed in the tetraalkylammonium cation are largely inefficient and new substituents must be developed. The reported results foster progress of task-specific ionic liquids.

  11. Competitive Solvation of the Imidazolium Cation by Water and Methanol

    CERN Document Server

    Chaban, Vitaly


    Imidazolium-based ionic liquids are widely used in conjunction with molecular liquids for various applications. Solvation, miscibility and similar properties are of fundamental importance for successful implementation of theoretical schemes. This work reports competitive solvation of the 1,3-dimethylimidazolium cation by water and methanol. Employing molecular dynamics simulations powered by semiempirical Hamiltonian (electronic structure level of description), the local structure nearly imidazolium cation is described in terms of radial distribution functions. Although water and methanol are chemically similar, water appears systematically more successful in solvating the 1,3-dimethylimidazolium cation. This result fosters construction of future applications of the ternary ion-molecular systems.

  12. Pyridine radical cation and its fluorine substituted derivatives (United States)

    Bondybey, V.E.; English, J.H.; Shiley, R.H.


    The spectra and relaxation of the pyridine cation and of several of its fluorinated derivatives are studied in low temperature Ne matrices. The ions are generated by direct photoionization of the parent compounds. Of the compounds studied, laser induced → and → fluorescence is observed only for the 2, 6‐difluoropyridine cation. The analysis of the spectrum indicates that the ion is planar both in the and states. The large variety in the spectroscopic and relaxation behavior of fluoropyridine radical cations is explained in terms of their electronic structure and of the differential shifts of the individual electronic states caused by the fluorine substitution.

  13. Novel cationic polyelectrolyte coatings for capillary electrophoresis. (United States)

    Duša, Filip; Witos, Joanna; Karjalainen, Erno; Viitala, Tapani; Tenhu, Heikki; Wiedmer, Susanne K


    The use of bare fused silica capillary in CE can sometimes be inconvenient due to undesirable effects including adsorption of sample or instability of the EOF. This can often be avoided by coating the inner surface of the capillary. In this work, we present and characterize two novel polyelectrolyte coatings (PECs) poly(2-(methacryloyloxy)ethyl trimethylammonium iodide) (PMOTAI) and poly(3-methyl-1-(4-vinylbenzyl)-imidazolium chloride) (PIL-1) for CE. The coated capillaries were studied using a series of aqueous buffers of varying pH, ionic strength, and composition. Our results show that the investigated polyelectrolytes are usable as semi-permanent (physically adsorbed) coatings with at least five runs stability before a short coating regeneration is necessary. Both PECs showed a considerably decreased stability at pH 11.0. The EOF was higher using Good's buffers than with sodium phosphate buffer at the same pH and ionic strength. The thickness of the PEC layers studied by quartz crystal microbalance was 0.83 and 0.52 nm for PMOTAI and PIL-1, respectively. The hydrophobicity of the PEC layers was determined by analysis of a homologous series of alkyl benzoates and expressed as the distribution constants. Our result demonstrates that both PECs had comparable hydrophobicity, which enabled separation of compounds with log Po/w > 2. The ability to separate cationic drugs was shown with β-blockers, compounds often misused in doping. Both coatings were also able to separate hydrolysis products of the ionic liquid 1,5-diazabicyclo[4.3.0]non-5-ene acetate at highly acidic conditions, where bare fused silica capillaries failed to accomplish the separation.

  14. IRMPD action spectroscopy of alkali metal cation-cytosine complexes: effects of alkali metal cation size on gas phase conformation. (United States)

    Yang, Bo; Wu, R R; Polfer, N C; Berden, G; Oomens, J; Rodgers, M T


    The gas-phase structures of alkali metal cation-cytosine complexes generated by electrospray ionization are probed via infrared multiple photon dissociation (IRMPD) action spectroscopy and theoretical calculations. IRMPD action spectra of five alkali metal cation-cytosine complexes exhibit both similar and distinctive spectral features over the range of ~1000-1900 cm(-1). The IRMPD spectra of the Li(+)(cytosine), Na(+)(cytosine), and K(+)(cytosine) complexes are relatively simple but exhibit changes in the shape and shifts in the positions of several bands that correlate with the size of the alkali metal cation. The IRMPD spectra of the Rb(+)(cytosine) and Cs(+)(cytosine) complexes are much richer as distinctive new IR bands are observed, and the positions of several bands continue to shift in relation to the size of the metal cation. The measured IRMPD spectra are compared to linear IR spectra of stable low-energy tautomeric conformations calculated at the B3LYP/def2-TZVPPD level of theory to identify the conformations accessed in the experiments. These comparisons suggest that the evolution in the features in the IRMPD action spectra with the size of the metal cation, and the appearance of new bands for the larger metal cations, are the result of the variations in the intensities at which these complexes can be generated and the strength of the alkali metal cation-cytosine binding interaction, not the presence of multiple tautomeric conformations. Only a single tautomeric conformation is accessed for all five alkali metal cation-cytosine complexes, where the alkali metal cation binds to the O2 and N3 atoms of the canonical amino-oxo tautomer of cytosine, M(+)(C1).

  15. Isomerization of propargyl cation to cyclopropenyl cation: Mechanistic elucidations and effects of lone pair donors

    Indian Academy of Sciences (India)

    Zodinpuia Pachuau; Kiew S Kharnaior; R H Duncan Lyngdoh


    This ab initio study examines two pathways (one concerted and the other two-step) for isomerization of the linear propargyl cation to the aromatic cyclopropenyl cation, also probing the phenomenon of solvation of this reaction by simple lone pair donors (NH3, H2O, H2S and HF) which bind to the substrate at two sites. Fully optimized geometries at the B3LYP/6-31G(d) level were used, along with single point QCISD(T)/6-311+G(d,p) and accurate G3 level calculations upon the DFT optimized geometries. For the unsolvated reaction, the two-step second pathway is energetically favoured over the one-step first pathway. Lone pair donor affinity for the various C3H$^{+}_{3}$ species follows the uniform order NH3 > H2S>H2O>HF. The activation barriers for the solvated isomerizations decrease in the order HF>H2O>H2S>NH3 for both pathways. The number of lone pairs on the donor heteroatom as well as the heteroatom electronegativity are factors related to both these trends. Compared to the unsolvated cases, the solvated reactions have transition states which are usually ‘later’ in position along the reaction coordinate, validating the Hammond postulate.

  16. Cation binding to 15-TBA quadruplex DNA is a multiple-pathway cation-dependent process. (United States)

    Reshetnikov, Roman V; Sponer, Jiri; Rassokhina, Olga I; Kopylov, Alexei M; Tsvetkov, Philipp O; Makarov, Alexander A; Golovin, Andrey V


    A combination of explicit solvent molecular dynamics simulation (30 simulations reaching 4 µs in total), hybrid quantum mechanics/molecular mechanics approach and isothermal titration calorimetry was used to investigate the atomistic picture of ion binding to 15-mer thrombin-binding quadruplex DNA (G-DNA) aptamer. Binding of ions to G-DNA is complex multiple pathway process, which is strongly affected by the type of the cation. The individual ion-binding events are substantially modulated by the connecting loops of the aptamer, which play several roles. They stabilize the molecule during time periods when the bound ions are not present, they modulate the route of the ion into the stem and they also stabilize the internal ions by closing the gates through which the ions enter the quadruplex. Using our extensive simulations, we for the first time observed full spontaneous exchange of internal cation between quadruplex molecule and bulk solvent at atomistic resolution. The simulation suggests that expulsion of the internally bound ion is correlated with initial binding of the incoming ion. The incoming ion then readily replaces the bound ion while minimizing any destabilization of the solute molecule during the exchange.

  17. New force field parameters for metalloproteins I: Divalent copper ion centers including three histidine residues and an oxygen-ligated amino acid residue. (United States)

    Wise, Olivia; Coskuner, Orkid


    Transition metal ion complexation with proteins is ubiquitous across such diverse fields as neurodegenerative and cardiovascular diseases and cancer. In this study, the structures of divalent copper ion centers including three histidine and one oxygen-ligated amino acid residues and the relative binding affinities of the oxygen-ligated amino acid residues with these metal ion centers, which are debated in the literature, are presented. Furthermore, new force field parameters, which are currently lacking for the full-length metal-ligand moieties, are developed for metalloproteins that have these centers. These new force field parameters enable investigations of metalloproteins possessing these binding sites using molecular simulations. In addition, the impact of using the atom equivalence and inequivalence atomic partial charge calculation procedures on the simulated structures of these metallopeptides, including hydration properties, is described.

  18. Silica surfaces lubrication by hydrated cations adsorption from electrolyte solutions. (United States)

    Donose, Bogdan C; Vakarelski, Ivan U; Higashitani, Ko


    Adsorption of hydrated cations on hydrophilic surfaces has been related to a variety of phenomena associated with the short-range interaction forces and mechanisms of the adhesive contact between the surfaces. Here we have investigated the effect of the adsorption of cations on the lateral interaction. Using lateral force microscopy (LFM), we have measured the friction force between a silica particle and silica wafer in pure water and in electrolyte solutions of LiCl, NaCl, and CsCl salts. A significant lubrication effect was demonstrated for solutions of high electrolyte concentrations. It was found that the adsorbed layers of smaller and more hydrated cations have a higher lubrication capacity than the layers of larger and less hydrated cations. Additionally, we have demonstrated a characteristic dependence of the friction force on the sliding velocity of surfaces. A mechanism for the observed phenomena based on the microstructures of the adsorbed layers is proposed.

  19. Degradation Mechanism of Cationic Red X-GRL by Ozonation

    Institute of Scientific and Technical Information of China (English)

    Wei Rong ZHAO; Xin Hua XU; Hui Xiang SHI; Da Hui WANG


    The degradation mechanism of Cationic Red X-GRL was investigated when the intermediates, the nitrate ion and the pH were analyzed in the ozonation. The degradation of the Cationic Red X-GRL includes the de-auxochrome stage, the decolour stage, and the decomposition of fragment stage. During the degradation process, among the six nitrogen atoms of Cationic Red X-GRL, one is transferred into a nitrate ion, one becomes the form of an amine compound, and the rest four are transformed into two molecules of nitrogen. In the course of the ozonation of Cationic Red X-GRL, the direct attack of ozone is the main decolour effect.

  20. DFT study on the cycloreversion of thietane radical cations. (United States)

    Domingo, Luis R; Pérez-Ruiz, Raúl; Argüello, Juan E; Miranda, Miguel A


    The molecular mechanism of the cycloreversion (CR) of thietane radical cations has been analyzed in detail at the UB3LYP/6-31G* level of theory. Results have shown that the process takes place via a stepwise mechanism leading to alkenes and thiobenzophenone; alternatively, formal [4+2] cycloadducts are obtained. Thus, the CR of radical cations 1a,b(•+) is initiated by C2-C3 bond breaking, giving common intermediates INa,b. At this stage, two reaction pathways are feasible involving ion molecule complexes IMCa,b (i) or radical cations 4a,b(•+) (ii). Calculations support that 1a(•+) follows reaction pathway ii (leading to the formal [4+2] cycloadducts 5a). By contrast, 1b(•+) follows pathway i, leading to trans-stilbene radical cation (2b(•+)) and thiobenzophenone.

  1. Affinity of Smectite and Divalent Metal Ions (Mg2+, Ca2+, Cu2+) with L-leucine: An Experimental and Theoretical Approach Relevant to Astrobiology (United States)

    Pandey, Pramod; Pant, Chandra Kala; Gururani, Kavita; Arora, Priyanka; Pandey, Neetu; Bhatt, Preeti; Sharma, Yogesh; Negi, Jagmohan Singh; Mehata, Mohan Singh


    Earth is the only known planet bestowed with life. Several attempts have been made to explore the pathways of the origin of life on planet Earth. The search for the chemistry which gave rise to life has given answers related to the formation of biomonomers, and their adsorption on solid surfaces has gained much attention for the catalysis and stabilization processes related to the abiotic chemical evolution of the complex molecules of life. In this communication, surface interactions of L-leucine (Leu) on smectite (SMT) group of clay (viz. bentonite and montmorillonite) and their divalent metal ion (Mg2+, Ca2+ and Cu2+) incorporated on SMT has been studied to find the optimal conditions of time, pH, and concentration at ambient temperature (298 K). The progress of adsorption was followed spectrophotometrically and further characterized by FTIR, SEM/EDS and XRD. Leu, a neutral/non polar amino acid, was found to have more affinity in its zwitterionic form towards Cu2+- exchanged SMT and minimal affinity for Mg2+- exchanged SMT. The vibrational frequency shifts of —NH3 + and —COO- favor Van der Waal's forces during the course of surface interaction. Quantum calculations using density functional theory (DFT) have been applied to investigate the absolute value of metal ion affinities of Leu (Leu—M2+ complex, M = Mg2+, Ca2+, Cu2+) with the help of their physico-chemical parameters. The hydration effect on the relative stability and geometry of the individual species of Leu—M2+ × (H2O)n, ( n =2 and 4) has also been evaluated within the supermolecule approach. Evidence gathered from investigations of surface interactions, divalent metal ions affinities and hydration effects with biomolecules may be important for better understanding of chemical evolution, the stabilization of biomolecules on solid surfaces and biomolecular-metal interactions. These results may have implications for understanding the origin of life and the preservation of biomarkers.

  2. Affinity of Smectite and Divalent Metal Ions (Mg(2+), Ca(2+), Cu(2+)) with L-leucine: An Experimental and Theoretical Approach Relevant to Astrobiology. (United States)

    Pandey, Pramod; Pant, Chandra Kala; Gururani, Kavita; Arora, Priyanka; Pandey, Neetu; Bhatt, Preeti; Sharma, Yogesh; Negi, Jagmohan Singh; Mehata, Mohan Singh


    Earth is the only known planet bestowed with life. Several attempts have been made to explore the pathways of the origin of life on planet Earth. The search for the chemistry which gave rise to life has given answers related to the formation of biomonomers, and their adsorption on solid surfaces has gained much attention for the catalysis and stabilization processes related to the abiotic chemical evolution of the complex molecules of life. In this communication, surface interactions of L-leucine (Leu) on smectite (SMT) group of clay (viz. bentonite and montmorillonite) and their divalent metal ion (Mg(2+), Ca(2+) and Cu(2+)) incorporated on SMT has been studied to find the optimal conditions of time, pH, and concentration at ambient temperature (298 K). The progress of adsorption was followed spectrophotometrically and further characterized by FTIR, SEM/EDS and XRD. Leu, a neutral/non polar amino acid, was found to have more affinity in its zwitterionic form towards Cu(2+)- exchanged SMT and minimal affinity for Mg(2+)- exchanged SMT. The vibrational frequency shifts of -NH3 (+) and -COO(-) favor Van der Waal's forces during the course of surface interaction. Quantum calculations using density functional theory (DFT) have been applied to investigate the absolute value of metal ion affinities of Leu (Leu-M(2+) complex, M = Mg(2+), Ca(2+), Cu(2+)) with the help of their physico-chemical parameters. The hydration effect on the relative stability and geometry of the individual species of Leu-M(2+) × (H2O)n, (n =2 and 4) has also been evaluated within the supermolecule approach. Evidence gathered from investigations of surface interactions, divalent metal ions affinities and hydration effects with biomolecules may be important for better understanding of chemical evolution, the stabilization of biomolecules on solid surfaces and biomolecular-metal interactions. These results may have implications for understanding the origin of life and the preservation of

  3. Magnetic and High-Frequency Dielectric Parameters of Divalent Ion-Substituted W-Type Hexagonal Ferrites (United States)

    Ali, Akbar; Grössinger, R.; Imran, Muhammad; Khan, M. Ajmal; Elahi, Asmat; Akhtar, Majid Niaz; Mustafa, Ghulam; Khan, Muhammad Azhar; Ullah, Hafeez; Murtaza, Ghulam; Ahmad, Mukhtar


    Polycrystalline W-type hexagonal ferrites with chemical formulae Ba0.5Sr0.5 Co2- x Me x Fe16O27 ( x = 0, 0.5, Me = Mn, Mg, Zn, Ni) have been prepared using sol-gel autocombustion. It has been reported in our earlier published work that all the samples exhibit a single-phase W-type hexagonal structure which was confirmed by x-ray diffraction (XRD) analysis. The values of bulk density lie in the range of 4.64-4.78 g/cm3 for all the samples which are quite high as compared to those for other types of hexaferrites. It was also observed that Zn-substituted ferrite reflects the highest (14.7 × 107 Ω-cm) whereas Mn-substituted ferrite has the lowest (11.3 × 107 Ω-cm) values of direct current (DC) electrical resistivity. The observed values of saturation magnetization ( M s) are found to be in the range of 62.01-68.7 emu/g depending upon the type of cation substitution into the hexagonal lattice. All the samples exhibit a typical soft magnetic character with low values of coercivity ( H c) that are in the range of 26-85 Oe. These ferrites may be promising materials for microwave absorbers due to their higher saturation magnetization and low coercivities. Both the dielectric constant and tangent loss decrease with increasing frequency in the lower frequency region and become constant in the higher frequency region. The much lower dielectric constant obtained in this study makes the investigated ferrites very useful for high-frequency applications, i.e. dielectric resonators and for camouflaging military targets such as ships, tanks and aircrafts, etc.

  4. Migration of Cations and Anions in Amorphous Polymer Electrolytes

    Institute of Scientific and Technical Information of China (English)

    N.A.Stolwijk; S.H.Obeidi; M.Wiencierz


    1 Results Polymer electrolytes are used as ion conductors in batteries and fuel cells.Simple systems consist of a polymer matrix complexing an inorganic salt and are fully amorphous at the temperatures of interest.Both cations and anions are mobile and contribute to charge transport.Most studies on polymer electrolytes use the electrical conductivity to characterize the ion mobility.However,conductivity measurements cannot discriminate between cations and anions.This paper reports some recent results fr...


    Institute of Scientific and Technical Information of China (English)

    W. Liu; Y. Ni; H. Xiao


    Hydrophilic and cationic montmorillonite is desirable for pitch control in the pulp and paper industry. In this paper, polyaminoamide - epichlorohydrin (PAE)modified montmorillonite was prepared. The modified montmorillonite was characterized using X-ray diffraction, FTIR and thermal gravimetric analysis. The amount of PAE intercalated and cationic charge densities of the modified montmorillonite were determined. Finally, it was found that both the solution and melt-intercalated samples with different charge densities exhibited strong interactions with dispersed colloidal rosin acid.

  6. Competition by meperidine for the organic cation renal excretory system. (United States)

    Acara, M; Gessner, T; Trudnowski, R J


    Renal tubular excretory transport of meperidine was studied using the Sperber preparation in chickens. When urine samples from infused and uninfused kidneys were analyzed for meperidine by gas chromatography, meperidine was always present in greater amounts in the urine from the infused kidney, demonstrating active tubular excretion. Meperidine at an infusion rate of 1 mumole/min, also inhibited the excretion of the organic cations choline and acetylcholine, indicating occupation of the renal organic cation excretory system in the chicken.

  7. Focused fluorescent probe library for metal cations and biological anions. (United States)

    Rhee, Hyun-Woo; Lee, Sang Wook; Lee, Jun-Seok; Chang, Young-Tae; Hong, Jong-In


    A focused fluorescent probe library for metal cations was developed by combining metal chelators and picolinium/quinolinium moieties as combinatorial blocks connected through a styryl group. Furthermore, metal complexes derived from metal chelators having high binding affinities for metal cations were used to construct a focused probe library for phosphorylated biomolecules. More than 250 fluorescent probes were screened for identifying an ultraselective probe for dTTP.

  8. Computer simulation of alkali metal cation-montmorillonite hydrates

    Energy Technology Data Exchange (ETDEWEB)

    Chang, Fang-Ru Chou [Columbia Univ., Palisades, NY (United States); Skipper, N.T. [Univ. College, London (United Kingdom); Sposito, G. [Lawrence Berkeley National Lab., CA (United States)


    Molecular structure in the interlayers of Li-, Na-, or K-Wyoming montmorillonite with one, two, or three adsorbed water layers was investigated for the first time by concurrent Monte Carlo and molecular dynamics (MD) simulation, based on the Matsouka-Clementi-Yoshimine, (MCY) model of water-water interactions. Calculated layer spacings, as well as interlayer-species self-diffusion coefficients, were in good agreement with available experimental data. Inner-sphere surface complexes of the cations with tetrahedral charge sites were observed for all hydrates, whereas outer-sphere surface complexes of the cations with octahedral charge sites, found also in the one-layer hydrate, tended to dissociate from the clay mineral basal planes into a diffuse layer in the two- and three-layer hydrates. Differences in the interlayer water structure among the hydrates mainly reflected cation solvation, although some water molecules were entrapped within cavities in the montmorillonite surface. All of the interlayer cation and water species exchanged on the time scale (0.2 ns) of the MD simulations. Comparisons with results obtained using, instead of the MCY model, the TIP4P model for water-water, cation-water, and cation-clay interactions indicated that layer spacings and interlayer species mobilities tend to be under-predicted by the TIP4P model.

  9. Complexation Between Cationic Diblock Copolymers and Plasmid DNA (United States)

    Jung, Seyoung; Reineke, Theresa; Lodge, Timothy

    Deoxyribonucleic acids (DNA), as polyanions, can spontaneously bind with polycations to form polyelectrolyte complexes. When the polycation is a diblock copolymer with one cationic block and one uncharged hydrophilic block, the polyelectrolyte complexes formed with plasmid DNA (pDNA) are often colloidally stable, and show great promise in the field of polymeric gene therapy. While the resulting properties (size, stability, and toxicity to biological systems) of the complexes have been studied for numerous cationic diblocks, the fundamentals of the pDNA-diblock binding process have not been extensively investigated. Herein, we report how the cationic block content of a diblock influences the pDNA-diblock interactions. pDNA with 7164 base pairs and poly(2-deoxy-2-methacrylamido glucopyranose)-block-poly(N-(2-aminoethyl) methacrylamide) (PMAG-b-PAEMA) are used as the model pDNA and cationic diblock, respectively. To vary the cationic block content, two PMAG-b-PAEMA copolymers with similar PMAG block lengths but distinct PAEMA block lengths and a PAEMA homopolymer are utilized. We show that the enthalpy change from pDNA-diblock interactions is dependent on the cationic diblock composition, and is closely associated with both the binding strength and the pDNA tertiary structure.

  10. Photochemical generation, isomerization, and oxygenation of stilbene cation radicals

    Energy Technology Data Exchange (ETDEWEB)

    Lewis, F.D.; Bedell, A.M.; Dykstra, R.E.; Elbert, J.E. (Northwestern Univ., Evanston, IL (USA)); Gould, I.R.; Farid, S. (Eastman Kodak Co., Rochester, NY (USA))


    The cation radicals of cis- and trans-stilbene and several of their ring-substituted derivatives have been generated in solution directly by means of pulsed-laser-induced electron transfer to singlet cyanoanthracenes or indirectly via electron transfer from biphenyl to the singlet cyanoanthracene followed by secondary electron transfer from the stilbenes to the biphenyl cation radical. Transient absorption spectra of the cis- and trans-stilbene cation radicals generated by secondary electron transfer are similar to those previously obtained in 77 K matrices. Quantum yields for radical ion-pair cage escape have been measured for direct electron transfer from the stilbenes to three neutral and one charged singlet acceptor. These values increase as the ion-pair energy increases due to decreased rate constants for radical ion-pair return electron transfer, in accord with the predictions of Marcus theory for highly exergonic electron transfer. Cage-escape efficiencies are larger for trans- vs cis-stilbene cation radicals, possibly due to the greater extent of charge delocalization in the planar trans vs nonpolar cis cation radicals. Cage-escape stilbene cation radicals can initiate a concentration-dependent one way cis- {yields} trans-stilbene isomerization reaction.

  11. Tunable states of interlayer cations in two-dimensional materials

    Energy Technology Data Exchange (ETDEWEB)

    Sato, K.; Numata, K. [Department of Environmental Sciences, Tokyo Gakugei University, Koganei, Tokyo 184-8501 (Japan); Dai, W. [Key Laboratory of Advanced Energy Materials Chemistry (Ministry of Education), College of Chemistry, Nankai University, Tianjin 300071 (China); Hunger, M. [Institute of Chemical Technology, University of Stuttgart, 70550 Stuttgart (Germany)


    The local state of cations inside the Ångstrom-scale interlayer spaces is one of the controlling factors for designing sophisticated two-dimensional (2D) materials consisting of 2D nanosheets. In the present work, the molecular mechanism on how the interlayer cation states are induced by the local structures of the 2D nanosheets is highlighted. For this purpose, the local states of Na cations in inorganic 2D materials, in which the compositional fluctuations of a few percent are introduced in the tetrahedral and octahedral units of the 2D nanosheets, were systematically studied by means of {sup 23}Na magic-angle-spinning (MAS) nuclear magnetic resonance (NMR) and {sup 23}Na multiple-quantum MAS (MQMAS) NMR spectroscopy. In contrast with an uniform distribution of Na cations expected so far, various well-defined cation states sensitive to the local structures of the 2D nanosheets were identified. The tunability of the interlayer cation states along with the local structure of the 2D nanosheets, as the smallest structural unit of the 2D material, is discussed.

  12. Synthesis and characterisation of cationically modified phospholipid polymers. (United States)

    Lewis, Andrew L; Berwick, James; Davies, Martyn C; Roberts, Clive J; Wang, Jin-Hai; Small, Sharon; Dunn, Anthony; O'Byrne, Vincent; Redman, Richard P; Jones, Stephen A


    Phospholipid-like copolymers based on 2-(methacryloyloxyethyl) phosphorylcholine were synthesised using monomer-starved free radical polymerisation methods and incorporating cationic charge in the form of the choline methacrylate monomer in amounts varying from 0 to 30 wt%, together with a 5 wt% silyl cross-linking agent in order to render them water-insoluble once thermally cured. Characterisation using a variety of techniques including nuclear magnetic resonance spectroscopy, high-pressure liquid chromatography and gel permeation chromatography showed the cationic monomer did not interfere with the polymerisation and that the desired amount of charge had been incorporated. Gravimetric and differential scanning calorimetry methods were used to evaluate the water contents of polymer membranes cured at 70 degrees C, which was seen to increase with increasing cation content, producing materials with water contents ranging from 50% to 98%. Surface plasmon resonance indicated that the coatings swelled rapidly in water, the rate and extent of swelling increasing with increasing cation level. Dynamic contact angle showed that coatings of all the polymers possessed a hydrophobic surface when dry in air, characteristic of the alkyl chains expressed at the surface (>100 degrees advancing angle). Rearrangement of the hydrophilic groups to the surface occurred once wet, to produce highly wettable surfaces with a decrease in advancing angle with increasing cation content. Atomic force microscopy showed all polymer films to be smooth with no features in topographical or phase imaging. Mechanical properties of the dry films were also unaffected by the increase in cation content.

  13. Modulatory role of bivalent cations on reward system. (United States)

    Nechifor, M; Chelărescu, D


    Bivalent cations (Ca, Mg, Zn, Mn etc.) modulate activity of reward system (RS). At physiologic levels they may influence all components of RS. There are influenced behavioral reactions at physiological stimuli and all essential elements of drug dependence (compulsive intake of substance, craving, reinforcement, withdrawal syndrom, relapse and reinstatement of intake) The fact that some cations (e.g. calcium) enhance some of the aspects of drug dependence and others (e.g. magnesium, zinc) decrease intensity of this process show that ratio between intra- and extracellular in the brain of these cations is important for the function of RS. Among actions of different cations at the level of RS there are important differences. Their mecahanism of action are common in part and specific in other. It is important the fact that modulatory action appear at physiologic cation concentrations (that could be reached at therapeutic doses). Modulatory action is related to ratio between concetrations of different bivalent cations and is exerted both in normal or pathologic conditions.

  14. Does the cation really matter? The effect of modifying an ionic liquid cation on an SN2 process. (United States)

    Tanner, Eden E L; Yau, Hon Man; Hawker, Rebecca R; Croft, Anna K; Harper, Jason B


    The rate of reaction of a Menschutkin process in a range of ionic liquids with different cations was investigated, with temperature-dependent kinetic data giving access to activation parameters for the process in each solvent. These data, along with molecular dynamics simulations, demonstrate the importance of accessibility of the charged centre on the cation and that the key interactions are of a generalised electrostatic nature.

  15. Redox Active Cation Intercalation/Deintercalation in Two-Dimensional Layered MnO2 Nanostructures for High-Rate Electrochemical Energy Storage. (United States)

    Xiong, Pan; Ma, Renzhi; Sakai, Nobuyuki; Bai, Xueyin; Li, Shen; Sasaki, Takayoshi


    Two-dimensional (2D) layered materials with a high intercalation pseudocapacitance have long been investigated for Li(+)-ion-based electrochemical energy storage. By contrast, the exploration of guest ions other than Li(+) has been limited, although promising. The present study investigates intercalation/deintercalation behaviors of various metal ions in 2D layered MnO2 with various interlayer distances, K-birnessite nanobelt (K-MnO2), its protonated form (H-MnO2), and a freeze-dried sample of exfoliated nanosheets. Series of metal ions, such as monovalent Li(+), Na(+), and K(+) and divalent Mg(2+), exhibit reversible intercalation during charge/discharge cycling, delivering high-rate pseudocapacitances. In particular, the freeze-dried MnO2 of exfoliated nanosheets restacked with the largest interlayer spacing and a less compact 3D network exhibits the best rate capability and a stable cyclability over 5000 cycles. Both theoretical calculation and kinetic analysis reveal that the increased interlayer distance facilitates the fast diffusion of cations in layered MnO2 hosts. The results presented herein provide a basis for the controllable synthesis of layered nanostructures for high-rate electrochemical energy storage using various single- and multivalent ions.

  16. Cation Uptake and Allocation by Red Pine Seedlings under Cation-Nutrient Stress in a Column Growth Experiment

    Energy Technology Data Exchange (ETDEWEB)

    Shi, Zhenqing; Balogh-Brunstad, Zsuzsanna; Grant, Michael R.; Harsh, James B.; Gill, Richard; Thomashow, Linda; Dohnalkova, Alice; Stacks, Daryl; Letourneau, Melissa; Keller, Chester K.


    Background and Aims Plant nutrient uptake is affected by environmental stress, but how plants respond to cation-nutrient stress is poorly understood. We assessed the impact of varying degrees of cation-nutrient limitation on cation uptake in an experimental plant-mineral system. Methods Column experiments, with red pine (Pinus resinosa Ait.) seedlings growing in sand/mineral mixtures, were conducted for up to nine months under a range of Ca- and K-limited conditions. The Ca and K were supplied from both minerals and nutrient solutions with varying Ca and K concentrations. Results Cation nutrient stress had little impact on carbon allocation after nine months of plant growth and K was the limiting nutrient for biomass production. The Ca/Sr and K/Rb ratio results allowed independent estimation of dissolution incongruency and discrimination against Sr and Rb during cation uptake processes. The fraction of K in biomass from biotite increased with decreasing K supply from nutrient solutions. The mineral anorthite was consistently the major source of Ca, regardless of nutrient treatment. Conclusions Red pine seedlings exploited more mineral K in response to more severe K deficiency. This did not occur for Ca. Plant discrimination factors must be carefully considered to accurately identify nutrient sources using cation tracers.

  17. Lack of association between a cationic protein and a cationic fluorosurfactant. (United States)

    Macakova, Lubica; Nordstierna, Lars; Karlsson, Göran; Blomberg, Eva; Furó, István


    Surface tension, 19F and 1H NMR spectroscopy, and cryotransmission electron microscopy are used to characterize the state of association in aqueous solutions of a fluorosurfactant CF3(CF2)nSO2NH(CH2)3-4N(CH3)3+ I- (n = 8, 6) with and without lysozyme added. In the absence of lysozyme, we find monomers, small aggregates, and large vesicles to coexist, with the individual fluorosurfactant molecules exchanging slowly (>1 ms) among those states. When both lysozyme and fluorosurfactant are present in the solution, they have no measurable influence on the physical state of the other. In contrast, a hydrogenated cationic surfactant with the same headgroup, hexadecyltrimethylammonium bromide, is shown to associate to lysozyme.

  18. Endocytosis of cationized ferritin by coated vesicles of soybean protoplasts. (United States)

    Tanchak, M A; Griffing, L R; Mersey, B G; Fowke, L C


    Soybean (Glycine max (L.) Merr.) protoplasts have been surface-labelled with cationized ferritin, and the fate of the label has been followed ultrastructurally. Endocytosis of the label occurs via the coated-membrane system. The pathway followed by the label, once it has been taken into the interior of the protoplast, appears to be similar to that found during receptor-mediated endocytosis in animal cells. Cationized ferritin is first seen in coated vesicles but rapidly appears in smooth vesicles. Labelled, partially coated vesicles are occasionally observed, indicating that the smooth vesicles may have arisen by the uncoating of coated vesicles. Structures which eventually become labelled with cationized ferritin include multivesicular bodies, dictyosomes, large smooth vesicles, and a system of partially coated reticula.

  19. Infrared Spectroscopic Investigation on CH Bond Acidity in Cationic Alkanes (United States)

    Matsuda, Yoshiyuki; Xie, Min; Fujii, Asuka


    We have demonstrated large enhancements of CH bond acidities in alcohol, ether, and amine cations through infrared predissociation spectroscopy based on the vacuum ultraviolet photoionization detection. In this study, we investigate for the cationic alkanes (pentane, hexane, and heptane) with different alkyl chain lengths. The σ electrons are ejected in the ionization of alkanes, while nonbonding electrons are ejected in ionization of alcohols, ethers, and amines. Nevertheless, the acidity enhancements of CH in these cationic alkanes have also been demonstrated by infrared spectroscopy. The correlations of their CH bond acidities with the alkyl chain lengths as well as the mechanisms of their acidity enhancements will be discussed by comparison of infrared spectra and theoretical calculations.

  20. Radical Addition to Iminium Ions and Cationic Heterocycles

    Directory of Open Access Journals (Sweden)

    Johannes Tauber


    Full Text Available Carbon-centered radicals represent highly useful reactive intermediates in organic synthesis. Their nucleophilic character is reflected by fast additions to electron deficient C=X double bonds as present in iminium ions or cationic heterocycles. This review covers diverse reactions of preformed or in situ-generated cationic substrates with various types of C-radicals, including alkyl, alkoxyalkyl, trifluoromethyl, aryl, acyl, carbamoyl, and alkoxycarbonyl species. Despite its high reactivity, the strong interaction of the radical’s SOMO with the LUMO of the cation frequently results in a high regioselectivity. Intra- and intermolecular processes such as the Minisci reaction, the Porta reaction, and the Knabe rearrangement will be discussed along with transition metal and photoredox catalysis or electrochemical methods to generate the odd-electron species.

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

    Institute of Scientific and Technical Information of China (English)

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


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

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

    Institute of Scientific and Technical Information of China (English)


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

  3. Cationic lipids delay the transfer of plasmid DNA to lysosomes. (United States)

    Wattiaux, R; Jadot, M; Laurent, N; Dubois, F; Wattiaux-De Coninck, S


    Plasmid 35S DNA, naked or associated with different cationic lipid preparations was injected to rats. Subcellular distribution of radioactivity in the liver one hour after injection, was established by centrifugation methods. Results show that at that time, 35S DNA has reached lysosomes. On the contrary, when 35S DNA was complexed with lipids, radioactivity remains located in organelles whose distribution after differential and isopycnic centrifugation, is clearly distinct from that of arylsulfatase, lysosome marker enzyme. Injection of Triton WR 1339, a specific density perturbant of lysosomes, four days before 35S DNA injection causes a density decrease of radioactivity bearing structures, apparent one hour after naked 35S DNA injection but visible only after more than five hours, when 35S DNA associated with a cationic lipid is injected. These observations show that cationic lipids delay the transfer to lysosomes, of plasmid DNA taken up by the liver.

  4. Surface hopping investigation of the relaxation dynamics in radical cations

    Energy Technology Data Exchange (ETDEWEB)

    Assmann, Mariana; Matsika, Spiridoula, E-mail: [Department of Chemistry, Temple University, Philadelphia, Pennsylvania 19122 (United States); Weinacht, Thomas [Department of Physics, Stony Brook University, Stony Brook, New York 11794 (United States)


    Ionization processes can lead to the formation of radical cations with population in several ionic states. In this study, we examine the dynamics of three radical cations starting from an excited ionic state using trajectory surface hopping dynamics in combination with multiconfigurational electronic structure methods. The efficiency of relaxation to the ground state is examined in an effort to understand better whether fragmentation of cations is likely to occur directly on excited states or after relaxation to the ground state. The results on cyclohexadiene, hexatriene, and uracil indicate that relaxation to the ground ionic state is very fast in these systems, while fragmentation before relaxation is rare. Ultrafast relaxation is facilitated by the close proximity of electronic states and the presence of two- and three-state conical intersections. Examining the properties of the systems in the Franck-Condon region can give some insight into the subsequent dynamics.

  5. Theoretical Studies on the Interactions of Cations with Diazine

    Institute of Scientific and Technical Information of China (English)

    CHEN Xing; WU Wen-Peng; ZHANG Jing-Lai; CAO Ze-Xing


    Density functional theory and MP2 calculations have been used to determine the geometries, stabilities, binding energies, and dissociative properties of cation-diazine complexes Mn+-C4H4N2 (Mn+ = Li+, B+, Al+, Be2+, Mg2+, Ca2+). The calculated results indicate that most complexes are stable except the π complexes of Ca2+-pyridazine, Ca2+-pyrazine, Al+-pyrimidine and Al+-pyrimidine. The σ complexes are generally much more stable than their π counterparts. Among the π complexes, the cation-pyrazine π complexes have slightly higher stability. The nature of the ion-molecule interactions has been discussed by the natural bond orbital analysis and frontier molecular orbital interactions. In these σ complexes, there is stronger covalent interaction between B+ and diazine. In the selected π complexes, B+ and Be2+ have stronger covalent interaction with diazine, while the other cations mainly have electrostatic interaction with diazine.

  6. Solubility and transport of cationic and anionic patterned nanoparticles (United States)

    Su, Jiaye; Guo, Hongxia; Olvera de La Cruz, Monica


    Diffusion and transport of nanoparticles (NPs) though nanochannels is important for desalination, drug delivery, and biomedicine. Their surface composition dictate their efficiency separating them by reverse osmosis, delivering into into cells, as well as their toxicity. We analyze bulk diffusion and transport through nanochannels of NPs with different hydrophobic-hydrophilic patterns achieved by coating a fraction of the NP sites with positive or negative charges via explicit solvent molecular dynamics simulations. The cationic NPs are more affected by the patterns, less water soluble, and have higher diffusion constants and fluxes than their anionic NPs counterparts. The NP-water interaction dependence on surface pattern and field strength explains these observations. For equivalent patterns, anionic NPs solubilize more than cationic NPs since the Coulomb interaction of free anionic NPs, which are much stronger than hydrophobic NP-water interactions, are about twice that of cationic NPs.

  7. Cationization of Alpha-Cellulose to Develop New Sustainable Products

    Directory of Open Access Journals (Sweden)

    Ana Moral


    Full Text Available Papermaking has been using high quantities of retention agents, mainly cationic substances and organic compounds such as polyamines. The addition of these agents is related to economic and environmental issues, increasing contamination of the effluents. The aim of this work is to develop a cationic polymer for papermaking purposes based on the utilization of alpha-cellulose. The cationization of mercerized alpha-cellulose with 3-chloro-2-hydroxypropyltrimethylammonium chloride (CHPTAC is governed by a pseudo-second-order reaction. The initial amorphous fraction of cellulose is reacted with CHPTAC until the equilibrium value of nitrogen substitution is reached. Nitrogen is incorporated as a quaternary ammonium group in the polymer. Also, the kinetic constant increased with decreasing crystallinity index, showing the importance of the previous alkalization stage. The use of modified natural polysaccharides is a sustainable alternative to synthetic, nonbiodegradable polyelectrolytes and thus is desirable with a view to developing new products and new processes.

  8. Sorption of his-tagged Protein G and Protein G onto chitosan/divalent metal ion sorbent used for detection of microcystin-LR. (United States)

    Demey, Hary; Tria, Scherrine A; Soleri, Romain; Guiseppi-Elie, Anthony; Bazin, Ingrid


    A highly sensitive, specific, simple, and rapid chemiluminescence enzyme immunoassay (CLEIA) was developed for the determination of microcystin-LR (MC-LR) by using strategies for oriented immobilization of functionally intact polyclonal antibodies on chitosan surface. Several physicochemical parameters such as metal ion adsorption, hexahistidine-tagged Protein G sorption, the dilution ratio polyclonal antibody concentration, and peroxidase-labeled MC-LR concentration were studied and optimized. The sorption in batch system of G-histidine and G-proteins was studied on a novel sorbent consisting of chitosan/divalent metal ions. Transition metals as Ni(++) and Zn(++) were immobilized through interaction with -NH2 groups of chitosan in order to supply a material capable to efficiently remove the proteins from aqueous solutions. The maximum uptake of divalent metals onto the chitosan material was found to be 230 mg g(-1) for Zn(++) and 62 mg g(-1) for Ni(++). Experimental data were evaluated using the Langmuir and Freundlich models; the results were well fitted with the Langmuir model; chitosan/Ni(++) foam was found to be the best sorbent for G-protein, maximum sorption capacity obtained was 17 mg g(-1), and chitosan/Zn(++) was found to be the best for G-histidine with a maximum sorption capacity of 44 mg g(-1). Kinetic data was evaluated with pseudo-first- and pseudo-second-order models; the sorption kinetics were in all cases better represented by a pseudo-second-order model. Under optimum conditions, the calibration curve obtained for MC-LR gave detection limits of 0.5 ± 0.06 μg L(-1), the 50 % inhibition concentration (IC50) was 2.75 ± 0.03 μg L(-1), and the quantitative detection range was 0.5-25 μg L(-1). The limit of detection (LOD) attained from the calibration curves and the results obtained demonstrate the potential use of CLEIA with chitosan support as a screening tool for the analysis of pollutants in environmental samples.

  9. Comparison of Cation Adsorption by Isostructural Rutile and Cassiterite

    Energy Technology Data Exchange (ETDEWEB)

    Machesky, Michael L. [Illinois State Water Survey, Champaign, IL; Wesolowski, David J [ORNL; Rosenqvist, Jorgen K [ORNL; Predota, M. [University of South Bohemia, Czech Republic; Vlcek, Lukas [ORNL; Ridley, Moira K [ORNL; Kohli, V [Oak Ridge National Laboratory (ORNL); Zhang, Zhan [Argonne National Laboratory (ANL); Fenter, Paul [Argonne National Laboratory (ANL); Cummings, Peter T [ORNL; Lvov, Serguei N. [Pennsylvania State University; Fedkin, Mark V [ORNL; Rodriguez-Santiago, V [Oak Ridge National Laboratory (ORNL); Kubicki, James D. [Pennsylvania State University; Bandura, Andrei V. [St. Petersburg State University, St. Petersburg, Russia


    Macroscopic net proton charging curves for powdered rutile and cassiterite specimens with the (110) Crystal face predominant, as a function of pH in RbCl and NaCl solutions, trace SrCl2 in NaCl, and trace ZnCl2 in NaCl and Na Triflate solutions, are compared to corresponding molecular-level information obtained from static DFT optimizations and classical MD simulations, as well as synchrotron X-ray methods. The similarities and differences in the macroscopic charging behavior of rutile and cassiterite largely reflect the cation binding modes observed at the molecular level. Cation adsorption is primarily inner-sphere on both isostructural (110) surfaces, despite predictions that outer-sphere binding should predominate on low bulk dielectric constant oxides such as cassiterite ( bulk 11). Inner-sphere adsorption is also significant for Rb and Na on neutral surfaces, whereas Cl- binding is predominately outer-sphere. As negative surface charge increases, relatively more Rb , Na , and especially Sr2 are bound in highly desolvated tetradentate fashion on the rutile (110) surface, largely accounting for enhanced negative charge development relative to cassiterite. Charging curves in the presence of Zn2 are very steep but similar for both oxides, reflective of Zn2 hydrolysis (and accompanying proton release) during the adsorption process, and the similar binding modes for ZnOH on both surfaces. These results suggest that differences in cation adsorption between high and low bulk dielectric constant oxides are more subtly related to the relative degree of cation desolvation accompanying inner-sphere binding (i.e., more tetradentate binding on rutile), rather than distinct inner- and outer-sphere adsorption modes. Cation desolvation may be favored at the rutile (110) surface in part because inner-sphere water molecules are bound further from and less tightly than on the cassiterite (110) surface. Hence, their removal upon inner-sphere cation binding is relatively more

  10. Comparison of cation adsorption by isostructural rutile and cassiterite. (United States)

    Machesky, Michael; Wesolowski, David; Rosenqvist, Jörgen; Předota, Milan; Vlcek, Lukas; Ridley, Moira; Kohli, Vaibhav; Zhang, Zhan; Fenter, Paul; Cummings, Peter; Lvov, Serguei; Fedkin, Mark; Rodriguez-Santiago, Victor; Kubicki, James; Bandura, Andrei


    Macroscopic net proton charging curves for powdered rutile and cassiterite specimens with the (110) crystal face predominant, as a function of pH in RbCl and NaCl solutions, trace SrCl(2) in NaCl, and trace ZnCl(2) in NaCl and Na Triflate solutions, are compared to corresponding molecular-level information obtained from static DFT optimizations and classical MD simulations, as well as synchrotron X-ray methods. The similarities and differences in the macroscopic charging behavior of rutile and cassiterite largely reflect the cation binding modes observed at the molecular level. Cation adsorption is primarily inner-sphere on both isostructural (110) surfaces, despite predictions that outer-sphere binding should predominate on low bulk dielectric constant oxides such as cassiterite (ε(bulk) ≈ 11). Inner-sphere adsorption is also significant for Rb(+) and Na(+) on neutral surfaces, whereas Cl(-) binding is predominately outer-sphere. As negative surface charge increases, relatively more Rb(+), Na(+), and especially Sr(2+) are bound in highly desolvated tetradentate fashion on the rutile (110) surface, largely accounting for enhanced negative charge development relative to cassiterite. Charging curves in the presence of Zn(2+) are very steep but similar for both oxides, reflective of Zn(2+) hydrolysis (and accompanying proton release) during the adsorption process, and the similar binding modes for ZnOH(+) on both surfaces. These results suggest that differences in cation adsorption between high and low bulk dielectric constant oxides are more subtly related to the relative degree of cation desolvation accompanying inner-sphere binding (i.e., more tetradentate binding on rutile), rather than distinct inner- and outer-sphere adsorption modes. Cation desolvation may be favored at the rutile (110) surface in part because inner-sphere water molecules are bound further from and less tightly than on the cassiterite (110) surface. Hence, their removal upon inner

  11. Determination of Cationic Surfactant by Laser Thermal Lens Spectrometry

    Institute of Scientific and Technical Information of China (English)


    A novel method for the determination of cationic surfactant by laser thermal lens spectrometry was developed. It was based on the reaction between 1-hydroxy-2-(5-nitro-2-Pyri-dylazo)-8-aminonaphthalene-3,6-disulfonic acid (5-NO2-PAH) and cationic surfactant to form 1:2 ionic association complex in a weakly basic medium (pH 9.44). The determination conditions and the mechanism were discussed. The method has been applied to the analysis of wastewater and moat water samples.

  12. Cationically polymerizable monomers derived from renewable sources. Annual performance report

    Energy Technology Data Exchange (ETDEWEB)

    Crivello, J.V.


    The objectives of this project are to design and synthesize novel monomers which orginate from renewable biological sources and to carry out their rapid, efficient, pollution-free and energy efficient cationic polymerization to useful products under the influence of ultraviolet light or heat. A summary of the results of the past year`s research on cationically polymerizable monomers derived from renewable sources is presented. Three major areas of investigation corresponding to the different classes of naturally occurring starting materials were investigated; epoxidized terpenes and natural rubber and vinyl ethers from alcohols and carbohydrates.

  13. Dilatometric, refractometric and viscometric study of lysozyme-cation interaction. (United States)

    Abad, C; Trueba, M; Campos, A; Figueruelo, J E


    The interaction between hen egg-white lysozyme and Cu(II) or Co(II) cations has been studied by dilatometry, equilibrium dialysis-differential refractometry and viscometry at different metal cation concentrations. Delta V isotherms in copper and cobalt solutions have been obtained from dilatometry. Preferential adsorption parameters and specific viscosity have been determined from refractometric and viscosimetric measurements. It has been observed that this interaction produces structural alterations in lysozyme. The magnitude of these conformational changes depends on the metal ion and protein concentration. The results obtained using the three techniques are in good agreement.


    Institute of Scientific and Technical Information of China (English)

    JinWang; KefuChen; FushanChent; ChuanshanZhao; RendangYang


    Cationic polyacrylamide (CPAM) which was prepared through complex initiation system in laboratory and cationic polyacrylamide (Ciba) were used asretention and drainage aids for bleached wheat strawpulp. The influences of (polydiallyldimethlammonium chloride) PDADMAC and PDADMAC/CPAMon Zeta potential and drainability of pulp was investigated. The dual drainage and retention systems suchas CPAM/modified bentonite, CPAM/colloidal SiO2,as well as their comparison between the two systemswere discussed, and the optimal dosages of additiveswere determined. The results showed that: the complex systems can further enhance filler retention,drainability of pulp and strength properties of paper.

  15. Divalent metal-ion transporter 1 is decreased in intestinal epithelial cells and contributes to the anemia in inflammatory bowel disease. (United States)

    Wu, Wei; Song, Yang; He, Chong; Liu, Changqin; Wu, Ruijin; Fang, Leilei; Cong, Yingzi; Miao, Yinglei; Liu, Zhanju


    Divalent metal-ion transporter 1 (DMT1) has been found to play an important role in the iron metabolism and hemogenesis. However, little is known about the potential role of DMT1 in the pathogenesis of anemia from patients with inflammatory bowel disease (IBD). Herein, we investigated expression of DMT1 in the intestinal mucosa by quantitative real-time polymerase chain reaction (qRT-PCR) and immunohistochemistry, and found that DMT1 was significantly decreased in the inflamed mucosa of active IBD patients compared with that in those patients at remission stage and healthy controls. To further study the mechanism, we cultured HCT 116 cell line in vitro. Expression of DMT1 in HCT116 was demonstrated to be markedly decreased under stimulation with TNF for 24 and 48 h, while JNK inhibitor (JNK-IN-7) could significantly reverse the decrease. Interestingly, anti-TNF therapy successfully improved anemia in clinical responsive Crohn's disease patients, and DMT1 was found to be markedly up-regulated in intestinal mucosa. Taken together, our studies demonstrate that decreased expression of DMT1 in intestinal mucosa leads to compromised absorption and transportation of iron and that blockade of TNF could rescue anemia and promote DMT1 expression in gut mucosa. This work provides a therapeutic approach in the management of anemia in IBD.

  16. Synthesis, structural characterization and biological studies of some nalidixic acid-metal complexes: Metalloantibiotic complexes of some divalent and trivalent metal ions (United States)

    Al-Khodir, Fatima A. I.; Refat, Moamen S.


    This article describes the synthesis, characterization, computational and biological assessments of some divalent and trivalent metal (Ca(II), Fe(III), Pd(II) and Au(III)) complexes of nalidixic acid (nixH). The structures of these complexes were assigned using elemental analyses and spectral measurements e.g., IR, Raman, 1H NMR, 13C NMR and electronic techniques. These results indicated that, nalidixic acid reacts as a bidentate ligand bound to the metal ion through the oxygen atoms of carbonyl and carboxylate groups. The molar conductance measurements of the complexes in DMSO correspond to be non-electrolyte nature. Thus, these complexes may be formulated as [Ca(nix)(Cl)(H2O)3]. H2O, [Fe(nix)(Cl)2(H2O)2]·3H2O, [Pd(nix)(Cl)(H2O)] and [Au(nix)(Cl)2]. Base on the Coats-Redfern and Horowitz-Metzeger methods, the kinetic thermodynamic parameters (E∗, ΔS∗, ΔH∗ and ΔG∗) of the thermal decomposition reactions have been calculated from thermogravimetric curves of TG and DTG. The nano-scale range of the nalidixic acid complexes have been discussed using X-ray powder diffraction (XRD), scanning electron microscope (SEM) and transmission electron microscopy (TEM) analyzer. The computational studies for the synthesized complexes have been estimated.

  17. Potentiometric studies on ternary complexes involving some divalent transition metal ions, gallic acid and biologically abundant aliphatic dicarboxylic acids in aqueous solutions

    Directory of Open Access Journals (Sweden)

    Abdelatty Mohamed Radalla


    Full Text Available Formation of binary and ternary complexes of the divalent transition metal ions, Cu2+, Ni2+, Co2+ and Zn2+ with gallic acid and the biologically important aliphatic dicarboxylic acids (adipic, succinic, malic, malonic, maleic, tartaric and oxalic acids were investigated by means of the potentiometric technique at 25 °C and I = 0.10 mol dm−3 NaNO3. The acid-base properties of the ligands were investigated and discussed. The acidity constants of gallic acid and aliphatic dicarboxylic acids were determined and used for determining the stability constants of the binary and ternary complexes formed in the aqueous medium under the above experimental conditions. The formation of the different 1:1 and 1:2 binary complexes and 1:1:1 ternary complexes are inferred from the corresponding potentiometric pH-metric titration curves. The ternary complex formation was found to occur in a stepwise manner. The stability constants of these binary and ternary systems were calculated. The values of Δ log K, percentage of relative stabilization (%R.S. and log X were evaluated and discussed. The concentration distribution of the various complex species formed in solution was evaluated and discussed. The mode of chelation of ternary complexes formed was ascertained by conductivity measurements.

  18. Alloyed copper chalcogenide nanoplatelets via partial cation exchange reactions. (United States)

    Lesnyak, Vladimir; George, Chandramohan; Genovese, Alessandro; Prato, Mirko; Casu, Alberto; Ayyappan, S; Scarpellini, Alice; Manna, Liberato


    We report the synthesis of alloyed quaternary and quinary nanocrystals based on copper chalcogenides, namely, copper zinc selenide-sulfide (CZSeS), copper tin selenide-sulfide (CTSeS), and copper zinc tin selenide-sulfide (CZTSeS) nanoplatelets (NPLs) (∼20 nm wide) with tunable chemical composition. Our synthesis scheme consisted of two facile steps: i.e., the preparation of copper selenide-sulfide (Cu2-xSeyS1-y) platelet shaped nanocrystals via the colloidal route, followed by an in situ cation exchange reaction. During the latter step, the cation exchange proceeded through a partial replacement of copper ions by zinc or/and tin cations, yielding homogeneously alloyed nanocrystals with platelet shape. Overall, the chemical composition of the alloyed nanocrystals can easily be controlled by the amount of precursors that contain cations of interest (e.g., Zn, Sn) to be incorporated/alloyed. We have also optimized the reaction conditions that allow a complete preservation of the size, morphology, and crystal structure as that of the starting Cu2-xSeyS1-y NPLs. The alloyed NPLs were characterized by optical spectroscopy (UV-vis-NIR) and cyclic voltammetry (CV), which demonstrated tunability of their light absorption characteristics as well as their electrochemical band gaps.

  19. Fusion Pore Diameter Regulation by Cations Modulating Local Membrane Anisotropy

    Directory of Open Access Journals (Sweden)

    Doron Kabaso


    Full Text Available The fusion pore is an aqueous channel that is formed upon the fusion of the vesicle membrane with the plasma membrane. Once the pore is open, it may close again (transient fusion or widen completely (full fusion to permit vesicle cargo discharge. While repetitive transient fusion pore openings of the vesicle with the plasma membrane have been observed in the absence of stimulation, their frequency can be further increased using a cAMP-increasing agent that drives the opening of nonspecific cation channels. Our model hypothesis is that the openings and closings of the fusion pore are driven by changes in the local concentration of cations in the connected vesicle. The proposed mechanism of fusion pore dynamics is considered as follows: when the fusion pore is closed or is extremely narrow, the accumulation of cations in the vesicle (increased cation concentration likely leads to lipid demixing at the fusion pore. This process may affect local membrane anisotropy, which reduces the spontaneous curvature and thus leads to the opening of the fusion pore. Based on the theory of membrane elasticity, we used a continuum model to explain the rhythmic opening and closing of the fusion pore.

  20. Cationic PAMAM dendrimers aggressively initiate blood clot formation. (United States)

    Jones, Clinton F; Campbell, Robert A; Brooks, Amanda E; Assemi, Shoeleh; Tadjiki, Soheyl; Thiagarajan, Giridhar; Mulcock, Cheyanne; Weyrich, Andrew S; Brooks, Benjamin D; Ghandehari, Hamidreza; Grainger, David W


    Poly(amidoamine) (PAMAM) dendrimers are increasingly studied as model nanoparticles for a variety of biomedical applications, notably in systemic administrations. However, with respect to blood-contacting applications, amine-terminated dendrimers have recently been shown to activate platelets and cause a fatal, disseminated intravascular coagulation (DIC)-like condition in mice and rats. We here demonstrate that, upon addition to blood, cationic G7 PAMAM dendrimers induce fibrinogen aggregation, which may contribute to the in vivo DIC-like phenomenon. We demonstrate that amine-terminated dendrimers act directly on fibrinogen in a thrombin-independent manner to generate dense, high-molecular-weight fibrinogen aggregates with minimal fibrin fibril formation. In addition, we hypothesize this clot-like behavior is likely mediated by electrostatic interactions between the densely charged cationic dendrimer surface and negatively charged fibrinogen domains. Interestingly, cationic dendrimers also induced aggregation of albumin, suggesting that many negatively charged blood proteins may be affected by cationic dendrimers. To investigate this further, zebrafish embryos were employed to more specifically determine the speed of this phenomenon and the pathway- and dose-dependency of the resulting vascular occlusion phenotype. These novel findings show that G7 PAMAM dendrimers significantly and adversely impact many blood components to produce rapid coagulation and strongly suggest that these effects are independent of classic coagulation mechanisms. These results also strongly suggest the need to fully characterize amine-terminated PAMAM dendrimers in regard to their adverse effects on both coagulation and platelets, which may contribute to blood toxicity.

  1. Cation binding site of cytochrome c oxidase: progress report. (United States)

    Vygodina, Tatiana V; Kirichenko, Anna; Konstantinov, Alexander A


    Cytochrome c oxidase from bovine heart binds Ca(2+) reversibly at a specific Cation Binding Site located near the outer face of the mitochondrial membrane. Ca(2+) shifts the absorption spectrum of heme a, which allowed earlier the determination of the kinetic and equilibrium characteristics of the binding, and, as shown recently, the binding of calcium to the site inhibits cytochrome oxidase activity at low turnover rates of the enzyme [Vygodina, Т., Kirichenko, A., Konstantinov, A.A (2013). Direct Regulation of Cytochrome c Oxidase by Calcium Ions. PloS ONE 8, e74436]. This paper summarizes further progress in the studies of the Cation Binding Site in this group presenting the results to be reported at 18th EBEC Meeting in Lisbon, 2014. The paper revises specificity of the bovine oxidase Cation Binding Site for different cations, describes dependence of the Ca(2+)-induced inhibition on turnover rate of the enzyme and reports very high affinity binding of calcium with the "slow" form of cytochrome oxidase. This article is part of a Special Issue entitled: 18th European Bioenergetic Conference. Guest Editors: Manuela Pereira and Miguel Teixeira.

  2. Structure and Reactivity of the Cysteine Methyl Ester Radical Cation

    NARCIS (Netherlands)

    Osburn, S.; Steill, J. D.; Oomens, J.; O' Hair, R. A. J.; Van Stipdonk, M.; Ryzhov, V.


    The structure and reactivity of the cysteine methyl ester radical cation, CysOMe(center dot+), have been examined in the gas phase using a combination of experiment and density functional theory (DFT) calculations. CysOMe(center dot+) undergoes rapid ion molecule reactions with dimethyl disulfide, a

  3. [Synthesis of functionalized cyanines. Fluorescence properties following complexation of cations]. (United States)

    Mazières, M R; Duprat, C; Sutra, E; Lamandé, L; Bergon, M; Bellan, J; Wolf, J G; Roques, C


    The ionophoric properties of podands containing dioxazaphosphocane moieties linked by inactive spacers were studied. To increase the detection sensibility of these compounds we introduced a cyanine as spacer. Fluorescence analysis demonstrated the interest of cyanines as active spacers since the complexation by cations as Ca2+ and Mg2+ gives an enhancement of the emission intensity.

  4. Metal Cations in G-Quadruplex Folding and Stability (United States)

    Bhattacharyya, Debmalya; Mirihana Arachchilage, Gayan; Basu, Soumitra


    This review is focused on the structural and physico-chemical aspects of metal cation coordination to G-Quadruplexes (GQ) and their effects on GQ stability and conformation. G-Quadruplex structures are non-canonical secondary structures formed by both DNA and RNA. G-quadruplexes regulate a wide range of important biochemical processes. Besides the sequence requirements, the coordination of monovalent cations in the GQ is essential for its formation and determines the stability and polymorphism of GQ structures. The nature, location and dynamics of the cation coordination and their impact on the overall GQ stability are dependent on several factors such as the ionic radii, hydration energy and the bonding strength to the O6 of guanines. The intracellular monovalent cation concentration and the localized ion concentrations determine the formation of GQs and can potentially dictate their regulatory roles. A wide range of biochemical and biophysical studies on an array of GQ enabling sequences have generated at a minimum the knowledge base that allows us to often predict the stability of GQs in presence of the physiologically relevant metal ions, however, prediction of conformation of such GQs is still out of the realm.

  5. Denatured Thermodynamics of Proteins in Weak Cation-exchange Chromatography

    Institute of Scientific and Technical Information of China (English)

    LI Rong; CHEN Guo-Liang


    The thermostability of some proteins in weak cation-exchange chromatography was investigated at 20-80 ℃. The results show that there is a fixed thermal denaturation transition temperature for each protein. The appearance of the thermal transition temperature indicates that the conformations of the proteins are destroyed seriously. The thermal behavior of the proteins in weak cation-exchange and hydrophobic interaction chromatographies were compared in a wide temperature range. It was found that the proteins have a higher thermostability in a weak cation-exchange chromatography system. The thermodynamic parameters(ΔH0, ΔS0) of those proteins were determined by means of Vant Hoff relationship(lnk-1/T). According to standard entropy change(ΔS0), the conformational change of the proteins was judged in the chromatographic process. The linear relationships between ΔH0 and ΔS0 can be used to evaluate "compensation temperature"(β) at the protein denaturation and identify the identity of the protein retention mechanism in weak cation-exchange chromatography.

  6. Synthesis and Cation Complexation of Lariat Calix[4 ] crowns

    Institute of Scientific and Technical Information of China (English)

    SHI Zheng-Wei; JIN Chuan-Ming; LU Guo-Yuan


    @@ Calixcrowns carrying bridging polyethyleneoxy moieties on the lower rim, which combine calixarene and crown ether in a single molecule, are a novel class of host compounds which have attracted increasing attention because of their increased ability for selective complexation of cations and neutral molecules compared with crown ethers or cal ixarenes.

  7. Two different cationic positions in Cu-SSZ-13? (United States)

    Hun Kwak, Ja; Zhu, Haiyang; Lee, Jong H; Peden, Charles H F; Szanyi, János


    H(2)-TPR and FTIR were used to characterize the nature of the Cu ions present in the Cu-SSZ-13 zeolite at different ion exchange levels. The results obtained are consistent with the presence of Cu ions at two distinct cationic positions in the SSZ-13 framework.

  8. Two different cationic positions in Cu-SSZ-13?

    Energy Technology Data Exchange (ETDEWEB)

    Kwak, Ja Hun; Zhu, Haiyang; Lee, Jong H.; Peden, Charles HF; Szanyi, Janos


    H2-TPR and FTIR were used to characterize the Cu ions present in Cu-SSZ-13 zeolite at different ion exchange levels. The results obtained are consistent with the presence of Cu ions in two distinct cationic positions of the SSZ-13 framework.

  9. Interactions between liposomes and cations in aqueous solution. (United States)

    Ruso, Juan M; Besada, Lina; Martínez-Landeira, Pablo; Seoane, Laura; Prieto, Gerardo; Sarmiento, Félix


    An investigation on the dependence of electrophoretic mobilities of unilamellar vesicles of phosphatidylcholine-cholesterol-phosphatidylinositol (PC-Chol-PI) on the concentration of several cations with variations in the relation charge/radius in the range Na+, K+, Cs+, Mg2+, Ca2+, Ba2+, Al3+, and La3+ has been realized. Plots of zeta potential against ion concentration exhibit a maximum for all the cations under study, the position of the maximum is greatly affected by the charge of the ion. From the feature of these plots two phenomenon were observed: an initial binding of cations into the slipping plane for ion concentration below the maximum and a phenomenon of vesicle association for concentration above the maximum. To confirm these observations measurements on dynamic light scattering were performed to obtain the corresponding size distribution of the liposomes at different ion concentrations. Finally the ability of the Stern isotherm to describe the adsorption of the cations to vesicles was tested by two methods. The two main parameters of the theory: the total number of adsorption sites per unit area, N1, and the equilibrium constant, K; (and consequently the free energy of adsorption, deltaG0ads) were calculated for the different ions, showing good agreement. The equilibrium constants of adsorption have been found to obey a linear relationship with ion radius the slope of which decreases with the ion charge.

  10. New cation-exchange membranes for hyperfiltration processes

    NARCIS (Netherlands)

    Velden, van der P.M.; Smolders, C.A.


    A new route for the preparation of cation exchange membranes from polystyrene-polyisoprene-polystyrene (SIS) block copolymers has been studied, using N-chlorosulfonyl isocyanate. At temperatures of 0° to 20°C, N-chlorosulfonyl isocyanate reacts readily with the olefin group in polyisoprenes, resulti

  11. Predictive model of cationic surfactant binding to humic substances

    NARCIS (Netherlands)

    Ishiguro, M.; Koopal, L.K.


    The humic substances (HS) have a high reactivity with other components in the natural environment. An important factor for the reactivity of HS is their negative charge. Cationic surfactants bind strongly to HS by electrostatic and specific interaction. Therefore, a surfactant binding model is devel

  12. Synthesis and Properties of Novel Cationic Maleic Diester Polymerizable Surfactants

    Institute of Scientific and Technical Information of China (English)


    Three new cationic polymerizable surfactants are synthesized by the reaction of alkylmaleic hemiester with glycidyltrimethylammonium chloride. Their structures are confirmed by 1H NMR, IR and elements analysis. The values of CMC and gCMC of these surfactants have been measured. One can obtain nearly monodisperse polystyrene latex by emulsion polymerization using the polymerizable surfactant.

  13. Gas-phase infrared photodissociation spectroscopy of cationic polyaromatic hydrocarbons

    NARCIS (Netherlands)

    Oomens, J.; van Roij, A. J. A.; Meijer, G.; von Helden, G.


    Infrared spectra of gas-phase cationic naphthalene, phenanthrene, anthracene, and pyrene are recorded in the 500-1600 cm(-1) range using multiphoton dissociation in an ion trap. Gas-phase polyaromatic hydrocarbons are photoionized by an excimer laser and stored in a quadrupole ion trap. Subsequent i

  14. Metal Cations in G-Quadruplex Folding and Stability (United States)

    Bhattacharyya, Debmalya; Mirihana Arachchilage, Gayan; Basu, Soumitra


    This review is focused on the structural and physicochemical aspects of metal cation coordination to G-Quadruplexes (GQ) and their effects on GQ stability and conformation. G-quadruplex structures are non-canonical secondary structures formed by both DNA and RNA. G-quadruplexes regulate a wide range of important biochemical processes. Besides the sequence requirements, the coordination of monovalent cations in the GQ is essential for its formation and determines the stability and polymorphism of GQ structures. The nature, location, and dynamics of the cation coordination and their impact on the overall GQ stability are dependent on several factors such as the ionic radii, hydration energy, and the bonding strength to the O6 of guanines. The intracellular monovalent cation concentration and the localized ion concentrations determine the formation of GQs and can potentially dictate their regulatory roles. A wide range of biochemical and biophysical studies on an array of GQ enabling sequences have generated at a minimum the knowledge base that allows us to often predict the stability of GQs in the presence of the physiologically relevant metal ions, however, prediction of conformation of such GQs is still out of the realm. PMID:27668212

  15. Cation Hydration Constants by Proton NMR: A Physical Chemistry Experiment. (United States)

    Smith, Robert L.; And Others


    Studies the polarization effect on water by cations and anions. Describes an experiment to illustrate the polarization effect of sodium, lithium, calcium, and strontium ions on the water molecule in the hydration spheres of the ions. Analysis is performed by proton NMR. (MVL)

  16. Planar Homotropenylium Cation : A Transition State with Reversed Aromaticity

    NARCIS (Netherlands)

    Gibson, Christopher M.; Havenith, Remco W. A.; Fowler, Patrick W.; Jenneskens, Leonardus W.


    In contrast to the equilibrium structure of the homoaromatic C-s homotropenylium cation, C8H9+ (1), which supports a pinched diatropic ring current, the C(2)v transition state (2) for inversion of the methylene bridge of 1 is antiaromatic and supports a two-lobe paratropic pi current, as detected by

  17. Cationic Organic/Inorganic Hybrids and Their Swelling Properties

    Institute of Scientific and Technical Information of China (English)

    E. S. Dragan; L. Ghimici; M. Cazacu


    @@ 1Introduction Specific properties of poly(dimethylsiloxanes), such as low glass transition temperature, low surface energy, good insulating properties, biological and chemical inertness, high diffusion coefficient of gases, make them very attractive for practical applications in the daily life. However, there is a great interest last time in the preparation of ionic organic/inorganic materials with new properties for new applications. Quaternary ammonium salt(QAS) groups included in siloxane copolymers could induce new interesting properties such as:permanent fungicidal and bactericidal properties, which make them very attractive as materials for sanitary applications, improved selectivity coefficients of the gas-separation membranes, ion-exchange properties and so forth. So far, QAS groups have been located in the side chain[1,2]. Our interest was focused on the preparation of some novel cationic polysiloxane copolymers containing QAS groups of both integral type and pendent type[3,4]. Our objectives for the present study concern the synthesis of some cationic organic/siloxane hybrid materials with swelling properties controlled by both the nature of cationic organic component and the ratio between the organic and inorganic counterparts. Such cationic hybrid materials could be of interest for the preparation of new stimuli-responsive hydrogels[5,6].

  18. Cation ordering and superstructures in natural layered double hydroxides. (United States)

    Krivovichev, Sergey V; Yakovenchuk, Victor N; Zolotarev, Andrey A; Ivanyuk, Gregory N; Pakhomovsky, Yakov A


    Layered double hydroxides (LDHs) constitute an important group of materials with many applications ranging from catalysis and absorption to carriers for drug delivery, DNA intercalation and carbon dioxide sequestration. The structures of LDHs are based upon double brucite-like hydroxide layers [M(2+)(n)M(3+)(m)(OH)(2(m+n)](m+), where M(2+) = Mg(2+), Fe(2+), Mn(2+), Zn(2+), etc.; M(3+) = Al(3+), Fe(3+), Cr(3+), Mn(3+), etc. Structural features of LDHs such as cation ordering, charge distribution and polytypism have an immediate influence upon their properties. However, all the structural studies on synthetic LDHs deal with powder samples that prevent elucidation of such fine details of structure architecture as formation of superstructures due to cation ordering. In contrast to synthetic materials, natural LDHs are known to form single crystals accessible to single-crystal X-ray diffraction analysis, which provides a unique possibility to investigate 3D cation ordering in LDHs that results in formation of complex superstructures, where 2D cation order is combined with a specific order of layer stacking (polytypism). Therefore LDH minerals provide an indispensable source of structural information for modeling of structures and processes happening in LDHs at the molecular and nanoscale levels.

  19. Cationic amphiphiles as delivery system for genes into eukaryotic cells

    NARCIS (Netherlands)

    Oberle, Volker; Zuhorn, Inge S.; Audouy, Sandrine; Bakowsky, Udo; Smisterová, Jarmila; Engberts, Jan B.F.N.; Hoekstra, Dick; Gregoriadis, G; McCormack, B


    Cationic liposomes, consisting of synthetic amphiphiles and a so-called helper lipid, rapidly form complexes with DNA, known as lipoplexes. When incubated with cells in culture, the DNA can be delivered into the cell and becomes expressed. Because of these properties, lipoplexes are considered a use

  20. Inward Cationic Diffusion and Percolation Transition in Glass-Ceramics

    DEFF Research Database (Denmark)

    Smedsklaer, Morten Mattrup; Yue, Yuanzheng; Mørup, Steen


    of crystallization. Below the critical value, the diffusion extent decreases only slightly with the degree of crystallization. No cationic diffusion is observed in the fully crystalline materials. The critical value might be associated with a percolation transition from an interconnected to a disconnected glass...

  1. Cationic starches on cellulose surfaces. A study of polyelectrolyte adsorption.

    NARCIS (Netherlands)

    Steeg, van de H.G.M.


    Cationic starches are used on a large scale in paper industry as wet-end additives. They improve dry strength. retention of fines and fillers, and drainage. Closure of the white water systems in the paper mills hase increased the concentration of detrimental substances. This might be the reason for

  2. Analysis of Adsorption, Ion Exchange, Thermodynamic Behaviour of Some Organic Cations on Dowex 50WX4-50/H+ Cation Exchanger in Aqueous Solutions

    Directory of Open Access Journals (Sweden)

    Ehteram A. Noor


    Full Text Available The equilibrium adsorption, ion exchange characteristics of various concentrations of some organic cations from aqueous solutions onto dowex 50WEX/H+ cation exchanger were studied at different temperatures in the range of 30-50 °C. The studied cations showed good adsorptive properties onto dowex 50WX4-5/H+ at different concentrations and temperatures. Main adsorption behaviour was ion exchange between hydrogen ions and the organic cations as indicated from the linear relation between the initial concentration of the organic cations and the released hydrogen ions. It was found that the adsorption affinity of dowex 50WX4-50/H+ towards the studied organic cations depends on the substituent type of the organic cations giving the following increasing order: 1-H < 2-OH < 3-OCH3. Thermodynamic parameters for the adsorption of the studied organic cations were evaluated and discussed. It was found that the adsorption 1-H organic cation was spontaneous, ordered, exothermic and favored with decreasing temperature. On the other hand the adsorption of both 2-OH and 3-OCH3 organic cations was found to be spontaneous and disordered with enthalpy change varies significantly with increasing organic cation concentration, suggesting dipole-dipole adsorption forces as new active sites for adsorption under conditions of relatively high concentrations. Freundlich and Dubinin-Radushkevich adsorption isotherm models reasonably describe the adsorption of the studied organic cations onto dowex 50WX4-50/H+ by segmented straight lines depending on the studied range of concentration, indicating the existence of two different sets of adsorption sites with substantial difference in energy of adsorption. According to Dubinin-Radushkevich adsorption isotherm model, physical-ion exchange mechanism was suggested for the adsorption of 1-H organic cation and both physical and chemical-ion exchange mechanisms were suggested for the adsorption of 2-OH and 3-OCH3 organic cations

  3. Influence of various functional groups on the relative stability of alkylperoxy triplet cations: A theoretical study (United States)

    Smith, Kenneth J.; Meloni, Giovanni


    CBS-QB3 energy calculations show that the formation of a stable triplet cation for alkylperoxy radicals is dependent on factors other than the stability of the daughter cations exclusively. We have found that in cases where the daughter ions are not capable of stabilizing the cation through hyperconjugation, it is possible for the triplet cation to be bound. In many circumstances, CBS-QB3 calculations have found bound triplet cation states with 'negative dissociation energies.' These results are attributed to the effects that electron donating/withdrawing substituents have on the spin and charge densities of the resulting cations.

  4. Photo-fragmentation spectroscopy of benzylium and 1-phenylethyl cations

    Energy Technology Data Exchange (ETDEWEB)

    Féraud, Géraldine; Dedonder-Lardeux, Claude; Jouvet, Christophe, E-mail: [Physique des Interactions Ioniques et Moleculaires, UMR CNRS 7345, Aix-Marseille Université, Avenue Escadrille Normandie-Niémen, 13397 Marseille Cedex 20 (France); Soorkia, Satchin [Institut des Sciences Moléculaires d’Orsay, CNRS UMR 8214, Université Paris Sud 11, 91405 Orsay Cedex (France)


    The electronic spectra of cold benzylium (C{sub 6}H{sub 5}-CH{sub 2}{sup +}) and 1-phenylethyl (C{sub 6}H{sub 5}-CH-CH{sub 3}{sup +}) cations have been recorded via photofragment spectroscopy. Benzylium and 1-phenylethyl cations produced from electrosprayed benzylamine and phenylethylamine solutions, respectively, were stored in a cryogenically cooled quadrupole ion trap and photodissociated by an OPO laser, scanned in parts of the UV and visible regions (600–225 nm). The electronic states and active vibrational modes of the benzylium and 1-phenylethyl cations as well as those of their tropylium or methyl tropylium isomers have been calculated with ab initio methods for comparison with the spectra observed. Sharp vibrational progressions are observed in the visible region while the absorption features are much broader in the UV. The visible spectrum of the benzylium cation is similar to that obtained in an argon tagging experiment [V. Dryza, N. Chalyavi, J. A. Sanelli, and E. J. Bieske, J. Chem. Phys. 137, 204304 (2012)], with an additional splitting assigned to Fermi resonances. The visible spectrum of the 1-phenylethyl cation also shows vibrational progressions. For both cations, the second electronic transition is observed in the UV, around 33 000 cm{sup −1} (4.1 eV) and shows a broadened vibrational progression. In both cases the S{sub 2} optimized geometry is non-planar. The third electronic transition observed around 40 000 cm{sup −1} (5.0 eV) is even broader with no apparent vibrational structures, which is indicative of either a fast non-radiative process or a very large change in geometry between the excited and the ground states. The oscillator strengths calculated for tropylium and methyl tropylium are weak. Therefore, these isomeric structures are most likely not responsible for these absorption features. Finally, the fragmentation pattern changes in the second and third electronic states: C{sub 2}H{sub 2} loss becomes predominant at higher

  5. Solubilization of pentanol by cationic surfactants and binary mixtures of cationic surfactants

    Energy Technology Data Exchange (ETDEWEB)

    Morgan, M.E.


    The research reported here has included studies of the solubilization of pentanol in hexadecylpyridinium chloride (CPC), trimethyletetradecylammonium chloride (C{sub 14}Cl), benzyldimethyltetradecylammonium chloride (C{sub 14}BzCl), benzyldimethylhexadecylpyridinium chloride (C{sub 16}BzCl), hexadecyltrimethylammonium bromide (CTAB), and binary mixtures of CPC + C{sub 16}BzCl and C{sub 14}Cl + C{sub 14}BzCl. Rather than using calorimetric methods, this project will employ headspace chromatography to measure solubilization of pentanol over a wide range of solute concentrations. While not yielding as much thermodynamic data as calorimetry, headspace chromatography is a more direct measure of the extent of solubilization. Using headspace chromatography, is a more direct measure of the extent of solubilization. Using headspace chromatography, this study will seek to determine whether strongly synergistic mixture ratios exist in the case of binary cationic surfactant systems. There are two equilibria in the pentanol-water-surfactant system: (1) The pentanol solubilized in micelles is in equilibrium with the monomeric pentanol in solution, and (2) the monomeric pentanol is in equilibrium with the pentanol in the vapor above the solution. To establish the link between the two equilibria, a sample of the vapor above pure liquid pentanol must be collected, in order to find the activity of pentanol in solution. Also, a calibration curve for various concentrations of pentanol in solution. From this type of data it is possible to infer both the concentration of pentanol solubilized in micelles and the concentrations of pentanol in the ``bulk`` solution outside the micelles. The method is equally applicable to systems containing a single surfactant as well as mixtures of surfactants.

  6. Measuring cation dependent DNA polymerase fidelity landscapes by deep sequencing.

    Directory of Open Access Journals (Sweden)

    Bradley Michael Zamft

    Full Text Available High-throughput recording of signals embedded within inaccessible micro-environments is a technological challenge. The ideal recording device would be a nanoscale machine capable of quantitatively transducing a wide range of variables into a molecular recording medium suitable for long-term storage and facile readout in the form of digital data. We have recently proposed such a device, in which cation concentrations modulate the misincorporation rate of a DNA polymerase (DNAP on a known template, allowing DNA sequences to encode information about the local cation concentration. In this work we quantify the cation sensitivity of DNAP misincorporation rates, making possible the indirect readout of cation concentration by DNA sequencing. Using multiplexed deep sequencing, we quantify the misincorporation properties of two DNA polymerases--Dpo4 and Klenow exo(---obtaining the probability and base selectivity of misincorporation at all positions within the template. We find that Dpo4 acts as a DNA recording device for Mn(2+ with a misincorporation rate gain of ∼2%/mM. This modulation of misincorporation rate is selective to the template base: the probability of misincorporation on template T by Dpo4 increases >50-fold over the range tested, while the other template bases are affected less strongly. Furthermore, cation concentrations act as scaling factors for misincorporation: on a given template base, Mn(2+ and Mg(2+ change the overall misincorporation rate but do not alter the relative frequencies of incoming misincorporated nucleotides. Characterization of the ion dependence of DNAP misincorporation serves as the first step towards repurposing it as a molecular recording device.

  7. Measurement of antioxidant activity with trifluoperazine dihydrochloride radical cation

    Directory of Open Access Journals (Sweden)

    M.N. Asghar


    Full Text Available A novel, rapid and cost-effective trifluoperazine dihydrochloride (TFPH decolorization assay is described for the screening of antioxidant activity. A chromogenic reaction between TFPH and potassium persulfate at low pH produces an orange-red radical cation with maximum absorption at 502 nm in its first-order derivative spectrum. TFPH was dissolved in distilled water to give a 100 mM solution. The TFPH radical cation solution was made by reacting 0.5 mL of the solution with K2S2O8 (final concentration: 0.1 mM and diluting to 100 mL with 4 M H2SO4 solution. A linear inhibition of color production was observed with linearly increasing amounts of antioxidants, with correlation coefficients (R² ranging from 0.999 to 0.983. The antioxidant capacity of standard solutions of an antioxidant was evaluated by comparing with the inhibition curve using Trolox as the standard. Comparison of antioxidant capacity determined with this newly developed TFPH assay and with the well-known 2,2'-azinobis-[3-ethylbenzthiazoline-6-sulfonic acid] (ABTS-persulfate decolorization assay indicated the efficacy and sensitivity of the procedure. The proposed assay is less expensive (costs about US$4 per 100 assays and requires only 20 min for preparation of radical cation solution in comparison with ABTS assay, in which almost 12-16 h are required for preparation of a stable ABTS radical cation solution. The present assay has the advantage over ABTS assay that it can be used to measure the antioxidant activity of the samples, which are naturally found at a pH as low as 1, because the radical cation itself has been stabilized at low pH.

  8. IR spectroscopy of cationized aliphatic amino acids: Stability of charge-solvated structure increases with metal cation size

    NARCIS (Netherlands)

    Drayss, M. K.; Armentrout, P. B.; Oomens, J.; Schaefer, M.


    Gas-phase structures of alkali metal cationized (Li+, Na+,K+, Rb+, and Cs+) proline (Pro) and N-methyl alanine have been investigated using infrared multiple photon dissociation (IRMPD) spectroscopy utilizing light generated by a free electron laser and computational modeling. Measured IRMPD spectra

  9. IR spectroscopy of cationized aliphatic amino acids: Stability of charge-solvated structure increases with metal cation size

    NARCIS (Netherlands)

    Drayß, M.K.; Armentrout, P.B.; Oomens, J.; Schäfer, M.


    Gas-phase structures of alkali metal cationized (Li+, Na+, K+, Rb+, and Cs+) proline (Pro) and N-methyl alanine have been investigated using infrared multiple photon dissociation (IRMPD) spectroscopy utilizing light generated by a free electron laser and computational modeling. Measured IRMPD spectr

  10. Variational first hyperpolarizabilities of 2,3-naphtho-15-crown-5 ether derivatives with cation-complexing: a potential and selective cation detector. (United States)

    Yu, Hai-Ling; Wang, Wen-Yong; Hong, Bo; Zong, Ying; Si, Yan-Ling; Hu, Zhong-Qiang


    Crown ethers, as a kind of heterocycle, have been the subject of great interest over recent decades due to their selective capability to bind to metal cations. The use of a constant crown ether, such as naphtho-15-crown-5 (N15C5), and varied metal cations (Li(+), Na(+), K(+), Be(2+), Mg(2+), Ca(2+), Co(2+), Ni(2+), Cu(2+)) makes it possible to determine the contributions of the metal cations to nonlinear optical (NLO) responses and to design an appropriate NLO-based cation detector. N15C5 and its metal cation derivatives have been systematically investigated by density functional theory. It is found that the dependency of the first hyperpolarizability relies on the metal cation, especially for transition metals. The decrease of the first hyperpolarizabilities for alkali metal cation derivatives is due to their relatively low oscillator strengths, whereas the significant increase of the first hyperpolarizabilities for transition metal cation derivatives can be further illustrated by their low transition energies, large amplitudes and separate distributions of first hyperpolarizability density. Thus, the alkali metal and transition metal cations are distinguishable and the transition metal cations are easier to detect by utilizing the variations in NLO responses.

  11. P507与Cyanex272协同萃取分离溶液中钴镍离子%Separation of Divalent Cobalt and Nickel Ions Using a Synergistic Solvent Extraction System with P507 and Cyanex272

    Institute of Scientific and Technical Information of China (English)

    刘美荣; 周桂英; 温建康


    Separation and recovery of divalent nickel and cobalt ions from a bioleaching solution were studied using a synergistic extraction system with P507and Cyanex272. The effects of initial pH value, volumetric ratio of P507 to Cyanex272 (P/C) in organic phase, and ratio of aqueous to organic phase (A/O) on the separation of divalent cobalt and nickel ions were studied. The results showed that the optimal conditions for the separation were: the saponification rate of organic phase 50% and saponification time 30 min, the organic phase composed of 10% [P507:Cyanex 272 at 3:2 (volume ratio)], 85% sulphonated kerosene and 5% TBP, A/O 3 to 1 and initial pH value 2.5. In these conditions, the extraction rate of divalent cobalt ion is 92.96%. At the A/O of 2 to 3, turbulence intensity of 225 r/min, time of 4 min, 98.68% of stripping rate of divalent cobalt ion could be obtained with 200 g/L of H2SO4 as the stripping agent, the separation of divalent nickel and cobalt ions was realized under the low initial pH value.%采用P507与Cyanex272协同萃取分离回收浸出液中的Ni2+,Co2+,考察了初始pH值、有机相复配比(P/C)和水油相比(A/O)的影响.结果表明,协萃优化条件为:有机相皂化率50%,皂化时间30 min;有机相组成为10%复配萃取剂[P507∶Cyanex272为3∶2(φ)]+85%磺化煤油+5% TBP;相比为3∶1,水相pH值为2.5.在此条件下,Co2+的一级萃取率为92.96%.利用200g/L硫酸反萃负载有机相,在相比2∶3、振荡强度225 r/min、时间4 min的条件下,Co2+的反萃率为98.68%,实现了低pH值下Ni2+和C02+的萃取分离.

  12. Pharmacology of the human cell voltage-dependent cation channel. Part II: inactivation and blocking

    DEFF Research Database (Denmark)

    Bennekou, Poul; Barksmann, Trine L.; Kristensen, Berit I.


    Human red cells; Nonselective voltage-dependent cation channel; NSVDC channel; Thiol group reagents......Human red cells; Nonselective voltage-dependent cation channel; NSVDC channel; Thiol group reagents...

  13. 21 CFR 872.3420 - Carboxymethylcellulose sodium and cationic polyacrylamide polymer denture adhesive. (United States)


    ... polyacrylamide polymer denture adhesive. 872.3420 Section 872.3420 Food and Drugs FOOD AND DRUG ADMINISTRATION....3420 Carboxymethylcellulose sodium and cationic polyacrylamide polymer denture adhesive. (a) Identification. A carboxymethylcellulose sodium and cationic polyacrylamide polymer denture adhesive is a...

  14. Preparing cationic cotton linter cellulose with high substitution degree by ultrasonic treatment. (United States)

    Zhang, Fulong; Pang, Zhiqiang; Dong, Cuihua; Liu, Zong


    As an important cellulose derivative, cationic cellulose has becoming an attractive material. However, it remains challenging to produce cationic cellulose with high substitute degree. In this paper, we successfully increased the substitute degree of cationic cellulose by introducing ultrasonic treatment, which efficiently breaks hydrogen bonds of the chemical structure of cationic cellulose. Properties of cationic cellulose were studied by scanning electron spectroscope (SEM), contact angle, X-ray diffraction (XRD) and thermogravimetric analysis (TGA). Experimental results show that the cationic cellulose has rougher surface and lower crystallinity degree as compared to the original sample. TGA analysis verifies that the thermostability of CLC decreases after the cationic modification. The residual of the cationic cellulose (25 wt%) after pyrolysis increases significantly as compared to that of the original cellulose (15 wt%).

  15. Comparison of cation adsorption by isostructural rutile and cassiterite.

    Energy Technology Data Exchange (ETDEWEB)

    Machesky, M.; Wesolowski, D.; Rosenqvist, J.; Predota, M.; Vlcek, L.; Ridley, M.; Kohli, V.; Zhang, Z.; Fenter, P.; Cummings, P.; Lvov, S.; Fedkin, M.; Rodriguez-Santiago, V.; Kupicki, J.; Bandura, A. (X-Ray Science Division); (Illinois State Water Survey); (Oak Ridge National Laboratory); (University of South Branisovska); (Texas Tech University); (Vanderbilt University); (The Pennsylvania State University); (St. Petersburg State University)


    Macroscopic net proton charging curves for powdered rutile and cassiterite specimens with the (110) crystal face predominant, as a function of pH in RbCl and NaCl solutions, trace SrCl{sub 2} in NaCl, and trace ZnCl{sub 2} in NaCl and Na Triflate solutions, are compared to corresponding molecular-level information obtained from static DFT optimizations and classical MD simulations, as well as synchrotron X-ray methods. The similarities and differences in the macroscopic charging behavior of rutile and cassiterite largely reflect the cation binding modes observed at the molecular level. Cation adsorption is primarily inner-sphere on both isostructural (110) surfaces, despite predictions that outer-sphere binding should predominate on low bulk dielectric constant oxides such as cassiterite ({epsilon}{sub bulk} {approx} 11). Inner-sphere adsorption is also significant for Rb{sup +} and Na{sup +} on neutral surfaces, whereas Cl{sup -} binding is predominately outer-sphere. As negative surface charge increases, relatively more Rb{sup +}, Na{sup +}, and especially Sr{sup 2+} are bound in highly desolvated tetradentate fashion on the rutile (110) surface, largely accounting for enhanced negative charge development relative to cassiterite. Charging curves in the presence of Zn{sup 2+} are very steep but similar for both oxides, reflective of Zn{sup 2+} hydrolysis (and accompanying proton release) during the adsorption process, and the similar binding modes for ZnOH{sup +} on both surfaces. These results suggest that differences in cation adsorption between high and low bulk dielectric constant oxides are more subtly related to the relative degree of cation desolvation accompanying inner-sphere binding (i.e., more tetradentate binding on rutile), rather than distinct inner- and outer-sphere adsorption modes. Cation desolvation may be favored at the rutile (110) surface in part because inner-sphere water molecules are bound further from and less tightly than on the

  16. Star-like superalkali cations featuring planar pentacoordinate carbon. (United States)

    Guo, Jin-Chang; Tian, Wen-Juan; Wang, Ying-Jin; Zhao, Xue-Feng; Wu, Yan-Bo; Zhai, Hua-Jin; Li, Si-Dian


    Superalkali cations, known to possess low vertical electron affinities (VEAs), high vertical detachment energies, and large highest occupied molecular orbital (HOMO)-lowest unoccupied molecular orbital (LUMO) energy gaps, are intriguing chemical species. Thermodynamically, such species need to be the global minima in order to serve as the promising targets for experimental realization. In this work, we propose the strategies of polyhalogenation and polyalkalination for designing the superalkali cations. By applying these strategies, the local-minimum planar pentacoordinate carbon (ppC) cluster CBe5 can be modified to form a series of star-like superalkali ppC or quasi-ppC CBe5X5 (+) (X = F, Cl, Br, Li, Na, K) cations containing a CBe5 moiety. Polyhalogenation and polyalkalination on the CBe5 unit may help eliminate the high reactivity of bare CBe5 molecule by covering the reactive Be atoms with noble halogen anions and alkali cations. Computational exploration of the potential energy surfaces reveals that the star-like ppC or quasi-ppC CBe5X5 (+) (X = F, Cl, Br, Li, Na, K) clusters are the true global minima of the systems. The predicted VEAs for CBe5X5 (+) range from 3.01 to 3.71 eV for X = F, Cl, Br and 2.12-2.51 eV for X = Li, Na, K, being below the lower bound of the atomic ionization potential of 3.89 eV in the periodic table. Large HOMO-LUMO energy gaps are also revealed for the species: 10.76-11.07 eV for X = F, Cl, Br and 4.99-6.91 eV for X = Li, Na, K. These designer clusters represent the first series of superalkali cations with a ppC center. Bonding analyses show five Be-X-Be three-center two-electron (3c-2e) σ bonds for the peripheral bonding, whereas the central C atom is associated with one 6c-2e π bond and three 6c-2e σ bonds, rendering (π and σ) double aromaticity. Born-Oppenheimer molecular dynamics simulations indicate that the CBe5 motif is robust in the clusters. As planar hypercoordination carbon species are often thermodynamically

  17. Diffusion of an organic cation into root cell walls. (United States)

    Meychik, N R; Yermakov, I P; Prokoptseva, O S


    Uptake of a cationic dye (methylene blue) by isolated root cell walls, roots of whole transpiring seedlings, and excised roots was investigated using 7-day-old seedlings of cucumber, maize, and wheat. The number of ionogenic groups per 1 g dry and wet weight of the root cell walls, their swelling capacity (K(cw)), time-dependence of methylene blue (M(cw)) ion exchange capacity, and diffusion coefficients of the cation diffusion in the polymer matrix of the cell walls (D(cw)) were determined. The M(cw) value depended on pH (or carboxyl group dissociation); it changed in accordance with the number of carboxyl groups per 1 g cell wall dry weight. This parameter decreased in the order: cucumber > wheat > maize. For description of experimental kinetic curves and calculation of cation diffusion coefficients, the equation for ion diffusion into a cylinder of infinite length was used. The chosen model adequately described cation diffusion in cell walls and roots. Diffusion coefficient values for cucumber, wheat, and maize were 3.1*10(-8), 1.3*10(-8), and 8.4*10(-8) cm(2)/sec, respectively. There was a statistically significant linear dependence between K(cw) and D(cw) values, which characterize the same property of the polymer matrix, rigidity of its polymer structure or the degree of cross-linkage or permeability. This also confirms the right choice of the model selected for calculation of methylene blue diffusion coefficients, because K(cw) and D(cw) values were obtained in independent experiments. The coefficients determined for methylene blue diffusion in transpiring seedling roots (D(ts)) and excised roots (D(er)) depended on the plant species. The rate of methylene blue diffusion into the excised roots was either 1.5-fold lower (cucumber) or 3-4-times lower (maize, wheat) than in cell walls. The values of diffusion coefficients in roots of whole seedlings were comparable which those for the cell walls. On the basis of the experimental data and results of calculations

  18. Adsorption performances and mechanisms of the newly synthesized N,N'-di (carboxymethyl) dithiocarbamate chelating resin toward divalent heavy metal ions from aqueous media

    Energy Technology Data Exchange (ETDEWEB)

    Jing Xiaosheng [State Key Laboratory of Pollution Control and Resource Reuse, School of the Environment, Nanjing University, Nanjing 210093 (China); Liu Fuqiang, E-mail: [State Key Laboratory of Pollution Control and Resource Reuse, School of the Environment, Nanjing University, Nanjing 210093 (China) and Engineering Technology Research Center of Organic Toxic Substance Control and Resource Reuse of Jiangsu Province, Nanjing 210046 (China); Yang Xin; Ling Panpan; Li Lanjuan [State Key Laboratory of Pollution Control and Resource Reuse, School of the Environment, Nanjing University, Nanjing 210093 (China); Long Chao; Li Aimin [State Key Laboratory of Pollution Control and Resource Reuse, School of the Environment, Nanjing University, Nanjing 210093 (China); Engineering Technology Research Center of Organic Toxic Substance Control and Resource Reuse of Jiangsu Province, Nanjing 210046 (China)


    N,N'-di (carboxymethyl) dithiocarbamate chelating resin (PSDC) was synthesized by anchoring the chelating agent of N,N'-di (carboxymethyl) dithiocarbamate to the chloromethylated PS-DVB (Cl-PS-DVB) matrix, as a new adsorbent for removing divalent heavy metal ions from waste-stream. The physicochemical structures of Cl-PS-DVB and PSDC were elaborately characterized using Fourier transform infrared spectroscopy (FT-IR), elemental analysis (EA), and were further morphologically characterized using BET and BJH methods. The adsorption performances of PSDC towards heavy metals such as Cu(II), Pb(II) and Ni(II) were systematically investigated, based upon which the adsorption mechanisms were deeply exploited. For the above target, the classic batch adsorption experiments were conducted to explore the kinetics and isotherms of the removal processes with pH-value, initial concentration, temperature, and contact time as the controlling parameters. The kinetic and isotherm data could be well elucidated with Lagergren-second-order equation and Langmuir model respectively. The strong affinity of PSDC toward these target soft acids could be well demonstrated with the electrostatic attraction and chelating interaction caused by IDA moiety and sulphur which were namely soft bases on the concept of hard and soft acids and bases (HASB). Thermodynamic parameters, involving {Delta}H{sup o}, {Delta}S{sup o} and {Delta}G{sup o} were also calculated from graphical interpretation of the experimental data. The standard heats of adsorption ({Delta}H{sup o}) were found to be endothermic and the entropy change values ({Delta}S{sup o}) were calculated to be positive for the adsorption of Cu(II), Pb(II) and Ni(II) ions onto the tested adsorbents. Negative values of {Delta}G{sup o} indicated that adsorption processes for all tested metal ions onto PSDC were spontaneous.

  19. Influence of divalent copper, manganese and zinc ions on fibril nucleation and elongation of the amyloid-like yeast prion determinant Sup35p-NM. (United States)

    Suhre, Michael H; Hess, Simone; Golser, Adrian V; Scheibel, Thomas


    There is a large body of evidence that divalent metal ions, particularly copper, might play a role in several protein folding pathologies like Alzheimer's disease, Parkinson's disease or the prion diseases. However, contribution of metal ions on pathogenesis and their molecular influence on the formation of amyloid structures is not clear. Therefore, the general influence of metals on the formation of amyloids is still controversially discussed. We have utilized the well established system of yeast Sup35p-NM to investigate the role of three different metal ions, Cu(2+), Mn(2+) and Zn(2+), on amyloidogenesis. Recently, it has been shown that the prion determining region NM of the Saccharomyces cerevisiae prion protein Sup35p, which is responsible for the yeast prion phenotype [PSI(+)], specifically binds Cu(2+) ions. We further characterized the affinity of NM for Cu(2+), which were found to be comparable to that of other amyloidogenic proteins like the mammalian prion protein PrP. The specific binding sites could be located in the aminoterminal N-region which is known to initiate formation of amyloidogenic nuclei. In the presence of Cu(2+), fibril nucleation was significantly delayed, probably due to influences of copper on the oligomeric ensemble of soluble Sup35p-NM, since Cu(2+) altered the tertiary structure of soluble Sup35p-NM, while no influences on fibril elongation could be detected. The secondary structure of soluble or fibrous protein and the morphology of the fibrils were apparently not altered when assembled in presence of Cu(2+). In contrast, Mn(2+) and Zn(2+) did not bind to Sup35p-NM and did not exhibit significant effects on the formation of NM amyloid fibrils.

  20. Selective divalent cobalt ions detection using Ag2O3-ZnO nanocones by ICP-OES method for environmental remediation.

    Directory of Open Access Journals (Sweden)

    Mohammed M Rahman

    Full Text Available Here, we have synthesized Ag2O3-ZnO nanocones (NCs by a wet-chemical route using reducing agents at low temperature. The structural, optical and morphological properties of Ag2O3-ZnO NCs were investigated by several conventional techniques such as powder XRD, XPS, FESEM, XEDS, FTIR and UV/vis. spectroscopy. The analytical parameters of prepared NCs were also calculated for a selective detection of divalent cobalt [Co(II] prior to its determination by inductively coupled plasma-optical emission spectrometry (ICP-OES. The selectivity of NCs toward various metal ions, including Cd(II, Co(II, Cr(III, Cu(II, Fe(III, Ni(II, and Zn(II was studied. Results of the selectivity study demonstrated that Ag2O3-ZnO NC phase was the most selective towards Co(II ion. The uptake capacity for Co(II ion was experimentally calculated to be ∼76.69 mgg-1. Moreover, adsorption isotherm data provided that the adsorption process was mainly monolayer on homogeneous adsorbent surfaces of Ag2O3-ZnO NCs. Kinetic study revealed that the adsorption of Co(II on Ag2O3-ZnO NCs phase followed the pseudo-second-order kinetic model. In addition, thermodynamic results provided that the adsorption mechanism of Co(II ions on Ag2O3-ZnO NCs was a spontaneous process and thermodynamically favorable. Finally, the proposed method was validated by applying it to real environmental water samples with reasonable results.

  1. High performance flocculating agents based on cationic polysaccharides in relation to coal fine suspension

    Energy Technology Data Exchange (ETDEWEB)

    Pal, S.; Sen, G.; Karmakar, N.C.; Mal, D.; Singh, R.P. [Birla Institute of Technology, Ranchi (India). Dept. of Applied Chemistry


    Five polysaccharides namely amylopectin, amylose, glycogen, guar gum and starch have been cationized by grafting with N-(3-chloro-2-hydroxypropyl) trimethyl ammonium chloride and studied for their flocculation behaviors. Of them, cationic glycogen (Cat Gly) is found to be the best for flocculation of coal suspended sample amongst cationic polysaccharides. Cat Gly was compared with some of the commercial flocculants.

  2. The Influence of Cationization on the Dyeing Performance of Cotton Fabrics with Direct Dyes

    Directory of Open Access Journals (Sweden)

    M. F. Shahin


    Full Text Available The effect of cationic modification of cotton fabrics, using cationic agent (Chromatech 9414 on direct dyeing characteristics was studied in this work. Cationization of cotton fabric at different conditions (pH, cationic agent concentration, temperature and time was investigated and the optimum conditions were determined . Nitrogen content of cotton samples pretreated with cationic agent was indicated. The results showed that increasing cationic agent concentration lead to higher nitrogen content on cotton fabric . The cationized cotton fabrics were dyed with two direct dyes (C.I. Direct Yellow 142 - C.I. Direct red 224 and the results were compared to untreated cotton fabrics. The parameters which may affect the dyeing process such as dye concn., addition of salt, time and temperature of dyeing were studied. The dyeing results illustrate that cationization improves the fabric dyeability compared to the uncationized cotton and the magnitude of increase in colour depth depends on the nitrogen content of the cationized cotton fabric .The results also refer to possibility of dyeing cationized cotton fabric with direct dyes without addition of electrolytes to give colour strength higher than that achieved on uncationized cotton using conventional dyeing method .Another important advantage of cationic treatment is in the saving of dye concn., energy ,dyeing time , rinse water and subsequently saving of waste water treatment , and finally minimizes the environmental pollution . The changes in surface morphology of fibres after cationization were identified by various methods such as wettability and scanning with the electron microscope. Different fastness properties were evaluated.

  3. 21 CFR 872.3480 - Polyacrylamide polymer (modified cationic) denture adhesive. (United States)


    ... adhesive. 872.3480 Section 872.3480 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND... polymer (modified cationic) denture adhesive. (a) Identification. A polyacrylamide polymer (modified cationic) denture adhesive is a device composed of polyacrylamide polymer (modified cationic) intended...

  4. Structure of ionic liquids with cationic silicon-substitutions (United States)

    Wu, Boning; Shirota, Hideaki; Lall-Ramnarine, Sharon; Castner, Edward W.


    Significantly lower viscosities result when a single alkyl carbon is replaced by a silicon atom on the side chain of an ionic liquid cation. To further explore this effect, we compare liquid structure factors measured using high-energy X-ray scattering and calculated using molecular dynamics simulations. Four ionic liquids are studied that each has a common anion, bis(trifluoromethylsulfonyl)amide ( NTf2 - ). The four cations for this series of NTf2 - -anion ionic liquids are 1-methyl-3-trimethylsilylmethylimidazolium (Si-mim+), 1-methyl-3-neopentylimidazolium (C-mim+), 1-methyl-3-pentamethyldisiloxymethylimidazolium (SiOSi-mim+), and 1-methyl-1-trimethylsilylmethylpyrrolidinium (Si-pyrr+). To achieve quantitative agreement between the structure factors measured using high-energy X-ray scattering and molecular dynamics simulations, new transferable parameters for silicon were calibrated and added to the existing force fields.

  5. Review on cation exchange selectivity coefficients for MX-80 bentonite

    Energy Technology Data Exchange (ETDEWEB)

    Domenech, C.; Arcos, D.; Duro, L. [ENVIROS, Passeig de Rubi, 29-31, 08197 Valldoreix (Spain); Sellin, P. [SKB, Brahegatan 47, SE-102 40 Stockholm (Sweden)


    Full text of publication follows: Bentonite is considered as engineered barrier in the near field of a nuclear waste repository due to its low permeability, what impedes groundwater flow to the nuclear waste, and its high retention capacity (sorption) of radionuclides in the eventuality of groundwater intrusion. One of the main retention processes occurring at the bentonite surface is ion exchange. This process may exert a strong control on the mobility of major pore water cations. Changes in major cation concentration, especially calcium, can affect the dissolution-precipitation of calcite, which in turn controls one of the key parameters in the system: pH. The cation exchange process is usually described according to the Gaines-Thomas convention: Ca{sup 2+} + 2 NaX = CaX{sub 2} + 2 Na{sup +}, K{sub Ca} = (N{sub Ca} x a{sup 2}{sub Na{sup +}})/(N{sup 2}{sub Na} x a{sub Ca{sup 2+}}) where K{sub Ca} is the selectivity coefficient for the Ca by Na exchange, ai is the activity of cation 'i' in solution and NJ the equivalent fractional occupancy of cation 'J' in bentonite. Parameters such as solid to liquid (S:L) ratio and dry density of the solid have an important influence on the value of selectivity coefficients (K{sub ex}). Although in most geochemical modelling works, K{sub ex} values are directly taken from experiments conducted at low S:L ratios and low dry densities, the expected conditions in a deep geological nuclear waste repository are higher S:L and higher bentonite density (1.6{sup -3} in the SKB design to obtain a fully water saturated density of around 2.0{sup -3}). Experiments focused at obtaining selectivity coefficients under the conditions of interest face the difficulty of achieving a proper extraction and analyses of pore water without disturbing the system by the sampling method itself. In this work we have conducted a complete analyses of published data on MX-80 bentonite cationic exchange in order to assess the

  6. S. Typhimurium strategies to resist killing by cationic antimicrobial peptides. (United States)

    Matamouros, Susana; Miller, Samuel I


    S. Typhimurium is a broad host range Gram-negative pathogen that must evade killing by host innate immune systems to colonize, replicate, cause disease, and be transmitted to other hosts. A major pathogenic strategy of Salmonellae is entrance, survival, and replication within eukaryotic cell phagocytic vacuoles. These phagocytic vacuoles and gastrointestinal mucosal surfaces contain multiple cationic antimicrobial peptides (CAMPs) which control invading bacteria. S. Typhimurium possesses several key mechanisms to resist killing by CAMPs which involve sensing CAMPs and membrane damage to activate signaling cascades that result in remodeling of the bacterial envelope to reduce its overall negative charge with an increase in hydrophobicity to decrease binding and effectiveness of CAMPs. Moreover Salmonellae have additional mechanisms to resist killing by CAMPs including an outer membrane protease which targets cationic peptides at the surface, and specific efflux pumps which protect the inner membrane from damage. This article is part of a Special Issue entitled: Bacterial Resistance to Antimicrobial Peptides.

  7. Preparation of sulfonated cation exchangers from petroleum asphaltites

    Energy Technology Data Exchange (ETDEWEB)

    Pokonova, Yu.V.; Pol' kin, G.B.; Proskuryakov, V.A.


    It was established that the reaction of petroleum asphaltite sulfonation is determined in the first step by the chemical reaction rate, and in the last --- by diffusion factors. The kinetic constants were found for each reaction step. Sulfonated cation exchangers were obtained having the characteristics: specific volume of the swollen cation exchanger 3.30 mL/g, bulk density of the air-dry product 0.58 g/mL., moisture content 23.4%, swelling in water 41.6%, mechanical strength 80.0%, static exchange capacity with respect to 0.1N NaOH solution 2.76 mg equiv/g, dynamic exchange capacity with respect to 0.0035N CaC1/sub 2/ solution for a specific load of 10 L/L.h 465 mg equiv/L.

  8. Cationic polymers for successful flocculation of marine microalgae. (United States)

    't Lam, G P; Vermuë, M H; Olivieri, G; van den Broek, L A M; Barbosa, M J; Eppink, M H M; Wijffels, R H; Kleinegris, D M M


    Flocculation of microalgae is a promising technique to reduce the costs and energy required for harvesting microalgae. Harvesting marine microalgae requires suitable flocculants to induce the flocculation under marine conditions. This study demonstrates that cationic polymeric flocculants can be used to harvest marine microalgae. Different organic flocculants were tested to flocculate Phaeodactylum tricornutum and Neochloris oleoabundans grown under marine conditions. Addition of 10 ppm of the commercial available flocculants Zetag 7557 and Synthofloc 5080H to P. tricornutum showed a recovery of, respectively, 98% ± 2.0 and 94% ± 2.9 after flocculation followed by 2h sedimentation. Using the same flocculants and dosage for harvesting N. oleoabundans resulted in a recovery of 52% ± 1.5 and 36% ± 11.3. This study shows that cationic polymeric flocculants are a viable option to pre-concentrate marine cultivated microalgae via flocculation prior to further dewatering.

  9. Mobility of alkali cations in polypyrrole-dodecyl sulfate

    Energy Technology Data Exchange (ETDEWEB)

    Kupila, E.L. [Department of Chemistry, University of Turku, 20500 Turku (Finland); Kankare, J. [Department of Chemistry, University of Turku, 20500 Turku (Finland)


    Due to the immobility of the large dodecyl sulfate anion, the mobile ions in polypyrrole-dodecyl sulfate are small ions from the solution. Virgin PP-dodecyl sulfate does not contain other ionic species, but already the first reduction causes the incorporation of cations into the membrane. Using in situ AC conductimetry on a double-band platinum electrode, we show that the insertion of cations from the solution into the PP membrane proceeds as a non-conducting zone advancing from the solution interface toward the substrate. The model allows to estimate ion mobilities in the membrane giving 8.6x10{sup -7}cm{sup 2}s{sup -1}V{sup -1} for K{sup +}. (orig.)

  10. Structure of heavy cation molecules: from experiment to simulation

    Energy Technology Data Exchange (ETDEWEB)

    Den Auwer, C.; Fillaux, C.; Guilbaud, P.; Guillaumont, D.; Moisy, P. [CEA Marcoule DEN/DRCP/SCPS, 30207 Bagnols sur Ceze (France); Conradson, S.D. [Los Alamos National Laboratory, Los Alamos, NM 87545 (United States); Di Giandomenico, V.; Le Naour, C.; Simoni, E. [IPN Orsay, 91405 Orsay (France); Hennig, C. [Forschungszentrum Rossendorf, ROBL at ESRF, 38043 Grenoble (France)


    For industrial, environmental and public health purposes, actinide chemistry has been the subject of considerable efforts since the 50's. Aqueous redox chemistry, ionic selective recognition, uptake by specific biomolecules or compartments of the geosphere are some of the major fields of investigation. The physical-chemical properties of the actinide elements strongly depend on the 5f/6d electronic configuration. X-ray photons are an ideal spectroscopic tool for structure and bonding in actinide molecules. At high photon energies, actinide Extended X-ray Absorption Fine Structure (EXAFS) is a structural probe of the cation coordination sphere. Furthermore, coupling EXAFS with molecular dynamics or quantum chemical calculations leads to a better description of the 'cation in its close environment', like polyhedron, disorder, solvent effects etc.. (authors)

  11. Microstructure characterization and cation distribution of nanocrystalline cobalt ferrite

    Energy Technology Data Exchange (ETDEWEB)

    Abbas, Y.M., E-mail: [Suez Canal University, Faculty of Science, Physics Department, Ismailia (Egypt); Mansour, S.A.; Ibrahim, M.H. [Suez Canal University, Faculty of Science, Physics Department, Ismailia (Egypt); Ali, Shehab E., E-mail: [Suez Canal University, Faculty of Science, Physics Department, Ismailia (Egypt)


    Nanocrystalline cobalt ferrite has been synthesized using two different methods: ceramic and co-precipitation techniques. The nanocrystalline ferrite phase has been formed after 3 h of sintering at 1000 deg. C. The structural and microstructural evolutions of the nanophase have been studied using X-ray powder diffraction and the Rietveld method. The refinement result showed that the type of the cationic distribution over the tetrahedral and octahedral sites in the nanocrystalline lattice is partially an inverse spinel. The transmission electronic microscope analysis confirmed the X-ray results. The magnetic properties of the samples were characterized using a vibrating sample magnetometer. - Highlights: > The refinement result showed that the cationic distribution over the sites in the lattice is partially an inverse spinel. > The transmission electronic microscope analysis confirmed the X-ray results. > The magnetic properties of the samples were characterized using a vibrating sample magnetometer.

  12. Sulfonated polyvinyl chloride fibers for cation-exchange microextraction. (United States)

    Xu, Li; Lee, Hian Kee


    Polyvinyl chloride (PVC) fiber was derivatized by concentrated sulfuric acid to yield sulfonated PVC (PVC-SO3H). The PVC-SO3H fiber had dual properties as a sorbent, based on cation-exchange and hydrophobicity. In the present study, the novel fiber was used directly as an individual device for extraction purposes in the cation-exchange microextraction of anaesthetics, followed by high-performance liquid chromatography-UV analysis. The results demonstrated that this PVC-SO3H fiber-based microextraction afforded convenient operation and cost-effective application to basic analytes. The limits of detection for four anaesthetics ranged from 1.2 to 6.0 ng/mL. No carryover (because of its disposable usage), and no loss of sorbent phase (which normally occurs in stir-bar sorptive extraction) during extraction were observed.

  13. Flow behaviour of gellan sol with selected cations. (United States)

    Sharma, Shipra; Bhattacharya, Suvendu


    An understanding of the flow behaviour of the sols before gel formation is important for developing nutrient enriched gels. The influence of cations like CaCl2 (0.05 and 0.1 %, w/w) and FeSO4 (0.05 and 0.1 %, w/w) on the rheological properties of 1 % gellan sol (w/w) prior to gelling was investigated. The apparent viscosity, reported at a shear-rate of 100 s(-1), indicated that the gellan dispersion without any cation possessed lower values compared to other samples containing different cations. The Cross model provided the best fit (0.97 ≤ r ≤ 0.99, p ≤ 0.01) compared to moderate fitting to power law model (0.94 ≤ r ≤ 0.98). Among the different Cross model parameters, the zero-shear viscosity (ηo) increased with the addition of CaCl2 and FeSO4, and with an increase in their concentrations. Zero-shear viscosity values were 0.46 Pas for gellan sol, 0.79 Pas for gellan with 0.05 % (w/w) CaCl2, 1.41 Pas for gellan with 0.1 % CaCl2, 3.85 Pas for gellan with 0.05 % FeSO4 and 4.33 Pas for gellan with 0.1 % FeSO4. An increase in cation concentration from 0.05 to 0.10 % (w/w) marginally increased the relaxation time (λ) values indicating the development of more solid characteristics in the sol.

  14. Identification of bilinear systems using differential evolution algorithm

    Indian Academy of Sciences (India)

    Saban Ozer; Hasan Zorlu


    In this work, a novel identification method based on differential evolution algorithm has been applied to bilinear systems and its performance has been compared to that of genetic algorithm. Box–Jenkins system and different type bilinear systems have been identified using differential evolution and genetic algorithms. The simulation results have shown that bilinear systems can be successfully and efficiently identified using these algorithms.


    Institute of Scientific and Technical Information of China (English)

    LinLi; BingyueLiu; YafengCao


    The cationic graft copolymer was synthesized byreversed phase emulsion copolymerization of starchwith diallydimethyl ammoniumlchlorid (DADMAC)and acrylamide (AM). The copolymerization wascarried out using (NH4)2S2Os-NH2CONH2 redox asinitiator and selecting Span-20 as emulsifier. Theeffects of emulsifier content in oil phase, volumeratio of oil to water, initiator concentration and moleratio of DADMAC to AM on the graftcopolymerization were discussed. The optimumcondition of synthetics was found with theorthogonal test method.

  16. Natural zeolite reactivity towards ozone: The role of compensating cations

    Energy Technology Data Exchange (ETDEWEB)

    Valdes, Hector, E-mail: [Laboratorio de Tecnologias Limpias (F. Ingenieria), Universidad Catolica de la Santisima Concepcion, Alonso de Ribera 2850, Concepcion (Chile); Alejandro, Serguei; Zaror, Claudio A. [Departamento de Ingenieria Quimica (F. Ingenieria), Universidad de Concepcion, Concepcion (Chile)


    Highlights: Black-Right-Pointing-Pointer Chemical and thermal treatment enhances catalytic activity of natural zeolite. Black-Right-Pointing-Pointer Modified natural zeolite exhibits high stability after thermal treatment. Black-Right-Pointing-Pointer Reducing the compensating cation content leads to an increase on ozone abatement. Black-Right-Pointing-Pointer Surface active atomic oxygen was detected using the DRIFT technique. Black-Right-Pointing-Pointer The highest reactivity toward ozone was performed by NH4Z3 zeolite sample. - Abstract: Among indoor pollutants, ozone is recognised to pose a threat to human health. Recently, low cost natural zeolites have been applied as alternative materials for ozone abatement. In this work, the effect of compensating cation content of natural zeolite on ozone removal is studied. A Chilean natural zeolite is used here as starting material. The amount of compensating cations in the zeolite framework was modified by ion exchange using an ammonium sulphate solution (0.1 mol L{sup -1}). Characterisation of natural and modified zeolites were performed by X-ray powder diffraction (XRD), nitrogen adsorption at 77 K, elemental analysis, X-ray fluorescence (XRF), thermogravimetric analysis coupled with mass spectroscopy (TGA-MS), and temperature-programmed desorption of ammonia (NH{sub 3}-TPD). Ozone adsorption and/or decomposition on natural and modified zeolites were studied by diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS). Results show that the zeolite compensating cation content affects ozone interaction with zeolite active sites. Ammonium ion-exchange treatments followed by thermal out-gassing at 823 K, reduces ozone diffusion resistance inside the zeolite framework, increasing ozone abatement on zeolite surface active sites. Weak and strong Lewis acid sites of zeolite surface are identified here as the main active sites responsible of ozone removal.

  17. Electronic absorption spectrum of triacetylene cation for astronomical considerations. (United States)

    Chakrabarty, S; Rice, C A; Mazzotti, F J; Dietsche, R; Maier, J P


    The A(2)Πg ← X(2)Πu electronic transition (4800-6000 Å) of triacetylene cation was measured in an ion trap, where the vibrational and rotational degrees of freedom were equilibrated to 25 K. The rotational profile of the origin band is predicted by a collisional-radiative rate model under conditions expected in diffuse interstellar clouds. Variation in the density of the surrounding gas, rotational temperature, and velocity dispersion are taken into account.


    Institute of Scientific and Technical Information of China (English)

    Hongjie Zhang; Huiren Hu; Fushan Chen


    In this paper, the cationic polyacrylamide (CPAM)with high molecular weight was prepared in aqueous solution through a complex initiator system. The CPAM was characterized by Fourier transform infrared spectroscopy (FTIR) and 13C nuclear magnetic resonance spectroscopy (13C NMR), and the charge density of the CPAM was determined by colloid titration. The results obtained indicated that the copolymerization technology used in the experiment was successful.

  19. Transformation of anthracene on various cation-modified clay minerals. (United States)

    Li, Li; Jia, Hanzhong; Li, Xiyou; Wang, Chuanyi


    In this study, anthracene was employed as a probe to explore the potential catalytic effect of clay minerals in soil environment. Clay minerals saturated with various exchangeable cations were tested. The rate of anthracene transformation follows the order: Fe-smectite > Cu-smectite > Al-smectite ≈ Ca-smectite ≈ Mg-smectite ≈ Na-smectite. This suggests that transition-metal ions such as Fe(III) play an important role in anthracene transformation. Among Fe(III)-saturated clays, Fe(III)-smectite exhibits the highest catalytic activity followed by Fe(III)-illite, Fe(III)-pyrophyllite, and Fe(III)-kaolinite, which is in agreement with the interlayer Fe(III) content. Moreover, effects by two common environmental factors, pH and relative humidity (RH), were evaluated. With an increase in pH or RH, the rate of anthracene transformation decreases rapidly at first and then is leveled off. GC-MS analysis identifies that the final product of anthracene transformation is 9,10-anthraquinone, a more bioavailable molecule compared to anthracene. The transformation process mainly involves cation-π bonding, electron transfer leading to cation radical, and further oxidation by chemisorbed O2. The present work provides valuable insights into the abiotic transformation and the fate of PAHs in the soil environment and the development of contaminated land remediation technologies.

  20. Drug loading to lipid-based cationic nanoparticles (United States)

    Cavalcanti, Leide P.; Konovalov, Oleg; Torriani, Iris L.; Haas, Heinrich


    Lipid-based cationic nanoparticles are a new promising option for tumor therapy, because they display enhanced binding and uptake at the neo-angiogenic endothelial cells, which a tumor needs for its nutrition and growth. By loading suitable cytotoxic compounds to the cationic carrier, the tumor endothelial and consequently also the tumor itself can be destroyed. For the development of such novel anti-tumor agents, the control of drug loading and drug release from the carrier matrix is essential. We have studied the incorporation of the hydrophobic anti-cancer agent Paclitaxel (PXL) into a variety of lipid matrices by X-Ray reflectivity measurements. Liposome suspensions from cationic and zwitterionic lipids, comprising different molar fractions of Paclitaxel, were deposited on planar glass substrates. After drying at controlled humidity, well ordered, oriented multilayer stacks were obtained, as proven by the presence of bilayer Bragg peaks to several orders in the reflectivity curves. The presence of the drug induced a decrease of the lipid bilayer spacing, and with an excess of drug, also Bragg peaks of drug crystals could be observed. From the results, insight into the solubility of Paclitaxel in the model membranes was obtained and a structural model of the organization of the drug in the membrane was derived. Results from subsequent pressure/area-isotherm and grazing incidence diffraction (GID) measurements performed with drug/lipid Langmuir monolayers were in accordance with these conjectures.

  1. Cationic porphyrin derivatives for application in photodynamic therapy of cancer (United States)

    Prack McCormick, Bárbara P.; Florencia Pansa, M.; Milla Sanabria, Laura N.; Carvalho, Carla M. B.; Faustino, M. Amparo F.; Neves, Maria Graça P. M. S.; Cavaleiro, José A. S.; Rumie Vittar, Natalia B.; Rivarola, Viviana A.


    Current studies in photodynamic therapy (PDT) against cancer are focused on the development of new photosensitizers (PSs), with higher phototoxic action. The aim of this study was to compare the therapeutic efficiency of tri-cationic meso-substituted porphyrin derivatives (Tri-Py+-Me-PF, Tri-Py+-Me-Ph, Tri-Py+-Me-CO2Me and Tri-Py+-Me-CO2H) with the well-known tetra-cationic T4PM. The phototoxic action of these derivatives was assessed in human colon adenocarcinoma cells by cell viability, intracellular localization and nuclear morphology analysis. In the experimental conditions used we determined that after light activation -PF, -Ph and -CO2Me cause a more significant decline of cell viability compared to -CO2H and T4PM. These results suggest that the nature of the peripheral substituent influences the extent of cell photodamage. Moreover, we have demonstrated that PS concentration, physicochemical properties and further light activation determine the PDT response. All porphyrins were clearly localized as a punctuated pattern in the cytoplasm of the cells, and the PDT scheme resulted in apoptotic cell death after 3 h post-PDT. The tri-cationic porphyrin derivatives Tri-Py+-Me-PF, Tri-Py+-Me-Ph and Tri-Py+-Me-CO2Me showed a promising ability, making them good photosensitizer candidates for oncological PDT.

  2. Natural zeolite reactivity towards ozone: the role of compensating cations. (United States)

    Valdés, Héctor; Alejandro, Serguei; Zaror, Claudio A


    Among indoor pollutants, ozone is recognised to pose a threat to human health. Recently, low cost natural zeolites have been applied as alternative materials for ozone abatement. In this work, the effect of compensating cation content of natural zeolite on ozone removal is studied. A Chilean natural zeolite is used here as starting material. The amount of compensating cations in the zeolite framework was modified by ion exchange using an ammonium sulphate solution (0.1 mol L(-1)). Characterisation of natural and modified zeolites were performed by X-ray powder diffraction (XRD), nitrogen adsorption at 77K, elemental analysis, X-ray fluorescence (XRF), thermogravimetric analysis coupled with mass spectroscopy (TGA-MS), and temperature-programmed desorption of ammonia (NH(3)-TPD). Ozone adsorption and/or decomposition on natural and modified zeolites were studied by diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS). Results show that the zeolite compensating cation content affects ozone interaction with zeolite active sites. Ammonium ion-exchange treatments followed by thermal out-gassing at 823 K, reduces ozone diffusion resistance inside the zeolite framework, increasing ozone abatement on zeolite surface active sites. Weak and strong Lewis acid sites of zeolite surface are identified here as the main active sites responsible of ozone removal.

  3. Solidification cracking in austenitic stainless steel welds

    Indian Academy of Sciences (India)

    V Shankar; T P S Gill; S L Mannan; S Sundaresan


    Solidification cracking is a significant problem during the welding of austenitic stainless steels, particularly in fully austenitic and stabilized compositions. Hot cracking in stainless steel welds is caused by low-melting eutectics containing impurities such as S, P and alloy elements such as Ti, Nb. The WRC-92 diagram can be used as a general guide to maintain a desirable solidification mode during welding. Nitrogen has complex effects on weld-metal microstructure and cracking. In stabilized stainless steels, Ti and Nb react with S, N and C to form low-melting eutectics. Nitrogen picked up during welding significantly enhances cracking, which is reduced by minimizing the ratio of Ti or Nb to that of C and N present. The metallurgical propensity to solidification cracking is determined by elemental segregation, which manifests itself as a brittleness temperature range or BTR, that can be determined using the varestraint test. Total crack length (TCL), used extensively in hot cracking assessment, exhibits greater variability due to extraneous factors as compared to BTR. In austenitic stainless steels, segregation plays an overwhelming role in determining cracking susceptibility.

  4. Selective Facet Reactivity During Cation Exchange in Cadmium Sulfide Nanorods

    Energy Technology Data Exchange (ETDEWEB)

    Sadtler, Bryce; Demchenko, Denis; Zheng, Haimei; Hughes, Steven; Merkle, Maxwell; Dahmen, Ulrich; Wang, Lin-Wang; Alivisatos, A. Paul


    The partial transformation of ionic nanocrystals through cation exchange has been used to synthesize nanocrystal heterostructures. We demonstrate that the selectivity for cation exchange to take place at different facets of the nanocrystal plays an important role in determining the resulting morphology of the binary heterostructure. In the case of copper I (Cu+) cation exchange in cadmium sulfide (CdS) nanorods, the reaction starts preferentially at the ends of the nanorods such that copper sulfide (Cu2S) grows inwards from either end. The resulting morphology is very different from the striped pattern obtained in our previous studies of silver I (Ag+) exchange in CdS nanorods where non-selective nucleation of silver sulfide (Ag2S) occurs. From interface formation energies calculated for several models of epitaxialconnections between CdS and Cu2S or Ag2S, we infer the relative stability of each interface during the nucleation and growth of Cu2S or Ag2S within the CdS nanorods. The epitaxial connections of Cu2S to the end facets of CdS nanorods minimize the formation energy, making these interfaces stable throughout the exchange reaction. However, as the two end facets of wurtzite CdS nanorods are crystallographically nonequivalent, asymmetric heterostructures can be produced.

  5. Naphthoxy Bounded Ferrocenium Salts as Cationic Photoinitiators for Epoxy Photopolymerization

    Directory of Open Access Journals (Sweden)

    Zh. Q. Li


    Full Text Available To improve the absorption and the bulk of arene ligands, two naphthoxy bounded ferrocenium salts as new cationic photoinitiators, (η6-α-naphthoxybenzene (η5-cyclopentadienyl iron hexafluorophosphate (NOFC-1 and (η6-β-naphthoxybenzene (η5-cyclopentadienyl iron hexafluorophosphate (NOFC-2, were synthesized, characterized, and studied. NOFC-1 and NOFC-2 were prepared by the reaction of nucleophilic substitution (SNAr with naphthol and chlorobenzene-cyclopentadienyliron salt. Their activity as cationic photoinitiators was studied using real-time infrared spectroscopy. The results obtained showed that NOFC-1 and NOFC-2 are capable of photoinitiating the cationic polymerization of epoxy monomer directly on irradiation with long-wavelength UV light (365 nm. Comparative studies also demonstrated that they exhibited better efficiency than cyclopentadienyl-Fe-cymene hexafluorophosphate (I-261. When NOFC-1 and NOFC-2 were used to efficiently initiate polymerization of epoxide, both rate of polymerization and final conversion increased using benzoyl peroxide (BPO as sensitizer. DSC studies showed that NOFC-1 and NOFC-2 photoinitiators in epoxides possess good thermal stability in the absence of light.

  6. Inner-sphere complexation of cations at the rutile-water interface: A concise surface structural interpretation with the CD and MUSIC model (United States)

    Ridley, Moira K.; Hiemstra, Tjisse; van Riemsdijk, Willem H.; Machesky, Michael L.


    Acid-base reactivity and ion-interaction between mineral surfaces and aqueous solutions is most frequently investigated at the macroscopic scale as a function of pH. Experimental data are then rationalized by a variety of surface complexation models. These models are thermodynamically based which in principle does not require a molecular picture. The models are typically calibrated to relatively simple solid-electrolyte solution pairs and may provide poor descriptions of complex multi-component mineral-aqueous solutions, including those found in natural environments. Surface complexation models may be improved by incorporating molecular-scale surface structural information to constrain the modeling efforts. Here, we apply a concise, molecularly-constrained surface complexation model to a diverse suite of surface titration data for rutile and thereby begin to address the complexity of multi-component systems. Primary surface charging curves in NaCl, KCl, and RbCl electrolyte media were fit simultaneously using a charge distribution (CD) and multisite complexation (MUSIC) model [Hiemstra T. and Van Riemsdijk W. H. (1996) A surface structural approach to ion adsorption: the charge distribution (CD) model. J. Colloid Interf. Sci. 179, 488-508], coupled with a Basic Stern layer description of the electric double layer. In addition, data for the specific interaction of Ca 2+ and Sr 2+ with rutile, in NaCl and RbCl media, were modeled. In recent developments, spectroscopy, quantum calculations, and molecular simulations have shown that electrolyte and divalent cations are principally adsorbed in various inner-sphere configurations on the rutile 1 1 0 surface [Zhang Z., Fenter P., Cheng L., Sturchio N. C., Bedzyk M. J., Předota M., Bandura A., Kubicki J., Lvov S. N., Cummings P. T., Chialvo A. A., Ridley M. K., Bénézeth P., Anovitz L., Palmer D. A., Machesky M. L. and Wesolowski D. J. (2004) Ion adsorption at the rutile-water interface: linking molecular and macroscopic

  7. inner-sphere complexation of cations at the rutile-water interface: A concise surface structural interpretation with the CD and MUSIC model

    Energy Technology Data Exchange (ETDEWEB)

    Ridley, Mora K. [Texas Tech University, Lubbock; Hiemstra, T [Oak Ridge National Laboratory (ORNL); Van Riemsdijk, Willem H. [Wageningen University and Research Centre, The Netherlands; Machesky, Michael L. [Illinois State Water Survey, Champaign, IL


    Acid base reactivity and ion-interaction between mineral surfaces and aqueous solutions is most frequently investigated at the macroscopic scale as a function of pH. Experimental data are then rationalized by a variety of surface complexation models. These models are thermodynamically based which in principle does not require a molecular picture. The models are typically calibrated to relatively simple solid-electrolyte solution pairs and may provide poor descriptions of complex multicomponent mineral aqueous solutions, including those found in natural environments. Surface complexation models may be improved by incorporating molecular-scale surface structural information to constrain the modeling efforts. Here, we apply a concise, molecularly-constrained surface complexation model to a diverse suite of surface titration data for rutile and thereby begin to address the complexity of multi-component systems. Primary surface charging curves in NaCl, KCl, and RbCl electrolyte media were fit simultaneously using a charge distribution (CD) and multisite complexation (MUSIC) model [Hiemstra T. and Van Riemsdijk W. H. (1996) A surface structural approach to ion adsorption: the charge distribution (CD) model. J. Colloid Interf. Sci. 179, 488 508], coupled with a Basic Stern layer description of the electric double layer. In addition, data for the specific interaction of Ca2+ and Sr2+ with rutile, in NaCl and RbCl media, were modeled. In recent developments, spectroscopy, quantum calculations, and molecular simulations have shown that electrolyte and divalent cations are principally adsorbed in various inner-sphere configurations on the rutile 110 surface [Zhang Z., Fenter P., Cheng L., Sturchio N. C., Bedzyk M. J., Pr edota M., Bandura A., Kubicki J., Lvov S. N., Cummings P. T., Chialvo A. A., Ridley M. K., Be ne zeth P., Anovitz L., Palmer D. A., Machesky M. L. and Wesolowski D. J. (2004) Ion adsorption at the rutile water interface: linking molecular and macroscopic

  8. Effect of Divalent Ions (A = Ca, Ba and Sr Substitution in La-A-Mn-O Manganite on Structural, Magnetic and Electrical Transport Properties

    Directory of Open Access Journals (Sweden)

    K. P. Lim


    Full Text Available Problem statement: Microstructure of the grain will influence the properties of a polycrystalline manganites when different dopant is introduced. In this work, an effort had been made to investigate the influence of Ca, Ba and Sr substitution in La site. Approach: Polycrystalline manganites compound of La0.67A0.33MnO3 where A = Ba, Sr and Ca had been prepared via conventional solid-state reaction method. The structure, microstructure, magnetic and electrical properties had been investigated using XRD, SEM, VSM and four-point probe techniques. Results: XRD spectrums showed that LBMO and LCMO were in single-phase orthorhombic structure whereas LSMO was rhombohedral structure. Scanning electron micrographs showed that LSMO had smaller average grain size as compared to LBMO. However, for LCMO, there was no clear grain boundary that can be observed and all the grains were well connected. The difference in the microstructure image might be due to the variance A-site cation that differs in grain growth. The Curie temperature, Tc of LBMO and LSMO was 343.0 and 363.5 K, respectively. But the Tc for LCMO was lower then 300 K. The Tp for LCMO was 215 K while it was near or above 300K for LBMO and LSMO. All samples showed extrinsic Magnetoresistance (MR effect. Higher MR was observed well below Tc or Tp where MR value increased monotonically with the decrease of temperature. This was associated with the different grain and grain boundary formation when different cation was substituted. LCMO displayed the highest low-field MR value (-15.82% at 0.2 T, 90 K and high-field MR (-25.60% at 1 T, 300 K. Conclusion: Hence, electrical and magnetic transition temperature (Tp and Tc were affected by the average A-site cation radius.

  9. Alkali metal cation-hexacyclen complexes: effects of alkali metal cation size on the structure and binding energy. (United States)

    Austin, C A; Rodgers, M T


    Threshold collision-induced dissociation (CID) of alkali metal cation-hexacyclen (ha18C6) complexes, M(+)(ha18C6), with xenon is studied using guided ion beam tandem mass spectrometry techniques. The alkali metal cations examined here include: Na(+), K(+), Rb(+), and Cs(+). In all cases, M(+) is the only product observed, corresponding to endothermic loss of the intact ha18C6 ligand. The cross-section thresholds are analyzed to extract zero and 298 K M(+)-ha18C6 bond dissociation energies (BDEs) after properly accounting for the effects of multiple M(+)(ha18C6)-Xe collisions, the kinetic and internal energy distributions of the M(+)(ha18C6) and Xe reactants, and the lifetimes for dissociation of the activated M(+)(ha18C6) complexes. Ab initio and density functional theory calculations are used to determine the structures of ha18C6 and the M(+)(ha18C6) complexes, provide molecular constants necessary for the thermodynamic analysis of the energy-resolved CID data, and theoretical estimates for the M(+)-ha18C6 BDEs. Calculations using a polarizable continuum model are also performed to examine solvent effects on the binding. In the absence of solvent, the M(+)-ha18C6 BDEs decrease as the size of the alkali metal cation increases, consistent with the noncovalent nature of the binding in these complexes. However, in the presence of solvent, the ha18C6 ligand exhibits selectivity for K(+) over the other alkali metal cations. The M(+)(ha18C6) structures and BDEs are compared to those previously reported for the analogous M(+)(18-crown-6) and M(+)(cyclen) complexes to examine the effects of the nature of the donor atom (N versus O) and the number donor atoms (six vs four) on the nature and strength of binding.

  10. Kinetic Analysis of a Globin-Coupled Histidine Kinase, AfGcHK: Effects of the Heme Iron Complex, Response Regulator, and Metal Cations on Autophosphorylation Activity. (United States)

    Fojtikova, Veronika; Stranava, Martin; Vos, Marten H; Liebl, Ursula; Hranicek, Jakub; Kitanishi, Kenichi; Shimizu, Toru; Martinkova, Marketa


    The globin-coupled histidine kinase, AfGcHK, is a part of the two-component signal transduction system from the soil bacterium Anaeromyxobacter sp. Fw109-5. Activation of its sensor domain significantly increases its autophosphorylation activity, which targets the His183 residue of its functional domain. The phosphate group of phosphorylated AfGcHK is then transferred to the cognate response regulator. We investigated the effects of selected variables on the autophosphorylation reaction's kinetics. The kcat values of the heme Fe(III)-OH(-), Fe(III)-cyanide, Fe(III)-imidazole, and Fe(II)-O2 bound active AfGcHK forms were 1.1-1.2 min(-1), and their Km(ATP) values were 18.9-35.4 μM. However, the active form bearing a CO-bound Fe(II) heme had a kcat of 1.0 min(-1) but a very high Km(ATP) value of 357 μM, suggesting that its active site structure differs strongly from the other active forms. The Fe(II) heme-bound inactive form had kcat and Km(ATP) values of 0.4 min(-1) and 78 μM, respectively, suggesting that its low activity reflects a low affinity for ATP relative to that of the Fe(III) form. The heme-free form exhibited low activity, with kcat and Km(ATP) values of 0.3 min(-1) and 33.6 μM, respectively, suggesting that the heme iron complex is essential for high catalytic activity. Overall, our results indicate that the coordination and oxidation state of the sensor domain heme iron profoundly affect the enzyme's catalytic activity because they modulate its ATP binding affinity and thus change its kcat/Km(ATP) value. The effects of the response regulator and different divalent metal cations on the autophosphorylation reaction are also discussed.

  11. Effects of Hofmeister salt series on gluten network formation: Part I. Cation series. (United States)

    Tuhumury, H C D; Small, D M; Day, L


    Different cationic salts were used to investigate the effects of the Hofmeister salt series on gluten network formation. The effects of cationic salts on wheat flour dough mixing properties, the rheological and the chemical properties of the gluten extracted from the dough with different respective salts, were investigated. The specific influence of different cationic salts on the gluten structure formation during dough mixing, compared to the sodium ion, were determined. The effects of different cations on dough and gluten of different flours mostly followed the Hofmeister series (NH4(+), K(+), Na(+), Mg(2+) and Ca(2+)). The impacts of cations on gluten structure and dough rheology at levels tested were relatively small. Therefore, the replacement of sodium from a technological standpoint is possible, particularly by monovalent cations such as NH4(+), or K(+). However the levels of replacement need to take into account sensory attributes of the cationic salts.

  12. Trace Metals in Groundwater & Vadose Zone Calcite: In Situ Containment & Stabilization of Stronthium-90 & Other Divalent Metals & Radionuclides at Arid West DOE

    Energy Technology Data Exchange (ETDEWEB)

    Smith, Robert W


    microbial calcite precipitation on the partitioning and retention of strontium and other naturally occurring divalent metals in groundwater. * Identification of specific microbial characteristics that signify subsurface geochemical conditions conducive to ureolytically-driven calcite precipitation.

  13. Effects of different cations on properties of ionomers of maleated styrene-butadiene-styrene triblock copolymer%阳离子对顺酐化苯乙烯-丁二烯-苯乙烯三嵌段共聚物离聚体性能的影响

    Institute of Scientific and Technical Information of China (English)

    刘大刚; 谢洪泉; 高玉


    The ionomers containing different cations, such as sodium, lithium, potassium, calcium,zinc, lead, magnesium, and ethyl ammonium were synthesized from the ionization of maleated styrenebutadiene-styrene triblock copolymer ( SBS ) .Effects of different cations on the thermal, mechanical, oil resistance and adhesive properties of the ionomers were studied. The results showed that, in addition to the glass transition temperatures (Tg) of butadiene and styrene blocks, the ionomers exhibited third Tg, which is due to the dissociation of the ionic domains. For the monovalent alkali metal cation neutralized ionomers, the higher the ionic potential, the higher the dissociation temperature of ionic domains, tensile strength and lap shear strength to iron plates and the order from large to small was Li+ > Na+> K+; for the divalent cation neutralized ionomers, the dissociation temperature of ionic domains decreased in the order of Ca2+> Zn2+>Pb2+ , whereas the tensile strength decreased in the order of Ca2+> Zn2 + > Mg2 + , but all were lower than those of the monovalent alkali metal cation neutralized ionomers. The oil resistance of the divalent cation neutralized ionomers was better than that of the monovalent cation neutralized ionomers or SBS.The lap shear strength of zinc ion neutralized ionomer to iron plates was the highest of all, being 0. 594 MPa.%将顺酐化苯乙烯-丁二烯-苯乙烯三嵌段共聚物(SBS)离子化得到含不同阳离子的离聚体,考察了不同阳离子对离聚体热性能、物理机械性能、耐油性能和粘接性能的影响.结果表明,离聚体有3个玻璃化转变温度(Tg),其中2个是SBS固有的Tg,另一个是离子微区的离解温度;对于含1价阳离子的离聚体,离子电离势越高,离聚体的离解温度、拉伸强度和搭接剪切强度基本越高,即从大到小依次为含锂离聚体、含钠离聚体、含钾离聚体;含2价阳离子离聚体的离解温度从大到小依次为含钙离聚

  14. Reduced hepatic uptake and intestinal excretion of organic cations in mice with a targeted disruption of the organic cation transporter 1 (Oct1 [Slc22a1]) gene

    NARCIS (Netherlands)

    Jonker, JW; Wagenaar, E; Mol, CAAM; Buitelaar, M; Koepsell, H; Smit, JW; Schinkel, AH


    The polyspecific organic cation transporter 1 (OCT1 [SLC22A1]) mediates facilitated transport of small (hydrophilic) organic cations. OCT1 is localized at the basolateral membrane of epithelial cells in the liver, kidney, and intestine and could therefore be involved in the elimination of endogenous

  15. STXM / NEXAFS investigation of humic acid metal cation interaction (United States)

    Plaschke, M.; Rothe, J.; Denecke, M. A.; Geckeis, H.


    Waste matrix dissolution following water intrusion in a future underground nuclear waste repository is regarded as a possible failure scenario leading to the dispersal of radioactive substances in the environment. Dissolved actinides, carriers of the long term radiotoxicity, may interact with groundwater constituents or sediment and host rock phases. These processes can either enhance or retard actinide mobility in the aquifer surrounding the repository. Actinide species may be highly mobile occuring as ‘eigen-colloids' or actinides adsorbed on groundwater colloids. The latter include dissolved humic acids (HA), mineral particles like iron oxides/hydroxides or clays and mineral/organic associations. The chemical characterization of these carrier colloids and a molecular scale understanding of the actinide-colloid interaction is a prerequisite to reliable prediction of actinide mobility based on model calculations. Therefore, chemical speciation information along with micro-scale morphology information is mandatory. Scanning Transmission X-ray Microscopy (STXM) is a powerful technique to reveal the chemical functionality and morphology of organic matter on a sub-µm scale. Moreover, STXM benefits from the ability to characterize organic samples in a thin film of aqueous solution. Morphological and microchemical information can be obtained at the same time within the spectral ‘water window' (i.e., between the C 1s and O 1s absorption edges at 284 eV and 537 eV, respectively). This ensures that complex hydrated structures of HA are kept in their native state. STXM investigations of HA in contact with polyvalent metal cations are carried out at the NSLS and SLS endstations. STXM micrographs at the carbon K-edge of metal cation loaded HA show optically dense zones (densification of carbon) embedded in a matrix of less dense material. Carboxyl groups are proposed to act as the primary HA cation attachment sites. NEXAFS (Near Edge Absorption Fine Structure) spectra of

  16. Further Aspects of Ochratoxin A-Cation Interactions: Complex Formation with Zinc Ions and a Novel Analytical Application of Ochratoxin A-Magnesium Interaction in the HPLC-FLD System

    Directory of Open Access Journals (Sweden)

    Miklós Poór


    Full Text Available Ochratoxin A (OTA is a mycotoxin produced by different Aspergillus and Penicillium species. Since its mechanism of action is not fully understood yet, it is important to gain further insight into different interactions of OTA at the molecular level. OTA is found worldwide in many foods and drinks. Moreover, it can also be detected in human and animal tissues and body fluids, as well. Therefore, the development of highly sensitive quantitative methods for the determination of OTA is of utmost importance. OTA most likely forms complexes with divalent cations, both in cells and body fluids. In the present study, the OTA-zinc interaction was investigated and compared to OTA-magnesium complex formation using fluorescence spectroscopy and molecular modeling. Our results show that zinc(II ion forms a two-fold higher stable complex with OTA than magnesium(II ion. In addition, based on the enhanced fluorescence emission of OTA in its magnesium-bound form, a novel RP-HPLC-fluorescence detector (FLD method was also established. Our results highlight that the application of magnesium chloride in alkaline eluents results in an approximately two-fold increase in sensitivity using the HPLC-FLD technique.

  17. Increased cation conductance in human erythrocytes artificially aged by glycation. (United States)

    Kucherenko, Yuliya V; Bhavsar, Shefalee K; Grischenko, Valentin I; Fischer, Uwe R; Huber, Stephan M; Lang, Florian


    Excessive glucose concentrations foster glycation and thus premature aging of erythrocytes. The present study explored whether glycation-induced erythrocyte aging is paralleled by features of suicidal erythrocyte death or eryptosis, which is characterized by cell membrane scrambling with subsequent phosphatidylserine exposure at the cell surface and cell shrinkage. Both are triggered by increases of cytosolic Ca(2+) concentration ([Ca(2+)](i)), which may result from activation of Ca(2+) permeable cation channels. Glycation was accomplished by exposure to high glucose concentrations (40 and 100 mM), phosphatidylserine exposure estimated from annexin binding, cell shrinkage from decrease of forward scatter, and [Ca(2+)](i) from Fluo3-fluorescence in analysis via fluorescence-activated cell sorter. Cation channel activity was determined by means of whole-cell patch clamp. Glycation of total membrane proteins, immunoprecipitated TRPC3/6/7, and immunoprecipitated L-type Ca(2+) channel proteins was estimated by Western blot testing with polyclonal antibodies used against advanced glycation end products. A 30-48-h exposure of the cells to 40 or 100 mM glucose in Ringer solution (at 37 degrees C) significantly increased glycation of membrane proteins, hemoglobin (HbA(1c)), TRPC3/6/7, and L-type Ca(2+) channel proteins, enhanced amiloride-sensitive, voltage-independent cation conductance, [Ca(2+)](i), and phosphatidylserine exposure, and led to significant cell shrinkage. Ca(2+) removal and addition of Ca(2+) chelator EGTA prevented the glycation-induced phosphatidylserine exposure and cell shrinkage after glycation. Glycation-induced erythrocyte aging leads to eryptosis, an effect requiring Ca(2+) entry from extracellular space.

  18. Monomer and dimer radical cations of benzene, toluene, and naphthalene. (United States)

    Das, Tomi Nath


    Pulse radiolytic generation of monomeric and dimeric cations of benzene, toluene, and naphthalene in aqueous acid media at room temperature and their spectrophotometric characterization is discussed. Results presented include measurements of each aromatic's solubility in H(2)O-H(2)SO(4) and H(2)O-HClO(4) media over the acidity range pH 1 to H(0) -7.0, facile oxidative generation, and real-time identification of appropriate cationic transients with respective lambda(max) (nm) and epsilon (M(-1) cm(-1)) values measured as follows: C(6)H(6)(*+) (443, 1145 +/- 75), C(6)H(5)CH(3)(*+) (428, 1230 +/- 90), C(10)H(8)(*+) (381, 3650 +/- 225, and 687, 2210 +/- 160), (C(6)H(6))(2)(*+) (860, 2835 +/- 235), (C(6)H(5)CH(3))(2)(*+) (950, 1685 +/- 155), and (C(10)H(8))(2)(*+) (1040, 4170 +/- 320). Kinetic measurements reveal the respective formation rates of monomeric cations to be near-diffusion controlled, while the forward rate values for the dimeric species generation are marginally slower. The proton activity corrected pK(a) values are found to remain between -2.6 and -1.3 for the ArH(*+) species (C(6)H(6)(*+) most acidic, C(10)H(8)(*+) least acidic), while the pK(a) values of (ArH)(2)(*+) species vary from -5.0 to -3.0 ((C(6)H(6))(2)(*+) most acidic, (C(10)H(8))(2)(*+) least acidic). In H(0) -5 in aqueous H(2)SO(4), the respective stabilization energy of (C(6)H(6))(2)(*+), (C(6)H(5)CH(3))(2)(*+), and (C(10)H(8))(2)(*+) is estimated to be 16.6, 15.0, and 13.7 kcal mol(-1). Thus, the aqueous acid solution emerges as an alternative medium for typical radical-cationic studies, while offering compatibility for the deprotonated radical characterization near neutral pH.

  19. Protic Cationic Oligomeric Ionic Liquids of the Urethane Type

    DEFF Research Database (Denmark)

    Shevchenko, V. V.; Stryutsky, A. V.; Klymenko, N. S.;


    Protic oligomeric cationic ionic liquids of the oligo(ether urethane) type are synthesized via the reaction of an isocyanate prepolymer based on oligo(oxy ethylene)glycol with M = 1000 with hexamethylene-diisocyanate followed by blocking of the terminal isocyanate groups with the use of amine...... derivatives of imidazole, pyridine, and 3-methylpyridine and neutralization of heterocycles with ethanesulfonic acid and p-toluenesulfonic acid. The structures and properties of the synthesized oligomeric ionic liquids substantially depend on the structures of the ionic groups. They are amorphous at room...

  20. Synthesis of Branch Fluorinated Cationic Surfactant and Surface Properties

    Directory of Open Access Journals (Sweden)

    Hongke Wu


    Full Text Available A novel fluorinated quaternary ammonium salt cationic surfactant N,N,N-trimethyl-2-[[4-[[3,4,4,4-tetrafluoro-2-[1,2,2,2-tetrafluoro-1-(trifluoromethylethyl]-1,3-bis(tri-fluoromethyl-1-buten-1-yl]oxy]-benzoyl]amino]-iodide (FQAS was synthesized successfully, and its structure was characterized by FTIR, 1H-NMR, 19F-NMR, and MS. The surface activities of FQAS and the effect of temperature, electrolyte, and combination with hydrocarbon surfactant were investigated. The results showed that FQAS exhibited excellent surface activity and combination with hydrocarbon surfactant.

  1. Synthesis, Characterization, and Flocculation Properties of Branched Cationic Polyacrylamide

    Directory of Open Access Journals (Sweden)

    Weimin Sun


    Full Text Available A water soluble branched cationic polyacrylamide (BCPAM was synthesized using solution polymerization. The polymerization was initiated using potassium diperiodatocuprate, K5[Cu(HIO62](Cu(III, initiating the self-condensing vinyl copolymerization of acrylamide and acryloxyethyltrimethyl ammonium chloride (DAC monomer. The resulting copolymer was characterized by the use of Fourier-transform infrared (FTIR spectroscopy and nuclear magnetic resonance (NMR spectroscopy. Its flocculation properties were evaluated with standard jar tests of sewage. The effects of initiator concentration, monomer concentration, reaction temperature, and the mass ratio of monomers on intrinsic viscosity and flocculation properties of the product were determined using single-factor experiments and orthogonal experiment.

  2. Peak metamorphic temperatures from cation diffusion zoning in garnet

    DEFF Research Database (Denmark)

    Smit, Matthijs Arjen; Scherer, Erik; Mezger, Klaus


    A model that relates the characteristic diffusion length and average cooling rate to peak temperature was developed for chemical diffusion in spherical geometries on the basis of geospeedometry principles and diffusion theory. The model is quantitatively evaluated for cation diffusion profiles in...... is robust and provides a reliable means of estimating peak temperatures for different types of high-grade metamorphic rock. The tool could be of particular advantage in rocks where critical assemblages for conventional thermometry do not occur or have been replaced during retrogression....


    Institute of Scientific and Technical Information of China (English)

    Lin Li; Bingyue Liu; Yafeng Cao


    The cationic graft copolymer was synthesized by reversed phase emulsion copolymerization of starch with diallydimethyl ammoniumlchlorid (DADMAC)and acrylamide (AM). The copolymerization was carried out using (NH4)2S2O8-NH2CONH2 redox as initiator and selecting Span-20 as emulsifier. The effects of emulsifier content in oil phase, volume ratio of oil to water, initiator concentration and mole ratio of DADMAC to AM on the graft copolymerization were discussed. The optimum condition of synthetics was found with the orthogonal test method.

  4. Blackbody-induced radiative dissociation of cationic SF 6 clusters

    DEFF Research Database (Denmark)

    Toker, Jonathan; Rahinov, I.; Schwalm, D.;


    The stability of cationic SF5+(SF6)n−1 clusters was investigated by measuring their blackbody-induced radiative dissociation (BIRD) rates. The clusters were produced in a supersonic expansion ion source and stored in an electrostatic ion-beam trap at room temperature, where their abundances...... and lifetimes were measured. Using the “master equation” approach, relative binding energies of an SF6 unit in the clusters could be extracted from the storage-time dependence of the survival probabilities. The results allow for a deeper insight into the effect of a localized charge on the structure...... and stability of SF6-based clusters....

  5. Holographic Grating Formation in Cationic Photopolymers with Dark Reaction

    Institute of Scientific and Technical Information of China (English)

    WEI Hao-Yun; CAO Liang-Cai; GU Claire; XU Zhen-Feng; HE Ming-Zhao; HE Qing-Sheng; HE Shu-Rong; JIN Guo-Fan


    @@ We propose a new formula to describe the dynamics of holographic grating formation under low intensity pulse exposures in cationic photopolymers, in which the dark reaction contributes dominantly to the grating strength.The formula is based on the living polymerization mechanism and the diffusion-free approximation. The analytical solution indicates that the grating formation time depends on the termination rate constant, while the final grating strength depends linearly on the total exposure energy. These theoretical predictions are verified experimentally using the Aprilis HMC-400μm photopolymer. The results can provide guidelines for the control and optimization of the holographic recording conditions in practical applications.

  6. Properties of sulfonated cation-exchangers made from petroleum asphaltites

    Energy Technology Data Exchange (ETDEWEB)

    Pokonova, Yu.V.; Pol' kin, G.B.; Proskuryakov, V.A.


    The use of ion-exchangers in radiochemical technology is accompanied by changes of their properties under the influence of ionizing radiation. The rate of development of these processes depends on the nature and structure of the matrix and on the nature and amount of ionic groups. We have proposed a method of synthesis of ion-exchangers resistant to ..gamma.. radiation from petroleum asphaltites. Continuing these investigations, we prepared cation-exchangers by sulfonation of a mixture of petroleum asphaltites and acid asphalt. An investigation of their radiation resistance is described in this paper.

  7. Incorporation of Monovalent Cations in Sulfate Green Rust

    DEFF Research Database (Denmark)

    Christiansen, B. C.; Dideriksen, K.; Katz, A.;


    Green rust is a naturally occurring layered mixed-valent ferrous-ferric hydroxide, which can react with a range of redox-active compounds. Sulfate-bearing green rust is generally thought to have interlayers composed of sulfate and water. Here, we provide evidence that the interlayers also contain...... with water showed that Na+ and K+ were structurally fixed in the interlayer, whereas Rb+ and Cs+ could be removed, resulting in a decrease in the basal layer spacing. The incorporation of cations in the interlayer opens up new possibilities for the use of sulfate green rust for exchange reactions with both...

  8. EXAFS determination of cation local order in layered perovskites

    Energy Technology Data Exchange (ETDEWEB)

    Montero C, M. E.; Fuentes M, L.; Duarte M, J. A.; Fuentes C, L. [Centro de Investigacion en Materiales Avanzados S. C., Miguel de Cervantes Saavedra 120, Complejo Industrial Chihuahua, 31109 Chihuahua (Mexico); Garcia G, M. [Instituto de Fisica, UNAM, Ciudad Universitaria, 04510 Mexico D. F. (Mexico); Mehta, A.; Webb, S. [Stanford Synchrotron Radiation Laboratory, CA (United States)


    EXAFS analysis of Bi{sub 6}Ti{sub 3}Fe{sub 2}O{sub 18} Aurivillius ceramic was performed to elucidate the local environment of Fe cations. Experiments were performed at Stanford Synchrotron Radiation Laboratory, at T = 10, 30, 50, 75, 100 and 298 K, in fluorescence regime. EXAFS spectra were processed using the ab initio multiple scattering program FEFF6. Distances among representative atomic pairs were refined. As a basic result, the previous hypothesis suggested by X-ray diffraction experiments, regarding a preference of iron atoms for the centered perovskite layer of the unit cell, was confirmed. (Author)

  9. Spontaneous Superlattice Formation in Nanorods through PartialCation Exchange

    Energy Technology Data Exchange (ETDEWEB)

    Robinson, Richard D.; Sadtler, Bryce; Demchenko, Denis O.; Erdonmez, Can K.; Wang, Lin-Wang; Alivisatos, A. Paul


    Lattice mismatch strains are widely known to controlnanoscale pattern formation in heteroepitaxy, but such effects have notbeen exploited in colloidal nanocrystal growth. We demonstrate acolloidal route to synthesizing CdS-Ag2S nanorod superlattices throughpartial cation exchange. Strain induces the spontaneous formation ofperiodic structures. Ab initio calculations of the interfacial energy andmodeling of strain energies show that these forces drive theself-organization. The nanorod superlattices exhibit high stabilityagainst ripening and phase mixing. These materials are tunablenear-infrared emitters with potential applications as nanometer-scaleoptoelectronic devices.

  10. Cationic polyacrylamides enhance rates of starch and cellulose saccharification. (United States)

    Reye, John T; Maxwell, Kendra; Rao, Swati; Lu, Jian; Banerjee, Sujit


    Adding a cationic polyacrylamide (c-PAM) to either the amylase mediated hydrolysis of corn starch or the hydrolysis of wood fiber by cellulase can enhance the initial hydrolysis rates, although a rate decrease can occur under some conditions. Several c-PAMs can serve as catalysts and the same c-PAM can improve the efficiency of both amylase and cellulase. The initial amylase rate approximately doubles; the analogous cellulase hydrolysis rate increases by about 40%. c-PAMs increase the binding of enzyme to substrate.

  11. Ensemble classi…cation methods for autism disordered speech

    Directory of Open Access Journals (Sweden)

    Zoubir Abdeslem Benselama


    Full Text Available In this paper, we present the results of our investigation on Autism classifi…cation by applying ensemble classi…ers to disordered speech signals. The aim is to distinguish between Autism sub-classes by comparing an ensemble combining three decision methods, the sequential minimization optimization (SMO algorithm, the random forests (RF, and the feature-subspace aggregating approach (Feating. The conducted experiments allowed a reduction of 30% of the feature space with an accuracy increase over the baseline of 8.66% in the development set and 6.62% in the test set.

  12. Contributions of cation-π interactions to the collagen triple helix stability. (United States)

    Chen, Chia-Ching; Hsu, Wei; Hwang, Kuo-Chu; Hwu, Jih Ru; Lin, Chun-Cheng; Horng, Jia-Cherng


    Cation-π interactions are found to be an important noncovalent force in proteins. Collagen is a right-handed triple helix composed of three left-handed PPII helices, in which (X-Y-Gly) repeats dominate in the sequence. Molecular modeling indicates that cation-π interactions could be formed between the X and Y positions in adjacent collagen strands. Here, we used a host-guest peptide system: (Pro-Hyp-Gly)(3)-(Pro-Y-Gly-X-Hyp-Gly)-(Pro-Hyp-Gly)(3), where X is an aromatic residue and Y is a cationic residue, to study the cation-π interaction in the collagen triple helix. Circular dichroism (CD) measurements and Tm data analysis show that the cation-π interactions involving Arg have a larger contribution to the conformational stability than do those involving Lys, and Trp forms a weaker cation-π interaction with cationic residues than expected as a result of steric effects. The results also show that the formation of cation-π interactions between Arg and Phe depends on their relative positions in the strand. Moreover, the fluorinated and methylated Phe substitutions show that an electron-withdrawing or electron-donating substituent on the aromatic ring can modulate its π-electron density and the cation-π interaction in collagen. Our data demonstrate that the cation-π interaction could play an important role in stabilizing the collagen triple helix.

  13. Hydrogen release reactions of Al-based complex hydrides enhanced by vibrational dynamics and valences of metal cations. (United States)

    Sato, T; Ramirez-Cuesta, A J; Daemen, L; Cheng, Y-Q; Tomiyasu, K; Takagi, S; Orimo, S


    Hydrogen release from Al-based complex hydrides composed of metal cation(s) and [AlH4](-) was investigated using inelastic neutron scattering viewed from vibrational dynamics. The hydrogen release followed the softening of translational and [AlH4](-) librational modes, which was enhanced by vibrational dynamics and the valence(s) of the metal cation(s).

  14. Cation Guided Assembly: Crystal Structures of Two Ag(I) Complexes in Versatile Dimensionalities with Different Counter Cations

    Institute of Scientific and Technical Information of China (English)

    WANG, Jiang-Yun; GU, Wen; WANG, Wen-Zhen; LIU, Xin; LIAO, Dai-Zheng


    Assembly of [Ag(CN)2]- units with M(Ⅱ)-diamine complex cations [Cu(LN-N)2]2+, where LN-N represents1,2-diaminopropane (pn) and ethylenediamine (en), afforded two complexes, [Cu(pn)2][Ag2(CN)4] (1) and[Cu(en)2][Ag3(CN)5] (2), which were characterized by elemental analysis, IR, UV-Vis and ESR spectra. Single crystal X-ray analyses show that these complexes have 2D and 3D architectures through silver-silver interactions and other weak interactions. The luminescence behaviors of the two complexes were also studied by means of emission spectra.

  15. Molecular Dynamics Study of a Dual-Cation Ionomer Electrolyte. (United States)

    Chen, Xingyu; Chen, Fangfang; Jónsson, Erlendur; Forsyth, Maria


    The poly(N1222 )x Li1-x [AMPS] ionomer system (AMPS=2-acrylamido-2-methylpropane sulfonic acid) with dual cations has previously shown decoupled Li ion dynamics from polymer segmental motions, characterized by the glass-transition temperature, which can result in a conductive electrolyte material whilst retaining an appropriate modulus (i.e. stiffness) so that it can suppress dendrite formation, thereby improving safety when used in lithium-metal batteries. To understand this ion dynamics behavior, molecular dynamics techniques have been used in this work to simulate structure and dynamics in these materials. These simulations confirm that the Li ion transport is decoupled from the polymer particularly at intermediate N1222(+) concentrations. At 50 mol % N1222(+) concentration, the polymer backbone is more rigid than for higher N1222(+) concentrations, but with increasing temperature Li ion dynamics are more significant than polymer or quaternary ammonium cation motions. Herein we suggest an ion-hopping mechanism for Li(+) , arising from structural rearrangement of ionic clusters that could explain its decoupled behavior. Higher temperatures favor an aggregated ionic structure as well as enhancing these hopping motions. The simulations discussed here provide an atomic-level understanding of ion dynamics that could contribute to designing an improved ionomer with fast ion transport and mechanical robustness.


    Institute of Scientific and Technical Information of China (English)

    Songlin Wang; Wenxia Liu


    Layered double hydroxides consisting of layers with cationic charges may be potential candidates of cationic microparticles forming synergetic retention effect with anionic polyacrylamide. In this work, the layered double hydroxides with various molar ratios of Mg/Al were synthesized by co-precipitation of magnesium chloride and aluminum chloride and peptized by intense washing with water. The chemical formula, particle size, Zeta potential of the layered double hydroxide were analyzed. It was found that positively charged magnesium aluminum hydroxide with particle diameter in nanoparticle size could be prepared. The Zeta potential and particle size vary with the feed molar ratio of Mg/Al and the peptizing process, respectively. The Zeta potential is also pH dependent. The retention experiments carried out on DDJ show that when used together with anionic polyacrylamide, the positively charged colloidal double hydroxide greatly improves the retention of reed pulps. The chemical formula, particle size and Zeta potential of the colloidal double hydroxide all affect its retention behavior.

  17. The cation content of phospholipides from swine erythrocytes. (United States)



    Phospholipides from swine erythrocytes were isolated and separated into four reproducible fractions. One of the fractions seems to be pure phosphatidylserine. The others are almost certainly not single compounds, although the analytical data indicate that they represent mixtures considerably simpler than the parent mixture extracted from the cells. All four fractions contained Na(+) and K(+), but very little Ca(2+). Sodium was the predominant cation in two of the fractions under all conditions although the major intracellular cation was potassium. In the other two fractions the ratio Na/K varied with the extraction procedure largely because the quantity of K(+) seemed to depend on the solvent system used. There appear to be reasons to believe that the entire system of phospholipides binds Na(+) preferentially. In addition, it was observed that the quantity of Na(+) found in the lipide extracts varied when the extrusion of Na(+) from the cells was made to vary. Both of these observations are consistent with the possibility that the phospholipides play some part in the extrusion of Na(+) from these cells.

  18. Effects of cation concentration on photocatalytic performance over magnesium vanadates

    Energy Technology Data Exchange (ETDEWEB)

    Li, Peng [Catalytic Materials Group, Environmental Remediation Materials Unit, National Institute for Materials Science (NIMS), 1-1 Namiki, Tsukuba, Ibaraki 305-0044 (Japan); Zhou, Wei [Department of Physics, Tianjin University, 92 Weijin Road, Nankai District, Tianjin (China); Wang, Xin; Zhang, Yan; Wang, Defa [TU-NIMS Joint Research Center, School of Materials Science and Engineering, Tianjin University, 92 Weijin Road, Nankai District, Tianjin (China); Umezawa, Naoto, E-mail:, E-mail:; Abe, Hideki, E-mail:, E-mail: [Catalytic Materials Group, Environmental Remediation Materials Unit, National Institute for Materials Science (NIMS), 1-1 Namiki, Tsukuba, Ibaraki 305-0044 (Japan); TU-NIMS Joint Research Center, School of Materials Science and Engineering, Tianjin University, 92 Weijin Road, Nankai District, Tianjin (China); PRESTO, Japan Science and Technology Agency (JST), 4-1-8 Honcho, Kawaguchi, Saitama 332-0012 (Japan); Ye, Jinhua [Catalytic Materials Group, Environmental Remediation Materials Unit, National Institute for Materials Science (NIMS), 1-1 Namiki, Tsukuba, Ibaraki 305-0044 (Japan); TU-NIMS Joint Research Center, School of Materials Science and Engineering, Tianjin University, 92 Weijin Road, Nankai District, Tianjin (China); International Center for Materials Nanoarchitectonics (WPI-MANA), National Institute for Materials Science (NIMS), 1-1 Namiki, Tsukuba, Ibaraki 305-0044 (Japan)


    A series of magnesium vanadates (MgV {sub 2}O{sub 6}, Mg{sub 2}V {sub 2}O{sub 7}, and Mg{sub 3}V {sub 2}O{sub 8}) were synthesized to investigate the effect of cation concentration on photocatalytic performance. The samples were characterized by X-ray diffraction, field emission-scanning electron microscopy, UV-visible diffuse reflectance spectroscopy, and fluorescence spectroscopy. The photocatalytic O{sub 2} evolution experiments under visible light irradiation showed Mg{sub 2}V {sub 2}O{sub 7} exhibits the best performance, while Mg{sub 3}V {sub 2}O{sub 8} has the lowest activity. The density functional theory calculations indicated that the lowest unoccupied states of Mg{sub 3}V {sub 2}O{sub 8} are the mostly localized by the cation layers. The fluorescence spectra and fluorescence decay curves gave evident performances of excited states of magnesium vanadates and pointed out MgV {sub 2}O{sub 6} has a very short excited electron lift-time. Mg{sub 2}V {sub 2}O{sub 7} performs high photocatalytic activity because of its high electron mobility and long electron life-time.

  19. H2O Nucleation Around Noble Metal Cations (United States)

    Calaminici, Patrizia; Oropeza Alfaro, Pavel; Juarez Flores, Martin; Köster, Andreas; Beltran, Marcela; Ulises Reveles, J.; Khanna, Shiv N.


    First principle electronic structure calculations have been carried out to investigate the ground state geometry, electronic structure and binding energy of noble metal cations (H2O)n^+ clusters containing up to 10 H2O molecules. The calculations are performed with the density functional theory code deMon2k [1]. Due to the very flat potential energy surface of these systems special care to the numerical stability of energy and gradient calculation must be taken.Comparison of the results obtained with Cu^+, Ag^+ and Au^+ will be shown. This investigation provides insight into the structural arrangement of the water molecules around these metals and a microscopic understanding of the observed incremental binding energy in the case of the gold cation based on collision induced dissociation experiments. [1] A.M. Köster, P. Calaminici, M.E. Casida, R. Flores-Moreno, G. Geudtner, A. Goursot, T. Heine, A. Ipatov, F. Janetzko, J. Martin del Campo, S. Patchkovski, J.U. Reveles, A. Vela and D.R. Salahub, deMon2k, The deMon Developers, Cinvestav, 2006

  20. Cationic gadolinium chelate for magnetic resonance imaging of cartilaginous defects. (United States)

    Nwe, Kido; Huang, Ching-Hui; Qu, Feini; Warden-Rothman, Robert; Zhang, Clare Y; Mauck, Robert L; Tsourkas, Andrew


    The ability to detect meniscus defects by magnetic resonance arthrography (MRA) can be highly variable. To improve the delineation of fine tears, we synthesized a cationic gadolinium complex, (Gd-DOTA-AM4 )(2+) , that can electrostatically interact with Glycosaminoglycans (GAGs). The complex has a longitudinal relaxivity (r1) of 4.2 mM(-1) s(-1) and is highly stable in serum. Its efficacy in highlighting soft tissue tears was evaluated in comparison to a clinically employed contrast agent (Magnevist) using explants obtained from adult bovine menisci. In all cases, Gd-DOTA-AM4 appeared to improve the ability to detect the soft tissue defect by providing increased signal intensity along the length of the tear. Magnevist shows a strong signal near the liquid-meniscus interface, but much less contrast is observed within the defect at greater depths. This provides initial evidence that cationic contrast agents can be used to improve the diagnostic accuracy of MRA. Copyright © 2016 John Wiley & Sons, Ltd.

  1. Effect of cationic monomer on properties of fluorinated acrylate latex

    Institute of Scientific and Technical Information of China (English)

    Li Jun Chen


    Cationic fluorinated acrylate latex was prepared via semi-continuous emulsion copolymerization of cationic monomer and other monomers.The resultant latex and its film were characterized with dynamic light scattering detector and contact angle meter.Influences of amount of DMDAAC on the properties of resultant latex and its film were investigated in detail.Results show that the particle size of the latex has the minimum value and the zeta potential of the latex is increased when the amount of DMDAAC is increased.In addition,the particle size of the latex is unimodal distribution when the amount of DMDAAC is not more than 2.5%.However,the particle size of the latex is bimodal distribution when the amount of DMDAAC is more than 2.5%.The contact angle is varied slightly with the increase of amount of DMDAAC when it is not more than 2.5%.Nevertheless,the contact angle is decreased with the increase of the amount of DMDAAC when it is more than 25%.

  2. Stretch-activated cation channel from larval bullfrog skin

    DEFF Research Database (Denmark)

    Hillyard, Stanley D; Willumsen, Niels J; Marrero, Mario B


    Cell-attached patches from isolated epithelial cells from larval bullfrog skin revealed a cation channel that was activated by applying suction (-1 kPa to -4.5 kPa) to the pipette. Activation was characterized by an initial large current spike that rapidly attenuated to a stable value and showed...... was markedly reduced with N-methyl-D-glucamide (NMDG)-Cl Ringer's solution in the pipette. Neither amiloride nor ATP, which are known to stimulate an apical cation channel in Ussing chamber preparations of larval frog skin, produced channel activation nor did these compounds affect the response to suction....... Stretch activation was not affected by varying the pipette concentrations of Ca(2+) between 0 mmol l(-1) and 4 mmol l(-1) or by varying pH between 6.8 and 8.0. However, conductance was reduced with 4 mmol l(-1) Ca(2+). Western blot analysis of membrane homogenates from larval bullfrog and larval toad skin...

  3. Excited state dynamics of the astaxanthin radical cation (United States)

    Amarie, Sergiu; Förster, Ute; Gildenhoff, Nina; Dreuw, Andreas; Wachtveitl, Josef


    Femtosecond transient absorption spectroscopy in the visible and NIR and ultrafast fluorescence spectroscopy were used to examine the excited state dynamics of astaxanthin and its radical cation. For neutral astaxanthin, two kinetic components corresponding to time constants of 130 fs (decay of the S 2 excited state) and 5.2 ps (nonradiative decay of the S 1 excited state) were sufficient to describe the data. The dynamics of the radical cation proved to be more complex. The main absorption band was shifted to 880 nm (D 0 → D 3 transition), showing a weak additional band at 1320 nm (D 0 → D 1 transition). We found, that D 3 decays to the lower-lying D 2 within 100 fs, followed by a decay to D 1 with a time constant of 0.9 ps. The D 1 state itself exhibited a dual behavior, the majority of the population is transferred to the ground state in 4.9 ps, while a small population decays on a longer timescale of 40 ps. Both transitions from D 1 were found to be fluorescent.

  4. High and rapid alkali cation storage in ultramicroporous carbonaceous materials (United States)

    Yun, Young Soo; Lee, Seulbee; Kim, Na Rae; Kang, Minjee; Leal, Cecilia; Park, Kyu-Young; Kang, Kisuk; Jin, Hyoung-Joon


    To achieve better supercapacitor performance, efforts have focused on increasing the specific surface area of electrode materials to obtain higher energy and power density. The control of pores in these materials is one of the most effective ways to increase the surface area. However, when the size of pores decreases to a sub-nanometer regime, it becomes difficult to apply the conventional parallel-plate capacitor model because the charge separation distance (d-value) of the electrical double layer has a similar length scale. In this study, ultramicroporous carbonaceous materials (UCMs) containing sub-nanometer-scale pores are fabricated using a simple in situ carbonization/activation of cellulose-based compounds containing potassium. The results show that alkali cations act as charge carriers in the ultramicropores (<0.7 nm), and these materials can deliver high capacitances of ∼300 F g-1 at 0.5 A g-1 and 130 F g-1, even at a high current rate of 65 A g-1 in an aqueous medium. In addition, the UCM-based symmetric supercapacitors are stable over 10,000 cycles and have a high energy and power densities of 8.4 Wh kg-1 and 15,000 W kg-1, respectively. This study provides a better understanding of the effects of ultramicropores in alkali cation storage.

  5. Cationic Nanocylinders Promote Angiogenic Activities of Endothelial Cells

    Directory of Open Access Journals (Sweden)

    Jung Bok Lee


    Full Text Available Polymers have been used extensively taking forms as scaffolds, patterned surface and nanoparticle for regenerative medicine applications. Angiogenesis is an essential process for successful tissue regeneration, and endothelial cell–cell interaction plays a pivotal role in regulating their tight junction formation, a hallmark of angiogenesis. Though continuous progress has been made, strategies to promote angiogenesis still rely on small molecule delivery or nuanced scaffold fabrication. As such, the recent paradigm shift from top-down to bottom-up approaches in tissue engineering necessitates development of polymer-based modular engineering tools to control angiogenesis. Here, we developed cationic nanocylinders (NCs as inducers of cell–cell interaction and investigated their effect on angiogenic activities of human umbilical vein endothelial cells (HUVECs in vitro. Electrospun poly (l-lactic acid (PLLA fibers were aminolyzed to generate positively charged NCs. The aninolyzation time was changed to produce two different aspect ratios of NCs. When HUVECs were treated with NCs, the electrostatic interaction of cationic NCs with negatively charged plasma membranes promoted migration, permeability and tubulogenesis of HUVECs compared to no treatment. This effect was more profound when the higher aspect ratio NC was used. The results indicate these NCs can be used as a new tool for the bottom-up approach to promote angiogenesis.

  6. Source of Lake Vostok Cations Constrained with Strontium Isotopes (United States)

    Lyons, William; Welch, Kathleen; Priscu, John; Tranter, Martyn; Royston-Bishop, George


    Lake Vostok is the largest sub-glacial lake in Antarctica. The primary source of our current knowledge regarding the geochemistry and biology of the lake comes from the analysis of refrozen lake water associated with ice core drilling. Several sources of dissolved ions and particulate matter to the lake have been proposed, including materials from the melted glacier ice, the weathering of underlying geological materials, hydrothermal activity and underlying, ancient evaporitic deposits. A sample of Lake Vostok Type 1 accretion ice has been analyzed for its 87Sr/86Sr signature as well as its major cation and anion and Sr concentrations. The strontium isotope ratio of 0.71655 and the Ca/Sr ratio in the sample strongly indicate that the major source of the Sr is from aluminosilicate minerals from the continental crust. These data imply that at least a portion of the other cations in the Type 1 ice also are derived from continental crustal materials and not hydrothermal activity, the melted glacier ice, or evaporitic sources.

  7. Synthesis and rheological properties of cation-exchanged Laponite suspensions

    Energy Technology Data Exchange (ETDEWEB)

    Phuoc, Tran X. [National Energy Technology Lab. (NETL), Pittsburgh, PA, (United States); Univ. of Pittsburgh, PA (United States); Howard, Bret H. [National Energy Technology Lab. (NETL), Pittsburgh, PA, (United States); Chyu, Minking K. [National Energy Technology Lab. (NETL), Pittsburgh, PA, (United States); Univ. of Pittsburgh, PA (United States)


    In this paper we report our new approach to synthesize cation-exchanged Laponite suspensions. General observations of the prepared samples indicated that an aqueous suspension of 1 wt.% Laponite retained its free flowing liquid phase characteristics even after aging for several weeks. When bivalent cationic metals (Cu, Co, Ni) were ablated into the suspension, the strong charge of the crystal face was reduced and, on standing, the suspension gelled becoming highly viscous. This sol-gel transition was induced by the formation of a space-filled structure due to both van der Waals and electrostatic bonds between the positively charged rims and negatively charged faces. Rheological properties of such prepared suspensions were measured using a Brookfield DV-II Pro Viscometer with a small sample adapter (SSA18/13RPY). The yield strengths of 2.2 N/m2, 3.2 N/m2, and 1.7 N/m2 were measured for Ni-, Co-, and Cumodified Laponite suspensions, respectively. These yield strengths are sufficiently high for suspending weighting materials such as barite which requires the gel strength of about 0.5 N/m2.

  8. Synthesis and rheological properties of cation exchanged Laponite suspensions

    Energy Technology Data Exchange (ETDEWEB)

    Tran, X P; Howard, B; Chyu, M K


    In this paper we report our new approach to synthesize cation-exchanged Laponite suspensions. General observations of the prepared samples indicated that an aqueous suspension of 1 wt% Laponite retained its free flowing liquid phase characteristics even after aging for several weeks. When bivalent cationic metals (Cu, Co, Ni) were ablated into the suspension, the strong charge of the crystal face was reduced and, on standing, the suspension gelled becoming highly viscous. This sol-gel transition was induced by the formation of a space-filled structure due to both van derWaals and electrostatic bonds between the positively charged rims and negatively charged faces. Rheological properties of such prepared suspensions were measured using a Brookfield DV-H Pro Viscometer with a small sample adapter{SSA18/13RPY). The yield strengths of2.2 N/m2, 3.2 N/m2, and 1.7 N/m2 were measured for Ni-, Co-, and Cu-modified Laponite suspensions, respectively. These yield strengths are sufficiently high for suspending weighting materials such as barite which requires the gel strength of about 0.5 N/m2.

  9. Anionic and cationic Hofmeister effects on hydrophobic and hydrophilic surfaces. (United States)

    Schwierz, Nadine; Horinek, Dominik; Netz, Roland R


    Using a two-step modeling approach, we address the full spectrum of direct, reversed, and altered ionic sequences as the charge of the ion, the charge of the surface, and the surface polarity are varied. From solvent-explicit molecular dynamics simulations, we extract single-ion surface interaction potentials for halide and alkali ions at hydrophilic and hydrophobic surfaces. These are used within Poisson-Boltzmann theory to calculate ion density and electrostatic potential distributions at mixed polar/unpolar surfaces for varying surface charge. The resulting interfacial tension increments agree quantitatively with experimental data and capture the Hofmeister series, especially the anomaly of lithium, which is difficult to obtain using continuum theory. Phase diagrams that feature different Hofmeister series as a function of surface charge, salt concentration, and surface polarity are constructed from the long-range force between two surfaces interacting across electrolyte solutions. Large anions such as iodide have a high hydrophobic surface affinity and increase the effective charge magnitude on negatively charged unpolar surfaces. Large cations such as cesium also have a large hydrophobic surface affinity and thereby compensate an external negative charge surface charge most efficiently, which explains the well-known asymmetry between cations and anions. On the hydrophilic surface, the size-dependence of the ion surface affinity is reversed, explaining the Hofmeister series reversal when comparing hydrophobic with hydrophilic surfaces.

  10. Cation charge dependence of the forces driving DNA assembly. (United States)

    DeRouchey, Jason; Parsegian, V Adrian; Rau, Donald C


    Understanding the strength and specificity of interactions among biologically important macromolecules that control cellular functions requires quantitative knowledge of intermolecular forces. Controlled DNA condensation and assembly are particularly critical for biology, with separate repulsive and attractive intermolecular forces determining the extent of DNA compaction. How these forces depend on the charge of the condensing ion has not been determined, but such knowledge is fundamental for understanding the basis of DNA-DNA interactions. Here, we measure DNA force-distance curves for a homologous set of arginine peptides. All forces are well fit as the sum of two exponentials with 2.4- and 4.8-Å decay lengths. The shorter-decay-length force is always repulsive, with an amplitude that varies slightly with length or charge. The longer-decay-length force varies strongly with cation charge, changing from repulsion with Arg¹ to attraction with Arg². Force curves for a series of homologous polyamines and the heterogeneous protein protamine are quite similar, demonstrating the universality of these forces for DNA assembly. Repulsive amplitudes of the shorter-decay-length force are species-dependent but nearly independent of charge within each species. A striking observation was that the attractive force amplitudes for all samples collapse to a single curve, varying linearly with the inverse of the cation charge.

  11. Trace Metals in Groundwater & Vadose Zone Calcite: In Situ Containment & Stabilization of Stronthium-90 & Other Divalent Metals & Radionuclides at Arid West DOE

    Energy Technology Data Exchange (ETDEWEB)

    Smith, Robert W.


    Radionuclide and metal contaminants such as strontium-90 are present beneath U.S. Department of Energy (DOE) lands in both the groundwater (e.g., 100-N area at Hanford, WA) and vadose zone (e.g., Idaho Nuclear Technology and Engineering Center [INTEC] at the Idaho National Laboratory [INL]). In situ containment and stabilization of these contaminants is a cost-effective treatment strategy. However, implementing in situ containment and stabilization approaches requires definition of the mechanisms that control contaminant sequestration. We are investigating the in situ immobilization of radionuclides or contaminant metals (e.g., strontium-90) by their facilitated co-precipitation with calcium carbonate (primarily calcite) in groundwater and vadose zone systems. Our facilitated approach relies upon the hydrolysis of introduced urea to cause the acceleration of calcium carbonate precipitation (and trace metal co-precipitation) by (a) increasing pH and alkalinity and (b) liberating cations from the aquifer matrix by cation exchange reactions. Subsurface urea hydrolysis is catalyzed by the urease enzyme, which is produced in situ by native urea hydrolyzing microorganisms. Because the precipitation process tends to be irreversible and many western aquifers are saturated with respect to calcite, the co-precipitated metals and radionuclides will be effectively removed from the aqueous phase over the long term. We are currently conducting field based activities at both the INL Vadose Zone Research Park (VZRP), an uncontaminated surrogate site for the strontium-90 contaminated vadose zone at INTEC and at the strontium-90 contaminated aquifer of 100-N area of the Hanford site.

  12. 牛病毒性腹泻病二价弱毒活疫苗制备工艺研究%Study on Preparation Technique of Divalent Attenuated Virus Live Vaccine of Bovine Viral Diarrhea Virus

    Institute of Scientific and Technical Information of China (English)

    李海涛; 苗利光; 刘艳环; 朱言柱; 安亚雄; 王坤; 冯卓


    研究了BVDV2/JZ05-1和BVDV1/JZ05-3二价弱毒活疫苗的制备工艺.通过对BVDV2/JZ05-1和BVDV1/JZ05-3疫苗毒传代培养测定毒价后,试制出5批毒价分别是10.4TCID50/mL和105.6TCID50/mL的BVDV二价弱毒活疫苗,经检验符合试验设计要求.%The aim of this study was to explore the preparation technique of divalent attenuated virus live vaccine of bovine viral diarrhea virus 2/JZ05-1(BVDV2/JZ05-1) and BVDV1/JZ05-3.BVDV2/JZ05-1 and BVDV1/JZ05-3 were continuously cultivated in cell culture.The poison titor was examined.5 groups of divalent attenuated BVDV live vaccine were produced.The poison prices were 105.4TCID50/mL and 105.6TCID50/mL,respectively.The vaccines were examined and was within the range of the test design requirement.

  13. The influence of large cations on the electrochemical properties of tunnel-structured metal oxides (United States)

    Yuan, Yifei; Zhan, Chun; He, Kun; Chen, Hungru; Yao, Wentao; Sharifi-Asl, Soroosh; Song, Boao; Yang, Zhenzhen; Nie, Anmin; Luo, Xiangyi; Wang, Hao; Wood, Stephen M.; Amine, Khalil; Islam, M. Saiful; Lu, Jun; Shahbazian-Yassar, Reza


    Metal oxides with a tunnelled structure are attractive as charge storage materials for rechargeable batteries and supercapacitors, since the tunnels enable fast reversible insertion/extraction of charge carriers (for example, lithium ions). Common synthesis methods can introduce large cations such as potassium, barium and ammonium ions into the tunnels, but how these cations affect charge storage performance is not fully understood. Here, we report the role of tunnel cations in governing the electrochemical properties of electrode materials by focusing on potassium ions in α-MnO2. We show that the presence of cations inside 2 × 2 tunnels of manganese dioxide increases the electronic conductivity, and improves lithium ion diffusivity. In addition, transmission electron microscopy analysis indicates that the tunnels remain intact whether cations are present in the tunnels or not. Our systematic study shows that cation addition to α-MnO2 has a strong beneficial effect on the electrochemical performance of this material.

  14. Flexible polyelectrolyte conformation in the presence of cationic and anionic surfactants (United States)

    Passos, C. B.; Kuhn, P. S.; Diehl, A.


    In this work we have studied the conformation of flexible polyelectrolyte chains in the presence of cationic and anionic surfactant molecules. We developed a simple theoretical model for the formation of the polyelectrolyte-cationic surfactant complexes and mixed micelles formed by cationic and anionic surfactant molecules, in the framework of the Debye-Hückel-Bjerrum-Manning and Flory theories, with the hydrophobic interaction included explicitly as an effective short-ranged attraction between the surfactant hydrocarbon tails. This simple model allows us to calculate the extension of the polyelectrolyte-cationic surfactant complexes as a function of the anionic surfactant concentration, for different types of cationic and anionic surfactant molecules. A discrete conformational transition from a collapsed state to an elongated coil was found, for all surfactant chain lengths we have considered, in agreement with the experimental observations for the unfolding of ​DNA-cationic surfactant complexes.

  15. Resonance Raman and quantum chemical studies of short polyene radical cations

    DEFF Research Database (Denmark)

    Keszthelyi, T.; Wilbrandt, R.; Bally, T.


    The results of our investigations of the geometric and vibrational structures of some short conjugated polyene radical cations are reported. The radical cations of 1,3-butadiene and three of its deuterated isotopomers, trans- and cis-1,3-pentadiene, 2-methyl-1,3-butadiene, and E- and Z-1,3,5-hexa......The results of our investigations of the geometric and vibrational structures of some short conjugated polyene radical cations are reported. The radical cations of 1,3-butadiene and three of its deuterated isotopomers, trans- and cis-1,3-pentadiene, 2-methyl-1,3-butadiene, and E- and Z-1...... and to assist assignment of the resonance Raman spectra. A new and improved scaled quantum mechanical force field for the butadiene radical cation was also determined. The presence of more than one rotamer was observed in all the polyene radical cations we investigated. (C) 1997 Elsevier Science B.V....

  16. Improving reactive ink jet printing via cationization of cellulosic linen fabric. (United States)

    Rekaby, M; Abd-El Thalouth, J I; Abd El-Salam, Sh H


    Cellulose linen fabric samples subjected to cationization using different cationizing agents: dodecyl trimethyl ammonium bromide (DTAB), tetra methyl ammonium hydroxide (TMAH), and Quat-188, via pad batch technique, followed by ink jet printing with reactive dyes. The %N as well as the K/S of the cationized samples was found to be depends on: (a) the nature of the cationizing agent and (b) on the time of batching. As the latter increases both of the nitrogen content and K/S increases to a maximum depending on the nature of the reagent used. Further increase in the batching time up to 30 h is accompanied by a decrease in both the %N and K/S irrespective of the nature of the cationizing agent used. Cationization improves the printability of reactive dye ink jet printed linen fabrics with no remarkable effect on the overall color fastness properties.

  17. Cation-{pi}-interaction promoted aggregation of aromatic molecules and energy transfer within Y zeolites

    Energy Technology Data Exchange (ETDEWEB)

    Thomas, K.J.; Sunoj, R.B.; Chandrasekhar, J.; Ramamurthy, V.


    Photophysical studies of naphthalene confirm that aromatic molecules tend to aggregate within cation exchanged Y zeolites. Ground-state aggregation is traced to the presence of cation-aromatic {pi}-interaction. Solvents that can coordinate to the cation turn off the cation-aromatic interaction, and consequently aggregation does not occur in zeolites that are impregnated with the above solvents. The solvent that exhibits a maximum in such an effect is water. MP2 calculations on cation-benzene dimer indicate that cation-{pi}-interaction results in stabilization of the {pi}-stacked benzene dimer. Results of MP2 calculations are consistent with the formation of ground-state {pi}-stacked aggregates of naphthalene molecules within Y zeolites.

  18. Fabrication of patterned calcium cross-linked alginate hydrogel films and coatings through reductive cation exchange. (United States)

    Bruchet, Marion; Melman, Artem


    Calcium cross-linked alginate hydrogels are widely used in targeted drug delivery, tissue engineering, wound treatment, and other biomedical applications. We developed a method for preparing homogeneous alginate hydrogels cross-linked with Ca(2+) cations using reductive cation exchange in homogeneous iron(III) cross-linked alginate hydrogels. Treatment of iron(III) cross-linked alginate hydrogels with calcium salts and sodium ascorbate results in reduction of iron(III) cations to iron(II) that are instantaneously replaced with Ca(2+) cations, producing homogeneous ionically cross-linking hydrogels. Alternatively, the cation exchange can be performed by photochemical reduction in the presence of calcium chloride using a sacrificial photoreductant. This approach allows fabrication of patterned calcium alginate hydrogels through photochemical patterning of iron(III) cross-linked alginate hydrogel followed by the photochemical reductive exchange of iron cations to calcium.

  19. Probing optical band gaps at nanoscale from tetrahedral cation vacancy defects and variation of cation ordering in NiCo2O4 epitaxial thin films (United States)

    Dileep, K.; Loukya, B.; Silwal, P.; Gupta, A.; Datta, R.


    High resolution electron energy loss spectroscopy (HREELS) is utilized to probe the optical band gaps at the nanoscale in epitaxial NiCo2O4 (NCO) thin films with different structural order (cation/charge). The structure of NCO deviates from the ideal inverse spinel (non-magnetic and insulating) for films grown at higher temperatures (>500 °C) towards a mixed cation structure (magnetic with metallic conductivity) at lower deposition temperatures (<450 °C). This significantly modifies the electronic structure as well as the nature of the band gap of the material. Nanoscale regions with unoccupied tetrahedral A site cations are additionally observed in all the samples and direct measurement from such areas reveals considerably lower band gap values as compared to the ideal inverse spinel and mixed cation configurations. Experimental values of band gaps have been found to be in good agreement with the theoretical mBJLDA exchange potential based calculated band gaps for various cation ordering and consideration of A site cation vacancy defects. The origin of rich variation in cation ordering observed in this system is discussed.

  20. Early events following radiolytic and photogeneration of radical cations in hydrocarbons

    Energy Technology Data Exchange (ETDEWEB)

    Werst, D.W.; Trifunac, A.D.


    Real-time studies in hydrocarbons have revealed a richness of chemistry involving the initial ionic species produced in radiolysis and photoionization. A modified radical cation mechanism patterned after the core mechanism for alkane radiolysis-formation of radical cations and their disappearance via ion-molecule reactions - is capable of explaining a wide range of observations in high-energy photochemistry, and thus unifies two high-energy regimes. Fundamental studies of radical cations suggest strategies for mitigating radiation effects in materials.

  1. Early events following radiolytic and photogeneration of radical cations in hydrocarbons

    Energy Technology Data Exchange (ETDEWEB)

    Werst, D.W.; Trifunac, A.D.


    Real-time studies in hydrocarbons have revealed a richness of chemistry involving the initial ionic species produced in radiolysis and photoionization. A modified radical cation mechanism patterned after the core mechanism for alkane radiolysis-formation of radical cations and their disappearance via ion-molecule reactions - is capable of explaining a wide range of observations in high-energy photochemistry, and thus unifies two high-energy regimes. Fundamental studies of radical cations suggest strategies for mitigating radiation effects in materials.

  2. Click-based porous cationic polymers for enhanced carbon dioxide capture


    Dani, Alessandro; Magistris, Valentina Crocella Claudio; Santoro, Valentina; Yuan, Jiayin; Bordiga, Silvia


    Imidazolium based porous cationic polymers were synthesized using an innovative and facile approach, which takes advantage of the Debus Radziszewski reaction to obtain meso- and microporous polymers following click chemistry principles. In the obtained set of materials, click based porous cationic polymers have the same cationic backbone, whereas they bear the commonly used anions of imidazolium poly(ionic liquid)s. These materials show hierarchical porosity and a good specific surface area. ...

  3. Ternary mixtures of ionic liquids for better salt solubility, conductivity and cation transference number improvement (United States)

    Karpierz, E.; Niedzicki, L.; Trzeciak, T.; Zawadzki, M.; Dranka, M.; Zachara, J.; Żukowska, G. Z.; Bitner-Michalska, A.; Wieczorek, W.


    We hereby present the new class of ionic liquid systems in which lithium salt is introduced into the solution as a lithium cation-glyme solvate. This modification leads to the reorganisation of solution structure, which entails release of free mobile lithium cation solvate and hence leads to the significant enhancement of ionic conductivity and lithium cation transference numbers. This new approach in composing electrolytes also enables even three-fold increase of salt concentration in ionic liquids.

  4. A Photo Touch on Amines: New Synthetic Adventures of Nitrogen Radical Cations. (United States)

    Maity, Soumitira; Zheng, Nan


    Amines have been used as sacrificial electron donors to reduce photoexcited Ru(II) or Ir(III) complexes, during which they are oxidized to nitrogen radical cations. Recently, the synthetic potential of these nitrogen radical cations have caught synthetic organic chemists' attention. They have been exploited in various transformations yielding a number of elegant methods for amine synthesis. This article highlights recent developments on nitrogen radical cation chemistry under visible-light photocatalysis.

  5. Research on plasma and saliva levels of some bivalent cations in patients with chronic periodontitis (salivary cations in chronic periodontitis). (United States)

    Manea, A; Nechifor, M


    The purpose of this study was to determine whether chronic periodontitis can stand behind modifications in the salivary and blood concentration of some bivalent cations (Calcium, Magnesium, Zinc and Copper). For this purpose, we formed a group of 30 adult patients with clinically onset chronic periodontitis, and another one of 30 healthy patients as control. Both groups were free from acute oral pathology and general illnesses. The groups were divided again according to the habit of smoking. Total saliva samples were obtained as "first time in the morning", then weighed and processed. Cations were read on Atomic Absorption Spectrophotometer and by Ion Chromatography (Magnesium). The same patients were required to undergo laboratory blood tests for Calcium, Magnesium and Zinc. Data obtained was normalised, then statistically interpreted using two-tailed heteroscedastic t-Student tests. Our data confirmed the existence of a connection between salivary calcium, magnesium, zinc and copper, and of blood magnesium, and chronic periodontitis. Salivary calcium and magnesium are affected by smoking.

  6. Computational and analytical modeling of cationic lipid-DNA complexes. (United States)

    Farago, Oded; Grønbech-Jensen, Niels


    We present a theoretical study of the physical properties of cationic lipid-DNA (CL-DNA) complexes--a promising synthetically based nonviral carrier of DNA for gene therapy. The study is based on a coarse-grained molecular model, which is used in Monte Carlo simulations of mesoscopically large systems over timescales long enough to address experimental reality. In the present work, we focus on the statistical-mechanical behavior of lamellar complexes, which in Monte Carlo simulations self-assemble spontaneously from a disordered random initial state. We measure the DNA-interaxial spacing, d(DNA), and the local cationic area charge density, sigma(M), for a wide range of values of the parameter (c) representing the fraction of cationic lipids. For weakly charged complexes (low values of (c)), we find that d(DNA) has a linear dependence on (c)(-1), which is in excellent agreement with x-ray diffraction experimental data. We also observe, in qualitative agreement with previous Poisson-Boltzmann calculations of the system, large fluctuations in the local area charge density with a pronounced minimum of sigma(M) halfway between adjacent DNA molecules. For highly-charged complexes (large (c)), we find moderate charge density fluctuations and observe deviations from linear dependence of d(DNA) on (c)(-1). This last result, together with other findings such as the decrease in the effective stretching modulus of the complex and the increased rate at which pores are formed in the complex membranes, are indicative of the gradual loss of mechanical stability of the complex, which occurs when (c) becomes large. We suggest that this may be the origin of the recently observed enhanced transfection efficiency of lamellar CL-DNA complexes at high charge densities, because the completion of the transfection process requires the disassembly of the complex and the release of the DNA into the cytoplasm. Some of the structural properties of the system are also predicted by a continuum

  7. Study on synthesis and flocculation property of cation-polyacrylamide

    Institute of Scientific and Technical Information of China (English)

    NIE Rong-chun; GUO Li-ying; XU Chu-yang


    On the basis of flocculating settling experimentation on flotation waste coal in Wangfenggang coal preparation plant, influence of medical dosage and cationization (CD) of CPAM samples on coal slurry's flocculating effect was studied, difference of flocculating effect on coal slurry among different categories of polyacrylamide was discussed. Experi-mental results show that when the dosage of flocculant reaches 2~4 g/m3 flotation waste,and the CD of CPAM is 5%, flocculating effect is the best, light transmittance of super-natant liquor reaches 93%. Taking 3types of sample CPAM, PAM and PHP, which formula weight vary a little, to deal with the same concn of coal slurry, when medicine dosage is 3 g/m3, flocculating effect of CPAM is the best, light transmittance of supernatant liquor reaches 92%.

  8. Organic non-aqueous cation-based redox flow batteries

    Energy Technology Data Exchange (ETDEWEB)

    Jansen, Andrew N.; Vaughey, John T.; Chen, Zonghai; Zhang, Lu; Brushett, Fikile R.


    The present invention provides a non-aqueous redox flow battery comprising a negative electrode immersed in a non-aqueous liquid negative electrolyte, a positive electrode immersed in a non-aqueous liquid positive electrolyte, and a cation-permeable separator (e.g., a porous membrane, film, sheet, or panel) between the negative electrolyte from the positive electrolyte. During charging and discharging, the electrolytes are circulated over their respective electrodes. The electrolytes each comprise an electrolyte salt (e.g., a lithium or sodium salt), a transition-metal free redox reactant, and optionally an electrochemically stable organic solvent. Each redox reactant is selected from an organic compound comprising a conjugated unsaturated moiety, a boron cluster compound, and a combination thereof. The organic redox reactant of the positive electrolyte is selected to have a higher redox potential than the redox reactant of the negative electrolyte.

  9. Interpnictogen cations: exploring new vistas in coordination chemistry. (United States)

    Robertson, Alasdair P M; Gray, Paul A; Burford, Neil


    Pnictine derivatives can behave as both 2e(-) donors (Lewis bases) and 2e(-) acceptors (Lewis acids). As prototypical ligands in the coordination chemistry of transition metals, amines and phosphines also form complexes with p-block Lewis acids, including a variety of pnictogen-centered acceptors. The inherent Lewis acidity of pnictogen centers can be enhanced by the introduction of a cationic charge, and this feature has been exploited in recent years in the development of compounds resulting from coordinate Pn-Pn and Pn-Pn' interactions. These compounds offer the unusual opportunity for homoatomic coordinate bonding and the development of complexes that possess a lone pair of electrons at the acceptor center. This Review presents new directions in the systematic extension of coordination chemistry from the transition series into the p-block.

  10. A New Nanometer-Sized Ga(III-Oxyhydroxide Cation

    Directory of Open Access Journals (Sweden)

    William H. Casey


    Full Text Available A new 30-center Ga(III-oxy-hydroxide cation cluster was synthesized by hydrolysis of an aqueous GaCl3 solution near pH = 2.5 and crystallized using 2,6-napthalene disulfonate (NDS. The cluster has 30 metal centers and a nominal stoichiometry: [Ga30(μ4-O12(μ3-O4(μ3-OH4(μ2-OH42(H2O16](2,6-NDS6, where 2,6-NDS = 2,6-napthalene disulfonate This cluster augments the very small library of Group 13 clusters that have been isolated from aqueous solution and closely resembles one other Ga(III cluster with 32 metal centers that had been isolated using curcurbit ligands. These clusters have uncommon linked Ga(O4 centers and sets of both protonated and unprotonated μ3-oxo.

  11. Ab initio study of the transition-metal carbene cations

    Institute of Scientific and Technical Information of China (English)

    李吉海; 冯大诚; 冯圣玉


    The geometries and bonding characteristics of the first-row transition-metal carbene cations MCH2+ were investigated by ab initio molecular orbital theory (HF/LANL2DZ). All of MCH2+ are coplanar. In the closed shell structures the C bonds to M with double bonds; while in the open shell structures the partial double bonds are formed, because one of the σ and π orbitals is singly occupied. It is mainly the π-type overlap between the 2px orbital of C and 4px, 3dxz, orbitals of M+ that forms the π orbitals. The dissociation energies of C—M bond appear in periodic trend from Sc to Cu. Most of the calculated bond dissociation energies are close to the experimental ones.

  12. Cationic Conjugated Polymers-Induced Quorum Sensing of Bacteria Cells. (United States)

    Zhang, Pengbo; Lu, Huan; Chen, Hui; Zhang, Jiangyan; Liu, Libing; Lv, Fengting; Wang, Shu


    Bacteria quorum sensing (QS) has attracted significant interest for understanding cell-cell communication and regulating biological functions. In this work, we demonstrate that water-soluble cationic conjugated polymers (PFP-G2) can interact with bacteria to form aggregates through electrostatic interactions. With bacteria coated in the aggregate, PFP-G2 can induce the bacteria QS system and prolong the time duration of QS signal molecules (autoinducer-2 (AI-2)) production. The prolonged AI-2 can bind with specific protein and continuously regulate downstream gene expression. Consequently, the bacteria show a higher survival rate against antibiotics, resulting in decreased antimicrobial susceptibility. Also, AI-2 induced by PFP-G2 can stimulate 55.54 ± 12.03% more biofilm in E. coli. This method can be used to understand cell-cell communication and regulate biological functions, such as the production of signaling molecules, antibiotics, other microbial metabolites, and even virulence.

  13. Efficient intravesical therapy of bladder cancer with cationic doxorubicin nanoassemblies. (United States)

    Jin, Xun; Zhang, Peilan; Luo, Li; Cheng, Hao; Li, Yunzu; Du, Ting; Zou, Bingwen; Gou, Maling

    Nanoparticles have promising applications in drug delivery for cancer therapy. Herein, we prepared cationic 1,2-dioleoyl-3-trimethylammonium propane/methoxypoly (ethyleneglycol) (DPP) nanoparticles to deliver doxorubicin (Dox) for intravesical therapy of bladder cancer. The DPP micelles have a mean dynamic diameter of 18.65 nm and a mean zeta potential of +19.6 mV. The DPP micelles could prolong the residence of Dox in the bladder, enhance the penetration of Dox into the bladder wall, and improve cellular uptake of Dox. The encapsulation by DPP micelles significantly improved the anticancer effect of Dox against orthotopic bladder cancer in vivo. This work described a Dox-loaded DPP nanoparticle with potential applications in intravesical therapy of bladder cancer.

  14. Chiral DNA packaging in DNA-cationic liposome assemblies. (United States)

    Zuidam, N J; Barenholz, Y; Minsky, A


    Recent studies have indicated that the structural features of DNA-lipid assemblies, dictated by the lipid composition and cationic lipid-to-DNA ratio, critically affect the efficiency of these complexes in acting as vehicles for cellular delivery of genetic material. Using circular dichroism we find that upon binding DNA, positively-charged liposomes induce a secondary conformational transition of the DNA molecules from the native B form to the C motif. Liposomes composed of positively-charged and neutral 'helper' lipids, found to be particularly effective as transfecting agents, induce - in addition to secondary conformational changes - DNA condensation into a left-handed cholesteric-like phase. A structural model is presented according to which two distinct, yet inter-related modes of DNA packaging coexist within such assemblies. The results underline the notion that subtle changes in the components of a supramolecular assembly may substantially modulate the interplay of interactions which dictate its structure and functional properties.

  15. Investigation on the aggregation properties of cationic [60]fullerene derivative

    Institute of Scientific and Technical Information of China (English)

    WANG Guanwu; ZHAO Guoxia; YAN Lifeng


    The UV-Vis spectra, HRTEM and AFM images of cationic fullerene derivative 1 with ammonium head group directly connected to C60 skeleton in tetrahydrofuran (THF)-water (H2O) binary mixtures and in pure H2O were investigated. It was found that the UV-Vis spectra of ammonium 1 in the THF-H2O mixtures with THF% ≥ 20% were nearly overlapped, while those with THF% < 20% showed broadened and red-shifted peaks, indicating the formation of aggregates. Corresponding to the UV-Vis spectral changes,the solvatochromism of ammonium 1 in THF-H2O mixtures was observed. Ammonium 1 in binary THF-H2O mixtures existing as the monomer state could aggregate upon prolonged standing. Higher temperature and lower concentration speeded up the aggregation process.

  16. Quantitative mapping of intracellular cations in the human amniotic membrane (United States)

    Moretto, Ph.; Llabador, Y.; Simonoff, M.; Razafindrabe, L.; Bara, M.; Guiet-Bara, A.


    The effect of magnesium and taurine on the permeability of cell membranes to monovalent cations has been investigated using the Bordeaux nuclear microprobe. PIXE and RBS techniques have been used to provide quantitative measurements and ion distributions in the isolated amniotic membrane. This physiological model for cellular exchanges allowed us to reveal the distribution of most elements involved in cellular pathways and the modifications under different experimental conditions of incubation in physiological fluids. The PIXE microanalysis provided an original viewpoint on these mechanisms. Following this first study, the amnion compact lamina was found to play a role which was not, up to now, taken into account in the interpretation of electrophysiological experimentations. The release of some ionic species, such as K +, from the epithelial cells, during immersion in isotonic fluids, could have been hitherto underestimated.

  17. Electrochemical uranyl cation biosensor with DNA oligonucleotides as receptor layer. (United States)

    Jarczewska, Marta; Ziółkowski, Robert; Górski, Łukasz; Malinowska, Elżbieta


    The present study aims at the further development of the uranyl oligonucleotide-based voltammetric biosensor, which takes advantage of strong interaction between UO2(2+) and phosphate DNA backbone. Herein we report the optimization of working parameters of previously elaborated electrochemical DNA biosensor. It is shown that the sensor sensitivity is highly dependent on the oligonucleotide probe length and the incubation time of sensor in a sample solution. Consequently, the highest sensitivity was obtained for 10-nucleotide sequence and 60 min incubation time. The lower detection limit towards uranyl cation for developed biosensor was 30 nM. The influence of mixed monolayers and the possibility of developing a non-calibration device were also investigated. The selectivity of the proposed biosensor was significantly improved via elimination of adenine nucleobases from the DNA probe. Moreover, the regeneration procedure was elaborated and tested to prolong the use of the same biosensor for 4 subsequent determinations of UO2(2+).

  18. Cation-Induced Coiling of Vanadium Pentoxide Nanobelts

    Directory of Open Access Journals (Sweden)

    Liu Jun


    Full Text Available Abstract Single-crystalline V2O5·xH2O nanorings and microloops were chemically assembled via an ion-induced chemical spinning route in the designed hydrothermal system. The morphology and structure of products were investigated by means of scanning electron microscopy (SEM and transmission electron microscopy (TEM. X-ray powder diffraction (XRD measurement, energy-dispersive X-ray spectroscopy (EDS microanalysis and thermal gravimetric analysis (TGA revealed that the composition of nanorings and microloops is V2O5·1·1H2O. For these oxide nanorings and microloops, the cation-induced coiling growth mechanism of vanadium pentoxide nanobelts has been proposed on the basis of crystallographic structure of vanadium pentoxide. Our proposed chemical spinning process and the rational solution-phase synthesis route can also be extended to prepare novel 1D materials with layered or more complex structures.

  19. A spectroscopic study of interaction of cationic dyes with heparin

    Directory of Open Access Journals (Sweden)

    R. Nandini


    Full Text Available The interaction of two cationic dyes namely, acridine orange and pinacyanol chloride with an anionic polyelectrolyte, heparin, has been investigated by spectrophotometric method.The polymer induced metachromasy in the dyes resulting in the shift of the absorption maxima of the dyes towards shorter wavelengths. The stability of the complexes formed between acridine orange and heparin was found to be lesser than that formed between pinacyanol chloride and heparin. This fact was further confirmed by reversal studies using alcohols, urea and surfactants. The interaction of acridine orange with heparin has also been investigated fluorimetrically.The interaction parameters revealed that binding between acridine orange and heparin arises due to electrostatic interaction while that between pinacyanol chloride and heparin is found to involve both electrostatic and hydrophobic forces. The effect of the structure of the dye in inducing metachromasy has also been discussed.

  20. Aqueous behaviour of cationic surfactants containing a cleavable group. (United States)

    Samakande, Austin; Chaghi, Radhouane; Derrien, Gaelle; Charnay, Clarence; Hartmann, Patrice C


    The aggregation behaviour of two novel cationic RAFT agents (transfer surfactants); N,N-dimethyl-N-(4-(((phenylcarbonothioyl)thio)methyl)benzyl)ethanammonium bromide (PCDBAB) and N-(4-((((dodecylthio)-carbonothioyl)thio)methyl)benzyl)-N,N-dimethylethanammonium bromide (DCTBAB) in diluted solutions have been investigated by surface tension, conductimetry and microcalorimetry measurements. The thermodynamic parameters i.e. the critical micelle concentration (cmc), the degree of micelle ionization (alpha), the head group surface area (a 0), Delta H mic, Delta G mic and T Delta S mic are reported at 303 K. The thermodynamic parameters have been compared to those of the conventional surfactant cetyltrimethylammonium bromide (CTAB) in order to specify structural relationships. The obtained results have been discussed considering the hydrophobic behaviour of the S-C=S- linkage and the specific interactions that arise from the introduction of the benzene ring into the hydrophobic part.

  1. Note: Vibrationally mediated photodissociation of carbon dioxide cation (United States)

    Mao, Rui; Zhang, Qun; Chen, Min; He, Chao; Zhou, Dan-na; Bai, Xi-lin; Zhang, Limin; Chen, Yang


    The photodissociation dynamics of carbon dioxide cation, CO_2^ +, mediated by its different tilde A{}^2Π _{u,1/2} (\\upsilon _1,\\upsilon _2,0) vibronic states has been investigated by means of time-sliced velocity map imaging. Through analysis of the recorded translational energy release spectra of photofragment CO+, we found that the photodissociation of CO_2^ + exhibits drastic change in a rather narrow energy region. A conformational barrier in the CO_2^ + ( {tilde A{}^2A_1 } ) state is suggested to be ˜5600 cm-1 relative to the CO_2^ + ( {tilde A{}^2Π _{u,1/2} ( {0,0,0} )}) state, in reasonable agreement with previous prediction.

  2. Influence of hydration and cation binding on parvalbumin dynamics (United States)

    Zanotti, J.-M.; Parello, J.; Bellissent-Funel, M.-C.

    Due to structural characteristics, parvalbumin exerts a major role in intracellular Mg2+ and Ca2+ concentration regulation during the muscular contraction-relieving cycle. This structure-function relationship being established, we are investigating the structure-dynamics-function relationship to take into account the protein dynamics. Because of the strong incoherent neutron scattering cross section of hydrogen and of the abundance of this element in proteins, incoherent inelastic neutron scattering is a unique probe to study vibrations and localised motions in biological macromolecules. We take advantage of the complementarities in energy or time resolution of various neutron spectrometers (time of flight, backscattering, spin-echo) to probe the parvalbumin dynamics from a fraction of a picosecond to a few nanoseconds. Influences of hydration and of the nature of the cation on parvalbumin dynamics are discussed.

  3. Property Predictions for Nitrate Salts with Nitroxy-Functionalized Cations (United States)


    2-nitroxyethyl)-3-methyl-5-nitroim+ (40) 1-(2-nitroxyethyl)-5-nitroimidazole (40a) CH3X Pyrazolium Cations 1,2H-pyr+ (41) 1H- pyrazole (41a/44a) HX...4-nitro-1,2H-pyr+ (42) 4-nitro-1H- pyrazole (42a) HX 3,5-bis(nitroxymethyl)-1,2H-pyr+ (43) 3,5-bis(nitroxymethyl)-1H- pyrazole (43a) HX 1-methyl-2H...pyr+ (44) 1H- pyrazole (41a/44a) CH3X 1,2-dimethylpyr+ (45) 1-methylpyrazole (45a) CH3X 1-nitroxymethyl-2-methylpyr+ (46) 1-nitroxymethylpyrazole (46a

  4. Cationic Dihydrogen/Dihydride Complexes of Osmium: Structure and Dynamics

    Energy Technology Data Exchange (ETDEWEB)

    Egbert, Jonathan D.; Bullock, R. Morris; Heinekey, D. M.


    Reaction of Cp*Os(CO)2Cl with (Et3Si )(BArF4) under hydrogen gas affords the cationic hydrogen complex [Cp*Os(CO)2(H2)][BArF4] (1), (Cp* = C5Me5; ArF = C6F5). When this reaction is carried out with HD gas, complex 1-d1 results, with JHD = 24.5 Hz. When solutions of complex 1 are monitored by 1H NMR spectroscopy over several days, the gradual formation of a trans dihydride species is observed. Similarly, reaction of CpOs(dppm)Br with NaBArF*4 (ArF* = 3,5-(CF3)2C6H3) under hydrogen affords the cationic dihydride complex [CpOs(dppm)H2]BArF*4 (2). At 295 K, complex 2 exists as a 10:1 mixture of cis and trans isomers. The 1H NMR spectrum of the cis form in the hydride region exhibits a triplet with JHP = 6.5 Hz, due to rapid exchange of the hydrogen atoms. At low temperature, static spectra of the HH'PP' spin system can be obtained, revealing quantum mechanical exchange coupling between the two hydride ligands. The observed JHH' is temperature dependent, varying from 133 Hz at 141 K to 176 Hz at 198 K. This is the first report of detectable exchange coupling between pairs of chemically equivalent hydrogen atoms. Research at the University of Washington was supported by the National Science Foundation. Research at Brookhaven National Laboratory was carried out under contract DE-AC02-98CH10886 with the U.S. Department of Energy and was supported by its Division of Chemical Sciences, Office of Basic Energy Sciences. Research at Pacific Northwest National Laboratory (PNNL) was funded by LDRD funds. PNNL is operated by Battelle for the US Department of Energy.

  5. Non-Surface Activity of Cationic Amphiphilic Diblock Copolymers

    Energy Technology Data Exchange (ETDEWEB)

    Nayak, Rati Ranjan; Yamada, Tasuku; Matsuoka, Hideki, E-mail:, E-mail: [Department of Polymer Chemistry, Graduate School of Engineering, Kyoto University, Nishikyo-ku, Kyoto 615-8510 (Japan)


    Cationic amphiphilic diblock copolymers containing quaternized poly (2-vinylpyridine) chain as a hydrophilic segment (PIp-b-PNMe2VP) were synthesized by living anionic polymerization. By IR measurement, we confirmed the quaternization of the polymer (PIp-b-PNMe2VP), and determined the degree of quaternization by conductometric titration. The surface tension experiment showed that the polymers are non-surface active in nature. The foam formation of the polymer solutions was also investigated with or without added salt. Almost no foam formation behavior was observed without added salt, while a little foam was observed in the presence of 1M NaCl. The critical micelle concentration (cmc) of the diblock copolymers with 3 different chain lengths was measured by the static light scattering method. The cmc values obtained in this study were much lower than the values obtained for anionic non-surface active diblock polymers studied previously. The hydrodynamic radii of the polymer micelle increased slightly in the presence of 1 M NaCl. The transmission electron microscopic images revealed spherical micelles in pure water. In the presence of salt, the cmc values increased as was the case for anionic polymers, which is unlike conventional surfactant systems but consistent with non-surface active anionic block copolymers. The microviscosity of the micelle core was evaluated using Coumarin-153 as a fluorescent anisotropy probe using steady-sate fluorescence depolarization. Non-surface activity has been proved to be universal for ionic amphiphilic block copolymers both for anionic and cationic. Hence, the origin of non-surface activity is not the charged state of water surface itself, but should be an image charge repulsion at the air/water interface.

  6. Dilution thermodynamics of the biologically relevant cation mixtures

    Energy Technology Data Exchange (ETDEWEB)

    Kaczyński, Marek, E-mail:; Borowik, Tomasz, E-mail:; Przybyło, Magda, E-mail:; Langner, Marek, E-mail:


    Graphical abstract: - Highlights: • Dilution energetics of Ca{sup 2+} can be altered by the aqueous phase ionic composition. • Dissipated heat upon Ca{sup 2+} dilution is drastically reduced in the K{sup +} presence. • Reduction of the enthalpy change upon Ca{sup 2+} dilution is K{sup +} concentration dependent. • The cooperativity of Ca{sup 2+} hydration might be of great biological relevance providing a thermodynamic argument for the specific ionic composition of the intracellular environment. - Abstract: The ionic composition of intracellular space is rigorously controlled by a variety of processes consuming large quantities of energy. Since the energetic efficiency is an important evolutional criterion, therefore the ion fluxes within the cell should be optimized with respect to the accompanying energy consumption. In the paper we present the experimental evidence that the dilution enthalpies of the biologically relevant ions; i.e. calcium and magnesium depend on the presence of monovalent cations; i.e. sodium and potassium. The heat flow generated during the dilution of ionic mixtures was measured with the isothermal titration calorimetry. When calcium was diluted together with potassium the dilution enthalpy was drastically reduced as the function of the potassium concentration present in the solution. No such effect was observed when the potassium ions were substituted with sodium ones. When the dilution of magnesium was investigated the dependence of the dilution enthalpy on the accompanying monovalent cation was much weaker. In order to interpret experimental evidences the ionic cluster formation is postulated. The specific organization of such cluster should depend on ions charges, sizes and organization of the hydration layers.

  7. Cristallochimie de fluorozirconates d'élements trivalents. Corrélations entre caractéristiques structurales et spectroscopiques de quelques fluorures d'étain divalent


    Gervais, Jean-François


    L'étude du système TIF3-ZrF4 a permis de mettre en évidence deux composes: TI0,67Zr0,33F3,33 et TIZr3F15. Les structures dérivent du type ReO3 par insertion d'anions. La répartition cationique dans les phases MZr3F15 a par ailleurs été précisée en fonction de la taille du cation trivalent. Les fluorostannates des systèmes MF-SnF2 (M = Na, K, Rb, Cs, TI et NH4) ont été étudiés par spectroscopie Mössbauer de 4,2 a 293K. L'interprétation de l'ensemble des paramètres Mössbauer a été assoçiée à la...

  8. Binding properties of oxacalix[4]arenes derivatives toward metal cations; Interactions entre cations metalliques et derives des oxacalix[4]arenes

    Energy Technology Data Exchange (ETDEWEB)

    Mellah, B


    The objective of this work was to establish the binding properties of oxacalix[4]arene derivatives with different numbers of the oxa bridges, functional groups (ketones, pyridine, ester, amide and methoxy) and conformations. Their interactions with alkali and alkaline-earth, heavy and transition metal cations have been evaluated according to different approaches: (i) extraction of corresponding picrates from an aqueous phase into dichloromethane; (ii) determination of the thermodynamic parameters of complexation in methanol and/or acetonitrile by UV-spectrophotometry and micro-calorimetry; (iii) determination of the stoichiometry of the complexes by ESI-MS; (iv) {sup 1}H-NMR titrations allowing to localize the metal ions in the ligand cavity. In a first part dealing on homo-oxacalix[4]arenes, selectivities for Na{sup +}, K{sup +}, Ca{sup 2+}, Pb{sup 2+} and Mn{sup 2+} of ketones derivatives was shown. The presence of oxa bridge in these derivatives increases their efficiency while decreasing their selectivity with respect to related calixarenes. The pyridine derivative prefers transition and heavy metal cations, in agreement with the presence of the soft nitrogen atoms. In the second part, di-oxacalix[4]arene ester and secondary amide derivatives were shown to be less effective than tertiary amide counterparts but to present high selectivities for Li{sup +}, Ba{sup 2+}, Zn{sup 2+} and Hg{sup 2+}. A third part devoted to the octa-homo-tetra-oxacalix[4]arene tetra-methoxy shows that the 1:1 metal complexes formed are generally more stable than those of calixarenes, suggesting the participation of the oxygen atoms of the bridge in the complexation. Selectivity for Cs{sup +}, Ba{sup 2+}, Cu{sup 2+} and Hg{sup 2+} were noted. (author)

  9. Coordination Chemistry of Alkali and Alkaline-Earth Cations with Macrocyclic Ligands. (United States)

    Dietrich, Bernard


    Discusses: (l) alkali and alkaline-earth cations in biology (considering naturally occurring lonophores, their X-ray structures, and physiochemical studies); (2) synthetic complexing agents for groups IA and IIA; and (3) ion transport across membranes (examining neutral macrobicyclic ligands as metal cation carriers, transport by anionic carriers,…

  10. Chemical Surface, Thermal and Electrical Characterization of Nafion Membranes Doped with IL-Cations

    Directory of Open Access Journals (Sweden)

    María del Valle Martínez de Yuso


    Full Text Available Surface and bulk changes in a Nafion membrane as a result of IL-cation doping (1-butyl-3-methylimidazolium tetrafluoroborate or BMIM+BF4 and phenyltrimethylammonium chloride or TMPA+Cl− were studied by X-ray photoelectron spectroscopy (XPS, contact angle, differential scanning calorimetry (DSC and impedance spectroscopy (IS measurements performed with dry samples after 24 h in contact with the IL-cations BMIM+ and TMPA+. IL-cations were selected due to their similar molecular weight and molar volume but different shape, which could facilitate/obstruct the cation incorporation in the Nafion membrane structure by proton/cation exchange mechanism. The surface coverage of the Nafion membrane by the IL-cations was confirmed by XPS analysis and contact angle, while the results obtained by the other two techniques (DSC and IS seem to indicate differences in thermal and electrical behaviour depending on the doping-cation, being less resistive the Nafion/BMIM+ membrane. For that reason, determination of the ion transport number was obtained for this membrane by measuring the membrane or concentration potential with the samples in contact with HCl solutions at different concentrations. The comparison of these results with those obtained for the original Nafion membrane provides information on the effect of IL-cation BMIM+ on the transport of H+ across wet Nafion/BMIM+ doped membranes.


    NARCIS (Netherlands)



    A number of cationic amine drugs that are taken up by liver and excreted into bile may accumulate in acidified intracellular organelles such as lysosomes and endosomes. These studies were undertaken to assess directly the uptake and accumulation of three types of model organic cationic amines by end

  12. Chemical mechanical polishing of transparent conductive layers using spherical cationic polymer microbeads

    Energy Technology Data Exchange (ETDEWEB)

    Nagaoka, Shoji, E-mail: [Kumamoto Industrial Research Institute, 3-11-38 Higashimachi, Higashiku, Kumamoto 862-0901 (Japan); Department of Applied Chemistry and Biochemistry, Kumamoto University, 2-39-1 Kurokami, Chuouku, Kumamoto 860-8555 (Japan); Kumamoto Institute for Photo-Electro Organics (Phoenics), 3-11-38 Higashimachi, Higashiku, Kumamoto 862-0901 (Japan); Ryu, Naoya [Kumamoto Industrial Research Institute, 3-11-38 Higashimachi, Higashiku, Kumamoto 862-0901 (Japan); Yamanouchi, Akio [Department of Applied Chemistry and Biochemistry, Kumamoto University, 2-39-1 Kurokami, Chuouku, Kumamoto 860-8555 (Japan); Shirosaki, Tomohiro [Kumamoto Industrial Research Institute, 3-11-38 Higashimachi, Higashiku, Kumamoto 862-0901 (Japan); Kumamoto Institute for Photo-Electro Organics (Phoenics), 3-11-38 Higashimachi, Higashiku, Kumamoto 862-0901 (Japan); Horikawa, Maki [Kumamoto Industrial Research Institute, 3-11-38 Higashimachi, Higashiku, Kumamoto 862-0901 (Japan); Department of Applied Chemistry and Biochemistry, Kumamoto University, 2-39-1 Kurokami, Chuouku, Kumamoto 860-8555 (Japan); Kumamoto Institute for Photo-Electro Organics (Phoenics), 3-11-38 Higashimachi, Higashiku, Kumamoto 862-0901 (Japan); Sakurai, Hideo; Takafuji, Makoto; Ihara, Hirotaka [Department of Applied Chemistry and Biochemistry, Kumamoto University, 2-39-1 Kurokami, Chuouku, Kumamoto 860-8555 (Japan); Kumamoto Institute for Photo-Electro Organics (Phoenics), 3-11-38 Higashimachi, Higashiku, Kumamoto 862-0901 (Japan)


    Spherical cationic polymer microbeads were used to chemically mechanically polish transparent conductive oxide (TCO) layers without the need for inorganic abrasives. Poly(methyl acrylate) (PMA) was used as the polymer matrix. Surface cationization of the spherical PMA microbeads was achieved by aminolysis using 1,2-diaminoethane. The amino group content of the microbeads was controlled using the aminolysis reaction time. The surface roughness of the TCO polished using the cationic polymer microbeads was similar to that of TCO polished with an inorganic abrasive. The microbead-polished TCO layer was slightly thinner than the unpolished TCO layer. The sheet resistance of the TCO layer polished using the microbeads was lower than that polished using the inorganic abrasive. The TCO polishing ability of the microbeads was dependent on their cationic properties and softness. - Highlights: • Indium tin oxide (ITO) layer was planarized using cationic polymer microbeads. • Cationic polymer microbeads planarized, while retaining ITO layer thickness • Cationic polymer microbeads did not degrade the sheet resistance of ITO. • Cationic polymer microbeads could planarize the ITO surface without damaging.

  13. Concerted action of two cation filters in the aquaporin water channel

    DEFF Research Database (Denmark)

    Wu, Binghua; Steinbronn, Christina; Alsterfjord, Magnus;


    Aquaporin (AQP) facilitated water transport is common to virtually all cell membranes and is marked by almost perfect specificity and high flux rates. Simultaneously, protons and cations are strictly excluded to maintain ionic transmembrane gradients. Yet, the AQP cation filters have not been ide...

  14. Structures of dioxobipyridil-12-crown-4 and its complexes with silver (I) and copper (II) cations (United States)

    Starova, Galina L.; Denisova, Anna S.; Dem'yanchuk, Evgeniya M.


    The structures of dioxobipyridil-12-crown-4 ( bpy-CO-crown) and its complexes with copper (II) and silver (I) cations have been determined using single crystal X-ray-diffraction. The results have been compared with the literature data on the complexes of dcmbpy and its complex with silver (I) and copper (II) cations.

  15. Synthesis of phosphorylated calix[4]arene derivatives for the design of solid phases immobilizing uranyl cations

    Energy Technology Data Exchange (ETDEWEB)

    Maroun, E.B.; Hagege, A.; Asfari, Z. [Laboratoire de Chimie Analytique et Minerale, UMR 7178 ULP/CNRS/IN2P3 LC4, ECPM, Strasbourg Cedex (France); Basset, CH.; Quemeneur, E.; Vidaud, C. [CEA IBEB, SBTN, Centre de Marcoule, Bagnols-sur-Ceze (France)


    With the aim of developing supports for uranyl cations immobilisation, new 1, 3-alternate calix[4]arenes bearing both phosphonic acid functions as chelating sites and N-succinimide-4-oxa-butyrate as the anchoring arm were synthesised in good yields. The coupling of such calixarenes to a gel was performed and a successful immobilisation of uranyl cations was obtained. (authors)

  16. A Cationic Diode Based on Asymmetric Nafion® Film Deposits

    NARCIS (Netherlands)

    He, Daping; Madrid, Elena; Aaronson, Barak; Fan, Lian; Doughty, James; Mathwig, Klaus; Bond, Alan M; McKeown, Neil B; Marken, Frank


    A thin film of Nafion®, of approximately 5 microm thickness, asymmetrically deposited onto a 6 microm thick film of poly(ethylene terephthalate) (PET) fabricated with a 5, 10, 20, or 40 microm microhole, is shown to exhibit prominent ionic diode behaviour involving cation charge carrier ("cationic d

  17. Base cation deposition in Europe - Part II. Acid neutralization capacity and contribution to forest nutrition

    NARCIS (Netherlands)

    Draaijers, G.P.J.; Leeuwen, E.P. van; Jong, P.G.H. de; Erisman, J.W.


    An assessment was made of the capacity of base cations to neutralize acid deposition and of the contribution of base cation deposition to forest nutrition in Europe. In large parts of southern Europe more than 50% of the potential acid deposition was found counteracted by deposition of non-sea salt

  18. Real-Time Observation of Organic Cation Reorientation in Methylammonium Lead Iodide Perovskites

    NARCIS (Netherlands)

    Bakulin, Artem A.; Selig, Oleg; Bakker, Huib J.; Rezus, Yves L. A.; Mueller, Christian; Glaser, Tobias; Lovrincic, Robert; Sun, Zhenhua; Chen, Zhuoying; Walsh, Aron; Frost, Jarvist M.; Jansen, Thomas L. C.


    The introduction of a mobile and polarized organic moiety as a cation in 3D lead-iodide perovskites brings fascinating optoelectronic properties to these materials. The extent and the time scales of the orientational mobility of the organic cation and the molecular mechanism behind its motion remain

  19. Eutrophication of mangroves linked to depletion of foliar and soil base cations. (United States)

    Fauzi, Anas; Skidmore, Andrew K; Heitkönig, Ignas M A; van Gils, Hein; Schlerf, Martin


    There is growing concern that increasing eutrophication causes degradation of coastal ecosystems. Studies in terrestrial ecosystems have shown that increasing the concentration of nitrogen in soils contributes to the acidification process, which leads to leaching of base cations. To test the effects of eutrophication on the availability of base cations in mangroves, we compared paired leaf and soil nutrient levels sampled in Nypa fruticans and Rhizophora spp. on a severely disturbed, i.e. nutrient loaded, site (Mahakam delta) with samples from an undisturbed, near-pristine site (Berau delta) in East Kalimantan, Indonesia. The findings indicate that under pristine conditions, the availability of base cations in mangrove soils is determined largely by salinity. Anthropogenic disturbances on the Mahakam site have resulted in eutrophication, which is related to lower levels of foliar and soil base cations. Path analysis suggests that increasing soil nitrogen reduces soil pH, which in turn reduces the levels of foliar and soil base cations in mangroves.

  20. Modification of potato peel waste with base hydrolysis and subsequent cationization. (United States)

    Lappalainen, Katja; Kärkkäinen, Johanna; Joensuu, Päivi; Lajunen, Marja


    Potato peel waste (PW) is a starch containing biomaterial produced in large amounts by food processing industry. In this work, the treatment of PW by alkaline hydrolysis and cationization in the water phase is reported. In order to improve the cationization of starch, PW was hydrolyzed by heating with alkaline (NaOH) ethanol solution (80%) in a water bath. The impact of variable molar ratios of anhydroglucose unit (AGU):NaOH, heating temperatures and times was studied on the degradation of starch and the molecular size distribution of the product. The hydrolyzed PW was cationized subsequently in water by using glycidyltrimethylammonium chloride and catalyzed by NaOH under microwave irradiation or in an oil bath. The impact of the various reaction conditions on the cationization and degree of substitution of starch was studied. The degree of substitution of the cationized starch varied in the range of 0-0.35.