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Sample records for cationic liposome-dna complexes

  1. Synthesis of linear and cyclic peptide-PEG-lipids for stabilization and targeting of cationic liposome-DNA complexes.

    PubMed

    Ewert, Kai K; Kotamraju, Venkata Ramana; Majzoub, Ramsey N; Steffes, Victoria M; Wonder, Emily A; Teesalu, Tambet; Ruoslahti, Erkki; Safinya, Cyrus R

    2016-03-15

    Because nucleic acids (NAs) have immense potential value as therapeutics, the development of safe and effective synthetic NA vectors continues to attract much attention. In vivo applications of NA vectors require stabilized, nanometer-scale particles, but the commonly used approaches of steric stabilization with a polymer coat (e.g., PEGylation; PEG=poly(ethylene glycol)) interfere with attachment to cells, uptake, and endosomal escape. Conjugation of peptides to PEG-lipids can improve cell attachment and uptake for cationic liposome-DNA (CL-DNA) complexes. We present several synthetic approaches to peptide-PEG-lipids and discuss their merits and drawbacks. A lipid-PEG-amine building block served as the common key intermediate in all synthetic routes. Assembling the entire peptide-PEG-lipid by manual solid phase peptide synthesis (employing a lipid-PEG-carboxylic acid) allowed gram-scale synthesis but is mostly applicable to linear peptides connected via their N-terminus. Conjugation via thiol-maleimide or strain-promoted (copper-free) azide-alkyne cycloaddition chemistry is highly amenable to on-demand preparation of peptide-PEG-lipids, and the appropriate PEG-lipid precursors are available in a single chemical step from the lipid-PEG-amine building block. Azide-alkyne cycloaddition is especially suitable for disulfide-bridged peptides such as iRGD (cyclic CRGDKGPDC). Added at 10 mol% of a cationic/neutral lipid mixture, the peptide-PEG-lipids stabilize the size of CL-DNA complexes. They also affect cell attachment and uptake of nanoparticles in a peptide-dependent manner, thereby providing a platform for preparing stabilized, affinity-targeted CL-DNA nanoparticles. PMID:26874401

  2. A cationic liposome-DNA complexes adjuvant (JVRS-100) enhances the immunogenicity and cross-protective efficacy of pre-pandemic influenza A (H5N1) vaccine in ferrets.

    PubMed

    Liu, Feng; Sun, Xiangjie; Fairman, Jeffery; Lewis, David B; Katz, Jacqueline M; Levine, Min; Tumpey, Terrence M; Lu, Xiuhua

    2016-05-01

    Influenza A (H5N1) viruses continue to pose a public health threat. As inactivated H5N1 vaccines are poorly immunogenic, adjuvants are needed to improve the immunogenicity of H5N1 vaccine in humans. Here, we investigated the immunogenicity and cross-protective efficacy in ferrets of a clade 2.2-derived vaccine with addition of JVRS-100, an adjuvant consisting of cationic liposome-DNA complexes (CLDC). After the first vaccination, significantly higher levels of hemagglutination-inhibition (HAI) and neutralizing antibody titers were detected in ferrets immunized with adjuvanted vaccine compared to unadjuvanted vaccine. Following a second dose of adjuvanted vaccine, HAI antibody titers of ≥ 40 were detected against viruses from multiple H5N1 clades. HAI antibodies against newly isolated H5N2 and H5N8 viruses were also augmented by JVRS-100. Ferrets were challenged with a heterologous H5N1 virus. All ferrets that received two doses of adjuvanted vaccine exhibited mild illness, significantly reduced nasal wash virus titers and protection from lethal challenge. In contrast, ferrets that received unadjuvanted vaccine showed greater weight loss, high viral titers and 3 of 6 animals succumbed to the lethal challenge. Our results indicate that the addition of JVRS-100 to H5N1 vaccine enhanced immunogenicity and cross-protection against lethal H5N1 virus disease in ferrets. JVRS-100 warrants further investigation as a potential adjuvant for influenza vaccines. PMID:26967975

  3. Cell transfection in vitro and in vivo with nontoxic TAT peptide-liposome-DNA complexes

    NASA Astrophysics Data System (ADS)

    Torchilin, Vladimir P.; Levchenko, Tatyana S.; Rammohan, Ram; Volodina, Natalia; Papahadjopoulos-Sternberg, Brigitte; D'Souza, Gerard G. M.

    2003-02-01

    Liposomes modified with TAT peptide (TATp-liposomes) showed fast and efficient translocation into the cell cytoplasm with subsequent migration into the perinuclear zone. TATp-liposomes containing a small quantity (10 mol %) of a cationic lipid formed firm noncovalent complexes with DNA. Here, we present results demonstrating both in vitro and in vivo transfection with TATp-liposome-DNA complexes. Mouse NIH/3T3 fibroblasts and rat H9C2 cardiomyocytes were transfected with such complexes in vitro. The transfection with the TATp-liposome-associated pEGFP-N1 plasmid encoding for the green fluorescent protein (GFP) was high, whereas the cytotoxicity was lower than that of commonly used cationic lipid-based gene-delivery systems. Intratumoral injection of TATp-liposome-DNA complexes into the Lewis lung carcinoma tumor of mice also resulted in an expression of GFP in tumor cells. This transfection system should be useful for various protocols of cell treatment in vitro or ex vivo as well as for localized in vivo gene therapy.

  4. Patterned Threadlike Micelles and DNA-Tethered Nanoparticles: A Structural Study of PEGylated Cationic Liposome-DNA Assemblies.

    PubMed

    Majzoub, Ramsey N; Ewert, Kai K; Jacovetty, Erica L; Carragher, Bridget; Potter, Clinton S; Li, Youli; Safinya, Cyrus R

    2015-06-30

    The self-assembly of oppositely charged biomacromolecules has been extensively studied due to its pertinence in the design of functional nanomaterials. Using cryo electron microscopy (cryo-EM), optical light scattering, and fluorescence microscopy, we investigated the structure and phase behavior of PEGylated (PEG: poly(ethylene glycol)) cationic liposome-DNA nanoparticles (CL-DNA NPs) as a function of DNA length, topology (linear and circular), and ρ(chg) (the molar charge ratio of cationic lipid to anionic DNA). Although all NPs studied exhibited lamellar internal nanostructure, NPs formed with short (∼2 kbps), linear, polydisperse DNA were defect-rich and contained smaller domains. Unexpectedly, we found distinctly different equilibrium structures away from the isoelectric point. At ρ(chg) > 1, in the excess cationic lipid regime, threadlike micelles rich in PEG-lipid were found to coexist with NPs, cationic liposomes, and spherical micelles. At high concentrations these PEGylated threadlike micelles formed a well-ordered, patterned morphology with highly uniform intermicellar spacing. At ρ(chg) < 1, in the excess DNA regime and with no added salt, individual NPs were tethered together via long, linear DNA (48 kbps λ-phage DNA) into a biopolymer-mediated floc. Our results provide insight into what equilibrium nanostructures can form when oppositely charged macromolecules self-assemble in aqueous media. Self-assembled, well-ordered threadlike micelles and tethered nanoparticles may have a broad range of applications in bionanotechnology, including nanoscale lithograpy and the development of lipid-based multifunctional nanoparticle networks. PMID:26048043

  5. Actinide cation-cation complexes

    SciTech Connect

    Stoyer, N.J.; Seaborg, G.T.

    1994-12-01

    The +5 oxidation state of U, Np, Pu, and Am is a linear dioxo cation (AnO{sub 2}{sup +}) with a formal charge of +1. These cations form complexes with a variety of other cations, including actinide cations. Other oxidation states of actinides do not form these cation-cation complexes with any cation other than AnO{sub 2}{sup +}; therefore, cation-cation complexes indicate something unique about AnO{sub 2}{sup +} cations compared to actinide cations in general. The first cation-cation complex, NpO{sub 2}{sup +}{center_dot}UO{sub 2}{sup 2+}, was reported by Sullivan, Hindman, and Zielen in 1961. Of the four actinides that form AnO{sub 2}{sup +} species, the cation-cation complexes of NpO{sub 2}{sup +} have been studied most extensively while the other actinides have not. The only PuO{sub 2}{sup +} cation-cation complexes that have been studied are with Fe{sup 3+} and Cr{sup 3+} and neither one has had its equilibrium constant measured. Actinides have small molar absorptivities and cation-cation complexes have small equilibrium constants; therefore, to overcome these obstacles a sensitive technique is required. Spectroscopic techniques are used most often to study cation-cation complexes. Laser-Induced Photacoustic Spectroscopy equilibrium constants for the complexes NpO{sub 2}{sup +}{center_dot}UO{sub 2}{sup 2+}, NpO{sub 2}{sup +}{center_dot}Th{sup 4+}, PuO{sub 2}{sup +}{center_dot}UO{sub 2}{sup 2+}, and PuO{sub 2}{sup +}{center_dot}Th{sup 4+} at an ionic strength of 6 M using LIPAS are 2.4 {plus_minus} 0.2, 1.8 {plus_minus} 0.9, 2.2 {plus_minus} 1.5, and {approx}0.8 M{sup {minus}1}.

  6. Rab11 and Lysotracker Markers Reveal Correlation between Endosomal Pathways and Transfection Efficiency of Surface-Functionalized Cationic Liposome-DNA Nanoparticles.

    PubMed

    Majzoub, Ramsey N; Wonder, Emily; Ewert, Kai K; Kotamraju, Venkata Ramana; Teesalu, Tambet; Safinya, Cyrus R

    2016-07-01

    Cationic liposomes (CLs) are widely studied as carriers of DNA and short-interfering RNA for gene delivery and silencing, and related clinical trials are ongoing. Optimization of transfection efficiency (TE) requires understanding of CL-nucleic acid nanoparticle (NP) interactions with cells, NP endosomal pathways, endosomal escape, and events leading to release of active nucleic acid from the lipid carrier. Here, we studied endosomal pathways and TE of surface-functionalized CL-DNA NPs in PC-3 prostate cancer cells displaying overexpressed integrin and neuropilin-1 receptors. The NPs contained RGD-PEG-lipid or RPARPAR-PEG-lipid, targeting integrin, and neuropilin-1 receptors, respectively, or control PEG-lipid. Fluorescence colocalization using Rab11-GFP and Lysotracker enabled simultaneous colocalization of NPs with recycling endosome (Rab11) and late endosome/lysosome (Rab7/Lysotracker) pathways at increasing mole fractions of pentavalent MVL5 (+5 e) at low (10 mol %), high (50 mol %), and very high (70 mol %) membrane charge density (σM). For these cationic NPs (lipid/DNA molar charge ratio, ρchg = 5), the influence of membrane charge density on pathway selection and transfection efficiency is similar for both peptide-PEG NPs, although, quantitatively, the effect is larger for RGD-PEG compared to RPARPAR-PEG NPs. At low σM, peptide-PEG NPs show preference for the recycling endosome over the late endosome/lysosome pathway. Increases in σM, from low to high, lead to decreases in colocalization with recycling endosomes and simultaneous increases in colocalization with the late endosome/lysosome pathway. Combining colocalization and functional TE data at low and high σM shows that higher TE correlates with a larger fraction of NPs colocalized with the late endosome/lysosome pathway while lower TE correlates with a larger fraction of NPs colocalized with the Rab11 recycling pathway. The findings lead to a hypothesis that increases in σM, leading to enhanced

  7. PEGylated Cationic Liposome – DNA Complexation in Brine is Pathway-Dependent

    PubMed Central

    Silva, Bruno F.B.; Majzoub, Ramsey N.; Chan, Chia-Ling; Li, Youli; Olsson, Ulf; Safinya, Cyrus R.

    2013-01-01

    Cationic liposome-DNA (CL-DNA) complexes, are regarded as promising materials for safe and efficient delivery of genes for therapeutical applications. In order to be used in vivo, these complexes may be coated with a hydrophilic polymer (e.g. polyethylene-glycol, PEG) that provides steric stabilization towards adhesion of proteins and removal by the immune system. In this work we study the influence of the initial salt concentration (Cs) – which modulates the electrostatic interaction between oppositely charged vesicles and DNA – on the structure and stability of PEGylated CL-DNA particles. Previous small-angle X-ray scattering has shown that if non-PEGylated or PEGylated CL-DNA lamellar complexes are prepared in water, their structure is well defined with a high number of lipid membrane-DNA layers (larger than 20). Here we show that if these complexes are transferred to saline media (150 mM NaCl or DMEM, both near physiological conditions), this structure remains nearly unchanged. Conversely, if PEGylated complexes are prepared in saline media, their lamellar structure is much looser, with fewer number of layers. This pathway dependent behavior of PEGylated complex formation in brine is modulated by the liposome membrane charge density and the mole fraction of PEG 2000 in the membranes, with the average number of layers decreasing with increasing Cs and in going from 5 mol% to 10 mol% PEG-lipid. Each of these structures (high and low number of layers) is stable with time, suggesting that despite complex formation being thermodynamically favored, the complexation process in PEGylated membranes, which determines the number of layers per particle, is kinetically controlled. In the extreme case (when polymer repulsions from 10 mol% PEG-lipid are maximized and electrostatic attraction between PEGylated CLs and DNA are minimized at low membrane charge density) complex formation is suppressed at high Cs=150 mM. PMID:24060564

  8. Use of laser induced photoacoustic spectroscopy (LIPAS) to determine equilibrium constants of cation-cation complexes

    SciTech Connect

    Hannink, N.J.; Hoffman, D.C.; Silva, R.J.; Russo, R.E.

    1993-12-31

    Laser Induced PhotoAcoustic Spectroscopy (LIPAS) is a relatively new, photothermal technique to examine solutions. Studies in the past have shown it to be more sensitive than conventional absorption spectroscopy, while, yielding the same information thus allowing lower concentrations to be used. This study is using LIPAS to examine solutions to determine the equilibrium constants of cation-cation complexes. It has been found that actinyl(V) cations form cation-cation complexes with a variety of cations, including actinyl(VI) cations. The radioactive nature of the actinide elements requires special handling techniques and also require limits be placed on the amount of material that can be used. The sensitivity of some oxidation states of the actinides to oxygen also presents a problem. Preliminary results will be presented for actinyl(V)-actinyl(VI) cation-cation complexes that were studied using a remote LIPAS system incorporating fiber optics for transmission of laser signals.

  9. A novel cationic liposome formulation for efficient gene delivery via a pulmonary route

    NASA Astrophysics Data System (ADS)

    Li, Peng; Liu, Donghua; Sun, Xiaoli; Liu, Chunxi; Liu, Yongjun; Zhang, Na

    2011-06-01

    The clinical success of gene therapy for lung cancer is not only dependent on efficient gene carriers but also on a suitable delivery route. A pulmonary delivery route can directly deliver gene vectors to the lung which is more efficient than a systemic delivery route. For gene carriers, cationic liposomes have recently emerged as leading non-viral vectors in worldwide gene therapy clinical trials. However, cytotoxic effects or apoptosis are often observed which is mostly dependent on the cationic lipid used. Therefore, an efficient and safe cationic lipid, 6-lauroxyhexyl lysinate (LHLN), previously synthesized by our group was first used to prepare cationic liposomes. Physicochemical and biological properties of LHLN-liposomes were investigated. LHLN-liposome/DNA complexes showed positive surface charge, spherical morphology, a relatively narrow particle size distribution and strong DNA binding capability. Compared with Lipofectamine2000, the new cationic liposome formulation using LHLN exhibited not only lower cytotoxicity (P < 0.05) but also similar transfection efficiency in A549 and HepG2 lung cancer cells for in vitro tests. When administered by intratracheal instillation into rat lungs for in vivo evaluation, LHLN-liposome/DNA complexes exhibited higher pulmonary gene transfection efficiency than Lipofectamine2000/DNA complexes (P < 0.05). These results suggested that LHLN-liposomes may have great potential for efficient pulmonary gene delivery.

  10. Plant rhamnogalacturonan II complexation of heavy metal cations

    DOEpatents

    O`Neill, M.A.; Pellerin, P.J.M.; Warrenfeltz, D.; Vidal, S.; Darvill, A.G.; Albersheim, P.

    1999-03-02

    The present invention provides rhamnogalacturonan-II (RG-II) and relates to its ability to complex specific multivalent heavy metal cations. In the presence of boric acid, RG-II monomers form dimers that are cross-linked by a borate ester. The yield of such borate ester cross-linked dimers of RG-II is enhanced in the presence of specific heavy metal cations. The present invention further relates to the utility of RG-II in assays for the detection of specific heavy metal contamination; as a reagent useful in the removal of specific heavy metal cations contaminating foods and liquids, for example, fish, wines, etc.; as a pharmaceutical composition useful as an antidote in specific heavy metal cation poisoning; as a treatment for the detoxification of specific heavy metal cations from blood and/or tissues; and in a method of remediation of waters and soils contaminated with specific heavy metal cations. 15 figs.

  11. Plant rhamnogalacturonan II complexation of heavy metal cations

    DOEpatents

    O'Neill, Malcolm A.; Pellerin, Patrice J. M.; Warrenfeltz, Dennis; Vidal, Stephane; Darvill, Alan G.; Albersheim, Peter

    1999-01-01

    The present invention provides rhamnogalacturonan-II (RG-II) and relates to its ability to complex specific multivalent heavy metal cations. In the presence of boric acid, RG-II monomers form dimers that are cross-linked by a borate ester. The yield of such borate ester cross-linked dimers of RG-II is enhanced in the presence of specific heavy metal cations. The present invention further relates to the utility of RG-II in assays for the detection of specific heavy metal contamination; as a reagent useful in the removal of specific heavy metal cations contaminating foods and liquids, for example, fish, wines, etc.; as a pharmaceutical composition useful as an antidote in specific heavy metal cation poisoning; as a treatment for the detoxification of specific heavy metal cations from blood and/or tissues; and in a method of remediation of waters and soils contaminated with specific heavy metal cations.

  12. TLR9 and IRF3 Cooperate to Induce a Systemic Inflammatory Response in Mice Injected With Liposome:DNA

    PubMed Central

    Walker, Wendy E; Booth, Carmen J; Goldstein, Daniel R

    2010-01-01

    Liposome:DNA is a promising gene therapy vector. However, this vector can elicit a systemic inflammatory response syndrome (SIRS). Prior reports indicate that liposome:DNA vectors activate Toll-like receptor (TLR)9. We hypothesized that liposome:DNA vectors also activate the cytosolic DNA-sensing pathway, which signals via interferon (IFN) regulatory factor (IRF)3. To test this, we treated dendritic cells (DCs) with liposome:DNA in vitro and found that IRF3 was phosphorylated independent of TLR9. To test the contribution of this pathway in vivo, we injected a liposome:DNA vector into wild-type (WT), TLR9-knockout (KO), IRF3-KO, and TLR9-IRF3-double-KO (DKO) mice. WT mice exhibited a systemic inflammatory response, evidenced by elevations in serum cytokines, serum enzyme changes indicating organ damage, hypothermia, and mortality. The cytokine response was reduced in TLR9-KO, IRF3-KO, and TLR9-IRF3-DKO mice and all three groups survived. We found that IFN-γ-KO mice that receive liposome:DNA had a reduced cytokine response and 100% survival. CD11c+ and NK1.1+ cells produced IFN-γ and depleting CD11c+ cells reduced the cytokine response in mice injected with liposome:DNA. These findings may facilitate the development of immunologically inert gene therapy vectors and may provide general insight into the mechanisms of SIRS. PMID:20145605

  13. Complexation Between Cationic Diblock Copolymers and Plasmid DNA

    NASA Astrophysics Data System (ADS)

    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.

  14. A cationic gold complex cleaves BArF24.

    PubMed

    Weber, Simone G; Zahner, David; Rominger, Frank; Straub, Bernd F

    2012-11-28

    A sterically shielded cationic NHC gold complex IPr**Au-BArF(24) without solvent coordination has been prepared in situ in CH(2)Cl(2). The monovalent transition metal electrophile, a "soft proton", heterolytically activates the C-B bond of the weakly coordinating counterion tetrakis[3,5-bis(trifluoromethyl)phenyl]borate at room temperature. PMID:23073224

  15. Cation-Cation Interactions in [(UO2)2(OH)n](4-n) Complexes

    SciTech Connect

    Odoh, Samuel O.; Govind, Niranjan; Schreckenbach, Georg; De Jong, Wibe A.

    2013-10-07

    The structures and bonding of gas-phase [(UO2)2(OH)n]4-n (n=2-6) complexes have been studied using density functional theory (DFT), MP2 and CCSD(T) methods with particular emphasis on ground state structures featuring cation-cation interactions (CCIs) between the uranyl groups. An interesting trend is observed in the stabilities of members of this series of complexes. The structures of [(UO2)2(OH)2]2+, [(UO2)2(OH)4] and [(UO2)2(OH)6]2- featuring CCIs are found at higher energies (by 3-20 kcal/mol) in comparison to their conventional μ2-dihydroxo structures. In contrast, the CCI structures of [(UO2)2(OH)3]+ and [(UO2)2(OH)5]- are respectively almost degenerate with and lower in energy than the structures with the μ2-dihydroxo format. The origin of this trend lies in the ‘symmetry’-based need to balance the coordination numbers and effective atomic charges of each uranium center. The calculated IR vibrational frequencies provide signature probes that can be used in differentiating the lowenergy structures and in experimentally confirming the existence of the structures featuring CCIs. Analysis of the bonding in the structures of [(UO2)2(OH)3]+ and [(UO2)2(OH)5]- shows that the CCIs and bridging hydroxo between the dioxo-uranium units are mainly electrostatic in nature.

  16. Structure and Interactions in Polypeptide Cationic Lipid Complexes

    NASA Astrophysics Data System (ADS)

    Subramanian, G.; Hjelm, R. P.; Smith, G. S.; Safinya, C. R.

    1998-03-01

    Complexes of polypeptides and cationic lipids have elicited much interest recently because of their potential in developing novel biomolecular materials. We have investigated the solution structure of complexes made from the anionic polypeptide poly-L-glutamic acid (PGA), the cationic lipid DDAB, and the neutral lipid DLPC. X-ray scattering and SANS revealed the structure of the complexes to be multilamellar in nature with the PGA molecules sandwiched in between the lipid bilayers and that the PGA molecules are in the disordered state on the plane of the bilayers. Lipid dilution experiments at charge neutrality indicated that the "d" spacing of the complexes monotonically increases from 39Åupto 60Åat very high dilutions. While lipid chain stretching alone does not account for the increase in "d" spacing, we propose a "pinching" mechanism where the PGA and DDAB molecules are localized to form a tightly packed layer. Away from these "pinches" the system behaves as a pure DLPC membrane with an equilibrium spacing of 60ÅSupported by NSF-DMR-9624091, PRF-31352-AC7, and Los Alamos-STB/UC:96-108.

  17. Cationic Dihydrogen/Dihydride Complexes of Osmium: Structure and Dynamics

    SciTech Connect

    Egbert, Jonathan D.; Bullock, R. Morris; Heinekey, D. M.

    2007-03-22

    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.

  18. The Structure of DNA within Cationic Lipid/DNA Complexes

    PubMed Central

    Braun, Chad S.; Jas, Gouri S.; Choosakoonkriang, Sirirat; Koe, Gary S.; Smith, Janet G.; Middaugh, C. Russell

    2003-01-01

    The structure of DNA within CLDCs used for gene delivery is controversial. Previous studies using CD have been interpreted to indicate that the DNA is converted from normal B to C form in complexes. This investigation reexamines this interpretation using CD of model complexes, FTIR as well as Raman spectroscopy and molecular dynamics simulations to address this issue. CD spectra of supercoiled plasmid DNA undergo a significant loss of rotational strength in the signal near 275 nm upon interaction with either the cationic lipid dimethyldioctadecylammonium bromide or 1,2-dioleoyltrimethylammonium propane. This loss of rotational strength is shown, however, by both FTIR and Raman spectroscopy to occur within the parameters of the B-type conformation. Contributions of absorption flattening and differential scattering to the CD spectra of complexes are unable to account for the observed spectra. Model studies of the CD of complexes prepared from synthetic oligonucleotides of varying length suggest that significant reductions in rotational strength can occur within short stretches of DNA. Furthermore, some alteration in the hydrogen bonding of bases within CLDCs is indicated in the FTIR and Raman spectroscopy results. In addition, alterations in base stacking interactions as well as hydrogen bonding are suggested by molecular dynamics simulations. A global interpretation of all of the data suggests the DNA component of CLDCs remains in a variant B form in which base/base interactions are perturbed. PMID:12547792

  19. Insights into dynamic processes of cations in pyrochlores and other complex oxides

    SciTech Connect

    Uberuaga, Blas Pedro; Perriot, Romain

    2015-08-26

    Complex oxides are critical components of many key technologies, from solid oxide fuel cells and superionics to inert matrix fuels and nuclear waste forms. In many cases, understanding mass transport is important for predicting performance and, thus, extensive effort has been devoted to understanding mass transport in these materials. However, most work has focused on the behavior of oxygen while cation transport has received relatively little attention, even though cation diffusion is responsible for many phenomena, including sintering, radiation damage evolution, and deformation processes. Here, we use accelerated molecular dynamics simulations to examine the kinetics of cation defects in one class of complex oxides, A₂B₂O₇ pyrochlore. In some pyrochlore chemistries, B cation defects are kinetically unstable, transforming to A cation defects and antisites at rates faster than they can diffuse. When this occurs, transport of B cations occurs through defect processes on the A sublattice. Further, these A cation defects, either interstitials or vacancies, can interact with antisite disorder, reordering the material locally, though this process is much more efficient for interstitials than vacancies. Whether this behavior occurs in a given pyrochlore depends on the A and B chemistry. Pyrochlores with a smaller ratio of cation radii exhibit this complex behavior, while those with larger ratios exhibit direct migration of B interstitials. Similar behavior has been reported in other complex oxides such as spinels and perovskites, suggesting that this coupling of transport between the A and B cation sublattices, while not universal, occurs in many complex oxide.

  20. General features in the stoichiometry and stability of ionophore A23187-cation complexes in homogeneous solution.

    PubMed

    Chapman, C J; Puri, A K; Taylor, R W; Pfeiffer, D R

    1990-08-15

    Existing literature describing the stoichiometry and stability of complexes between A23187 and divalent cations in solution has been extended to include additional transition series cations, the heavy-metal cations Cd2+ and Pb2+, plus seven lanthanide series trivalent cations. Stability constants of 1:1 complexes between the ionophore and the divalent cations vary by 6.2 orders of magnitude between Cu2+ and Ba2+ which are the strongest and weakest complexes, respectively. Considering alkaline-earth and first-series transition cations together, the pattern of stability constants obeys the extended Irving-Williams series as is seen with many nonionophorous liganding agents. Cd2+ and Pb2+ are bound with an affinity similar to those of Mn2+ and Zn2+, whereas the lanthanides are bound with little selectivity and slightly higher stability. Titration of the ionophore in the 10(-5) M concentration range with di- and trivalent cations gives rise first to complexes of stoichiometry MA2 and subsequently to MA as the metal concentration is increased. The second stepwise stability constants for formation of the MA2 species exceeds the first constant by approximately 10-fold. With lanthanides, heavy metals, and transition-metal cations, OH-, at near physiological concentrations, competes significantly with free ionophore for binding to the 1:1 complexes. This competition is not apparent when Ca2+ or Mg2+ are the central cations. Possible implications of the 1:1 complex selectivity pattern, the ionophore-hydroxide competitive binding equilibria, and potential ternary complexes involving 1:1 ionophore:cation complexes and other anions present in biological systems are discussed with respect to the ionophore's transport selectivity and biological actions. PMID:2116770

  1. A spin-crossover ionic liquid from the cationic iron(III) Schiff base complex.

    PubMed

    Okuhata, Megumi; Funasako, Yusuke; Takahashi, Kazuyuki; Mochida, Tomoyuki

    2013-09-01

    A thermochromic magnetic ionic liquid containing a cationic iron(III) Schiff-base complex has been developed, whose color and magnetic moment change with temperature because of spin crossover in the liquid state. This spin-crossover behavior closely resembles that of a solid having the same cation. PMID:23872624

  2. Controlled complexation of plasmid DNA with cationic polymers: effect of surfactant on the complexation and stability of the complexes.

    PubMed

    Ikonen, Marjukka; Murtomäki, Lasse; Kontturi, Kyösti

    2008-10-01

    The aggregation of the cationic polymer-plasmid DNA complexes of two commonly used polymers, polyethyleneimine (PEI) and poly-l-lysine (PLL) were systematically compared. The complexation was studied in 5% glucose solution at 25 degrees C using dynamic light scattering and isothermal titration calorimetry. The aggregation of the complexes was controlled by addition of the surfactant polyoxyethylene stearate (POES). The stability of the complexes was evaluated using dextran sulphate (DS) as relaxing agent. The relaxation of the complexes in the presence of DS was studied using agarose gel electrophoresis. This study elucidates the role of surfactant in controlling the size of the PEI/pDNA complex and reveals the differences of the two polymers as complexing agents. PMID:18583110

  3. Complex formation of alkaline-earth cations with crown ethers and cryptands in methanol solutions

    SciTech Connect

    Buschman, H.J.

    1986-06-01

    The complexation of alkaline-earth cations by different crown ethers, azacrown ethers, and cryptands has been studied in methanol solutions by means of calorimetric and potentiometric titrations. The smallest monocyclic ligands examined from 2:1 complexes (ratio of ligand to cation) with cations which are too large to fit into the ligand cavity. With the smallest cryptand, only Sr/sup 2 +/ and Ba/sup 2 +/ ions are able to form exclusive complexes. In the case of the reaction of cryptand (211) with Ca/sup 2 +/, a separate estimation of stability constants for the formation of exclusive and inclusive complexes was possible for the first time. Higher values for stability constants are found for the reaction of alkaline-earth cations with cryptands compared to the reaction with alkali ions. This increase is only caused by favorable entropic contributions.

  4. The diastereoselective synthesis of octahedral cationic iridium hydride complexes with a stereogenic metal centre.

    PubMed

    Humbert, Nicolas; Mazet, Clément

    2016-08-23

    We report herein the highly diastereoselective synthesis of octahedral cationic Ir(iii) hydride complexes with a stereogenic metal centre following various strategies. The configurational stability of these compounds has also been investigated. PMID:27498763

  5. Infrared photodissociation spectroscopy of mass-selected silver and gold nitrosyl cation complexes.

    PubMed

    Li, Yuzhen; Wang, Lichen; Qu, Hui; Wang, Guanjun; Zhou, Mingfei

    2015-04-16

    The [M(NO)n](+) cation complexes (M = Au and Ag) are studied for exploring the coordination and bonding between nitric oxide and noble metal cations. These species are produced in a laser vaporization supersonic ion source and probed by infrared photodissociation spectroscopy in the NO stretching frequency region using a collinear tandem time-of-flight mass spectrometer. The geometric and electronic structures of these complexes are determined by comparison of the distinctive experimental spectra with simulated spectra derived from density functional theory calculations. All of these noble metal nitrosyl cation complexes are characterized to have bent NO ligands serving as one-electron donors. The spectrum of [Au(NO)2Ar](+) is consistent with 2-fold coordination with a near linear N-Au-N arrangement for this ion. The [Au(NO)n](+) (n = 3-4) cations are determined to be a mixture of 2-fold coordinated form and 3- or 4-fold coordinated form. In contrast, the spectra of [Ag(NO)n](+) (n = 3-6) provide evidence for the completion of the first coordination shell at n = 5. The high [Au(NO)n](+) and [Ag(NO)n](+) (n ≥ 3 for Au, n ≥ 4 for Ag) complexes each involve one or more (NO)2 dimer ligands, as observed in the copper nitrosyl cation complexes, indicating that ligand-ligand coupling plays an important role in the structure and bonding of noble metal nitrosyl cation complexes. PMID:25811327

  6. Insights into dynamic processes of cations in pyrochlores and other complex oxides

    DOE PAGESBeta

    Uberuaga, Blas Pedro; Perriot, Romain

    2015-08-26

    Complex oxides are critical components of many key technologies, from solid oxide fuel cells and superionics to inert matrix fuels and nuclear waste forms. In many cases, understanding mass transport is important for predicting performance and, thus, extensive effort has been devoted to understanding mass transport in these materials. However, most work has focused on the behavior of oxygen while cation transport has received relatively little attention, even though cation diffusion is responsible for many phenomena, including sintering, radiation damage evolution, and deformation processes. Here, we use accelerated molecular dynamics simulations to examine the kinetics of cation defects in onemore » class of complex oxides, A₂B₂O₇ pyrochlore. In some pyrochlore chemistries, B cation defects are kinetically unstable, transforming to A cation defects and antisites at rates faster than they can diffuse. When this occurs, transport of B cations occurs through defect processes on the A sublattice. Further, these A cation defects, either interstitials or vacancies, can interact with antisite disorder, reordering the material locally, though this process is much more efficient for interstitials than vacancies. Whether this behavior occurs in a given pyrochlore depends on the A and B chemistry. Pyrochlores with a smaller ratio of cation radii exhibit this complex behavior, while those with larger ratios exhibit direct migration of B interstitials. Similar behavior has been reported in other complex oxides such as spinels and perovskites, suggesting that this coupling of transport between the A and B cation sublattices, while not universal, occurs in many complex oxide.« less

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

    NASA Astrophysics Data System (ADS)

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

    2011-07-01

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

  8. Formation of Stable Cationic Lipid/DNA Complexes for Gene Transfer

    NASA Astrophysics Data System (ADS)

    Hofland, Hans E. J.; Shephard, Lee; Sullivan, Sean M.

    1996-07-01

    Stable cationic lipid/DNA complexes were formed by solubilizing cationic liposomes with 1% octylglucoside and complexing a DNA plasmid with the lipid in the presence of detergent. Removal of the detergent by dialysis yielded a lipid/DNA suspension that was able to transfect tissue culture cells up to 90 days after formation with no loss in activity. Similar levels of gene transfer were obtained by mixing the cationic lipid in a liposome form with DNA just prior to cell addition. However, expression was completely lost 24 hr after mixing. The transfection efficiency of the stable complex in 15% fetal calf serum was 30% of that obtained in the absence of serum, whereas the transient complex was completely inactivated with 2% fetal calf serum. A 90-day stability study comparing various storage conditions showed that the stable complex could be stored frozen or as a suspension at 4 degrees C with no loss in transfection efficiency. Centrifugation of the stable complex produced a pellet that contained approximately 90% of the DNA and 10% of the lipid. Transfection of cells with the resuspended pellet and the supernatant showed that the majority of the transfection activity was in the pellet and all the toxicity was in the supernatant. Formation of a stable cationic lipid/DNA complex has produced a transfection vehicle that can be stored indefinitely, can be concentrated with no loss in transfection efficiency, and the toxicity levels can be greatly reduced when the active complex is isolated from the uncomplexed lipid.

  9. Neutral and Cationic Alkyl Tantalum Imido Complexes: Synthesis and Migratory Insertion Reactions

    PubMed Central

    Anderson, Laura L.; Schmidt, Joseph A. R.; Arnold, John; Bergman, Robert G.

    2008-01-01

    The synthesis and reactivity of dibenzyl cationic tantalum imido complexes is described. The trialkyl tantalum imido compounds Bn3Ta=NCMe3 (1) and Np3Ta=NCMe3 (2) were synthesized as starting materials for the study of dialkyl cationic tantalum imido complexes. Compound 1 undergoes insertion reactions with diisopropylcarbodiimide and 2,6-dimethylphenylisocyanide to give (bisamidinate)imido complex 5 and (bisimino-acyl)imido complex 6, respectively. Treatment of compound 1 with B(C6F5)3 gives the zwitterionic tantalum complex [Bn2Ta=NCMe3][BnB(C6F5)3] (7) which is stabilized by η6-coordination of the benzyl triaryl borate anion. Coordination of the aryl anion can be displaced by three equivalents of pyridine to give the Lewis base complex 8. Treatment of compound 1 with [Ph3C][B(C6F5)4] gives the cationic tantalum imido complex [Bn2Ta=NCMe3][B(C6F5)4] (3). This salt forms insoluble aggregates unless trapped by THF coordination or an insertion reaction with an alkyne or an alkene. Cation 3 undergoes migratory insertion reactions with diphenylacetylene, phenylacetylene, norbornene, and cis-cyclooctene to give the corresponding alkenyl or modified alkyl imido complexes. The characterization of these products and the significance of these insertion reactions with respect to Ziegler-Natta polymerizations and hydroamination reactions are described. PMID:19079787

  10. Enhancing electrocatalytic hydrogen evolution by nickel salicylaldimine complexes with alkali metal cations in aqueous media.

    PubMed

    Shao, Haiyan; Muduli, Subas K; Tran, Phong D; Soo, Han Sen

    2016-02-18

    New salicylaldimine nickel complexes, comprising only earth-abundant elements, have been developed for electrocatalytic hydrogen evolution in aqueous media. The second-sphere ether functionalities on the periphery of the complexes enhance the electrocatalytic activity in the presence of alkali metal cations. The electrocatalysts demonstrate improved performances especially in the economical and sustainable seawater reaction medium. PMID:26779580

  11. Reversible piezochromic behavior of two new cationic iridium(III) complexes.

    PubMed

    Shan, Guo-Gang; Li, Hai-Bin; Cao, Hong-Tao; Zhu, Dong-Xia; Li, Peng; Su, Zhong-Min; Liao, Yi

    2012-02-14

    We demonstrate that two new cationic Ir(III) complexes exhibit an interesting piezochromism, and their emission color can be smartly switched by grinding and heating. This is the first example that the Ir(III) complexes display piezochromic phosphorescence. PMID:22237981

  12. Effect of the counter cation on the third order nonlinearity in anionic Au dithiolene complexes

    NASA Astrophysics Data System (ADS)

    Iliopoulos, K.; El-Ghayoury, A.; Derkowska, B.; Ranganathan, A.; Batail, P.; Gindre, D.; Sahraoui, B.

    2012-12-01

    In this work, we present the third order nonlinear optical investigation of two gold complexes, which differ by the nature of the counter cations. The impact of the different design in the architecture through a set of hydrogen bonds in the case of Au-Mel of the systems on the nonlinearity has been studied by means of the Z-scan setup under 532 nm, 30 ps laser excitation, allowing for the determination of the nonlinear absorption and refraction of the samples. Significant modification of the nonlinear optical response between the two metal complexes has been found suggesting a clear effect of the counter cation.

  13. Solvent extraction of lanthanoid picrates with crown ethers: preferential sandwich complexation and unique cation selectivities

    SciTech Connect

    Nakagawa, K.; Okada, S.; Inoue, Y.; Tai, A.; Hakushi, T.

    1988-11-15

    Quantitative solvent extractions of aqueous lanthanoid picrates with 15-crown-5 and 18-crown-6 were conducted at low ionic strength in the absence of background salts. An overwhelming preference for the sandwich complexation and unique cation selectivities were observed. The peak extraction constants were found for samarium with 15-crown-5 (1:2 stoichiometry) and for cerium and praseodymium with 18-crown-6 (1:1 and 1:2 stoichiometries, respectively). The facile sandwich complexation and unique cation selectivities are interpreted in terms of the heavy hydration of lanthanoid ions of high charge density.

  14. Cation transport by the respiratory NADH:quinone oxidoreductase (complex I): facts and hypotheses.

    PubMed

    Steffen, Wojtek; Steuber, Julia

    2013-10-01

    The respiratory complex I (electrogenic NADH:quinone oxidoreductase) has been considered to act exclusively as a H+ pump. This was questioned when the search for the NADH-driven respiratory Na+ pump in Klebsiella pneumoniae initiated by Peter Dimroth led to the discovery of a Na+-translocating complex in this enterobacterium. The 3D structures of complex I from different organisms support the idea that the mechanism of cation transport by complex I involves conformational changes of the membrane-bound NuoL, NuoM and NuoN subunits. In vitro methods to follow Na+ transport were compared with in vivo approaches to test whether complex I, or its individual NuoL, NuoM or NuoN subunits, extrude Na+ from the cytoplasm to the periplasm of bacterial host cells. The truncated NuoL subunit of the Escherichia coli complex I which comprises amino acids 1-369 exhibits Na+ transport activity in vitro. This observation, together with an analysis of putative cation channels in NuoL, suggests that there exists in NuoL at least one continuous pathway for cations lined by amino acid residues from transmembrane segments 3, 4, 5, 7 and 8. Finally, we discuss recent studies on Na+ transport by mitochondrial complex I with respect to its putative role in the cycling of Na+ ions across the inner mitochondrial membrane. PMID:24059520

  15. A porphyrin complex of Gold(I): (Phosphine)gold(I) azides as cation precursors

    PubMed Central

    Partyka, David V.; Robilotto, Thomas J.; Zeller, Matthias; Hunter, Allen D.; Gray, Thomas G.

    2008-01-01

    A silver- and Brönsted acid-free protocol for generating the (tricyclohexylphosphine)gold(I) cation from the corresponding azide complexes is disclosed. The gold(I) cations so liberated are trapped by complexation with octaethylporphyrin. The first structurally authenticated gold(I) porphyrin complex crystallizes with formula C72H112Au2F12N4P2Sb2, space group C2/c, a = 21.388 (4), b = 19.679 (4), c = 19.231 (3) Å; β = 111.030 (3)°. Solution spectroscopic studies indicate that the di-gold complex fragments on dissolution in organic solvents. Approximate density-functional theory calculations find an electrostatic origin for the binding of two gold(I) centers to the unprotonated nitrogen atoms, despite greater orbital density on the porphyrin meso carbons. PMID:18780788

  16. Cationic rhenium complexes ligated with N-heterocyclic carbenes - an overview.

    PubMed

    Hille, Claudia; Kühn, Fritz E

    2016-01-01

    This review provides an overview of the currently known cationic rhenium NHC complexes. Synthesis, structures and properties are described. The title compounds are potential candidates for both catalytic and medical applications. Besides the variety of ancillary ligands, which are in some cases easily substituted, functionalization can be carried out in the side chain or at the backbone of the carbene ligand as well as - in the case of biscarbene ligands - at the bridging moiety. Cationic Re NHC complexes are promising precursors for radiopharmaceuticals and diagnostics - not only because of the possibility to radiolabel the metal (steps in this direction have been made and described already) - but rather the opportunity to link the complexes to biomolecules via the different possibilities provided by the ligands. The development of OLEDs based on luminescent Re(i) carbene complexes renders another potential application. PMID:26587970

  17. Complexation of Trivalent Metal Cations to Mannuronate Type Alginate Models from a Density Functional Study.

    PubMed

    Menakbi, Chemseddine; Quignard, Francoise; Mineva, Tzonka

    2016-04-21

    Complexation of alginate models, built of β-d-mannuronic units (M) linked by a 1-4 glycosidic bridge, to Al(3+), Sc(3+), Cr(3+), Fe(3+), Ga(3+), and La(3+) cations was studied by applying the quantum chemical density functional theory (DFT) based method. The binding modes and energies were obtained for complexes with one, two, and three truncated alginate chain(s). In all the hydrated structures a monodentate binding mode is established to be the energetically most favored with shorter M(3+)···O(COO(-)) bonds than M(3+)···O(OH) bonds. Coordination bond lengths are found to be specific to each cation and to depend very little on the water in the coordination sphere and on the number of saccharide units used to model an alginate chain. The binding energy tendency Fe(3+) ≈ Cr(3+) > Al(3+) ≈ Ga(3+) ≫ Sc(3+) ≥ La(3+) is not affected by the alginate models, the coordination to water molecules, and the number of chains. A significant covalent contribution that arises predominantly from a charge donation from the carboxylate oxygen to the metal cation was established from the orbital population analysis. An exothermic chain-chain association is predicted by the computed enthalpy variations. A comparison between the structural features of alginate complexation to trivalent and divalent cations is provided and discussed. PMID:27010554

  18. Hydrogen-bonded inclusion compounds with reversed polarity: anionic metal-complexes and cationic organic linkers.

    PubMed

    Prakash, M Jaya; Sevov, Slavi C

    2011-12-19

    Synthesized and structurally characterized is a new series of soft-host frameworks assembled by charge-assisted hydrogen bonds between an anionic metal complex (MC) and cationic organic linkers (OL), specifically [Co(en)(ox)(2)](-) and diprotonated 4,4'-bipyridinium (H(2)bpy) or 1,2-bis(4-pyridinium)ethylene (H(2)bpye). While frameworks built of cationic complexes and anionic organic linkers are already well-known, the seven new compounds described here represent the first series of frameworks with reversed polarity, that is, made of anionic complexes and cationic organic linkers. The compounds have a general formula [OL][MC](2)·n(guest), where the guest molecules 4,4'-biphenol (bp), 4-methoxyphenol (mp), 1,4-dimethoxybenzene (dmb), 1,6-dimethoxynaphtalene (dmn), and 4-nitroanisole (na). Structurally the compounds can be described as pillared-layer frameworks with layers constructed of MC anions and linked together by hydrogen-bonded cationic OL pillars. The guest molecules occupy the galleries between the pillars while their steric, electronic, and π-π and hydrogen-bonding capabilities influence the overall structure of the soft frameworks. PMID:22085246

  19. Theoretical study of alpha/beta-alanine and their protonated/alkali metal cationized complexes.

    PubMed

    Abirami, S; Xing, Y M; Tsang, C W; Ma, N L

    2005-01-27

    Density functional theory has been employed to model the structure and the relative stabilities of alpha/beta-alanine conformers and their protonated and alkali metal cationized complexes. In general, we find that the behavior of the beta-alanine (beta-Ala) system is quite similar to that of alpha-alanine (alpha-Ala). However, the presence of the methylene group (-CH2-) at the beta position in beta-Ala leads to a few key differences. First, the intramolecular hydrogen bonding patterns are different between free alpha- and beta-Ala. Second, the stability of zwitterionic species (in either the free ligand or alkali metal cationized complexes) is often enhanced in beta-Ala. Third, the preferred mode of alkali metal cation (M+) binding may also differ in alpha- and beta-Ala. Natural energy decomposition analysis has been applied here to gain further insight into the effects of the ligand, cation size, and mode of binding on the nature of interaction in these M+-Ala complexes. PMID:16833371

  20. Complexes of DNA with cationic peptides: conditions of formation and factors effecting internalization by mammalian cells.

    PubMed

    Dizhe, E B; Ignatovich, I A; Burov, S V; Pohvoscheva, A V; Akifiev, B N; Efremov, A M; Perevozchikov, A P; Orlov, S V

    2006-12-01

    This work was devoted to the study of conditions of the formation of DNA/K8 complex and analysis of factors effecting the entry of DNA/K8 complex into mammalian cells in comparison with DNA complexes with arginine-rich fragment (47-57) of human immunodeficiency virus (type 1) transcription factor Tat (Tat peptide). The stoichiometry of positively charged DNA/K8 complexes has been studied for the first time. Non-cooperative character of DNA-K8 interaction was revealed. It has been shown that along with the positive charge of such complexes, the presence of an excess of free K8 peptide in the culture medium is a necessary condition for maximal efficiency of cell transfection with DNA/K8 complexes. A stimulatory effect of free K8 peptide on the efficiency of mammalian cell transfection by DNA/K8 complexes is likely to be mediated by the interactions of cationic peptide K8 with negatively charged proteoglycans on the cell surface, which leads to protection of DNA/K8 complexes from disruption by cellular heparan sulfates. However, the protective role of free cationic peptides depends not only on their positive charge, but also on the primary structure of the peptide. In contrast with the results obtained for DNA complexes with molecular conjugates based on poly-L-lysine, the aggregation of DNA/K8 complexes leads to a significant increase in the expression of transferred gene. PMID:17223788

  1. Complexation of the calcium cation with antamanide: an experimental and theoretical study

    NASA Astrophysics Data System (ADS)

    Makrlík, Emanuel; Böhm, Stanislav; Vaňura, Petr; Ruzza, Paolo

    2015-06-01

    By using extraction experiments and γ-activity measurements, the extraction constant corresponding to the equilibrium Ca2+(aq) + 1 .Sr2+(nb) ? 1 .Ca2+(nb) + Sr2+(aq) occurring in the two-phase water-nitrobenzene system (1 = antamanide; aq = aqueous phase, nb = nitrobenzene phase) was determined as log Kex (Ca2+, 1 .Sr2+) = 1.6 ± 0.1. Further, the stability constant of the 1 .Ca2+ complex in nitrobenzene saturated with water was calculated for a temperature of 25 °C: log βnb (1 .Ca2+) = 10.9 ± 0.2. Finally, applying quantum mechanical density functional level of theory calculations, the most probable structure of the cationic complex species 1 .Ca2+ was derived. In the resulting complex, the 'central' cation Ca2+ is bound by six strong bonding interactions to the corresponding six carbonyl oxygen atoms of the parent ligand 1. Besides, the whole 1 .Ca2+ complex structure is stabilised by two intramolecular hydrogen bonds. The interaction energy of the considered 1 .Ca2+ complex, involving the Boys-Bernardi counterpoise corrections of the basis set superposition error, was found to be -1219.3 kJ/mol, confirming the formation of this cationic species.

  2. Morphological study of cationic polymer-anionic surfactant complex precipitated in solution during the dilution process.

    PubMed

    Miyake, M; Kakizawa, Y

    2010-01-01

    We investigated the phase diagrams and the morphology of the complexes that were formed by cationic polymers, cationic cellulose (CC) and cationic dextran (CD), and by anionic surfactant-based sodium poly(oxyethylene) lauryl ether sulfate (LES). The anionic charge of the LES-based surfactants was changed by adding an amphoteric surfactant, lauryl amidopropyl betaine acetate (LPB), or a nonionic surfactant, polyoxyethylene stearyl ether (C18EO25). We discuss the relationship between the complex aggregation process and the morphology of the precipitated complexes. The morphologies of CC complex aggregates, which precipitated during the dilution process in a model shampoo solution, changed from membranous forms to mesh-like forms by decreasing the charges of both the CC and the surfactant. Their touch on hair in the rinsing process changed from sticky to smooth and velvety, corresponding to their rheological properties. In contrast, CD complex aggregates had a membranous form and a smooth touch independently of the charges on the polymer and surfactant. These results suggested that the control of the charges of both the polymer and surfactant and the choice of polymer structure are important for excellent conditioning effects upon rinsing with shampoo. PMID:20716437

  3. Synthesis and chemistry of cationic d sup 0 metal alkyl complexes

    SciTech Connect

    Jordan, R.F.

    1990-01-01

    The long term goals of this project are to design and synthesize highly unsaturated, electrophilic metal complexes and to explore their use as catalysts, reagents, and/or model systems for olefin polymerization and C-H activation chemistry. During the 1990 budget year we have focused our attention on (i) the ligand C-H activation chemistry of Cp{sub 2}Zr(CH{sub 3})(THF){sup +} and related cationic, d{sup o} Zr alkyl complexes, and (ii) the synthesis of new classes of group 4 metal alkyl complexes with non-Cp{sub 2}M ligand environments.

  4. Complexation of the sodium cation with sodium ionophore III: Experimental and theoretical study

    NASA Astrophysics Data System (ADS)

    Makrlík, Emanuel; Kvíčala, Jaroslav; Vaňura, Petr

    2014-06-01

    By using extraction experiments and γ-activity measurements, the extraction constant corresponding to the equilibrium Na+(aq) + A-(aq) + 1(nb) ⇄ 1·Na+(nb) + A-(nb) occurring in the two-phase water - nitrobenzene system (A- = picrate, 1 = sodium ionophore III; aq = aqueous phase, nb = nitrobenzene phase) was determined as log Kex (1·Na+, A-) = 1.5 ± 0.1. Further, the stability constant of the 1·Na+ complex in nitrobenzene saturated with water was calculated for a temperature of 25 °C: log βnb (1·Na+) = 6.7 ± 0.1. Finally, applying quantum mechanical DFT calculations, the most probable structure of the nonhydrated 1·Na+ and hydrated 1·Na+·2H2O cationic complex species were derived. In both of these complexes, the “central” cation Na+ is bound by four bonding interactions to the corresponding four oxygen atoms of the parent ligand 1. Besides, in the case of 1·Na+·2H2O complex, the considered hydrated structure is stabilized by two water molecules bound to the “central” sodium cation.

  5. Effectiveness, against tuberculosis, of pseudo-ternary complexes: peptide-DNA-cationic liposome.

    PubMed

    Rosada, Rogério Silva; Silva, Célio Lopes; Santana, Maria Helena Andrade; Nakaie, Clóvis Ryuichi; de la Torre, Lucimara Gaziola

    2012-05-01

    We report the effects of a synthetic peptide designed to act as a nuclear localization signal on the treatment of tuberculosis. The peptide contains 21 amino acid residues with the following specific domains: nuclear localization signal from SV 40T, cationic shuttle sequence, and cysteamide group at the C-terminus. The peptide was complexed with the plasmid DNAhsp65 and incorporated into cationic liposomes, forming a pseudo-ternary complex. The same cationic liposomes, composed of egg chicken L-α-phosphatidylcholine, 1,2-dioleoyl-3-trimethylammonium-propane, and 1,2-dioleoyl-3-trimethylammonium-propane (2:1:1M), were previously evaluated as a gene carrier for tuberculosis immunization protocols with DNAhsp65. The pseudo-ternary complex presented a controlled size (250 nm), spherical-like shape, and various lamellae in liposomes as evaluated by transmission electron microscopy. An assay of fluorescence probe accessibility confirmed insertion of the peptide/DNA into the liposome structure. Peptide addition conferred no cytotoxicity in vitro, and similar therapeutic effects against tuberculosis were seen with four times less DNA compared with naked DNA treatment. Taken together, the results indicate that the pseudo-ternary complex is a promising gene vaccine for tuberculosis treatment. This work contributes to the development of multifunctional nanostructures in the search for strategies for in vivo DNA delivery. PMID:21999959

  6. Effect of vesicle size on tissue localization and immunogenicity of liposomal DNA vaccines.

    PubMed

    Carstens, Myrra G; Camps, Marcel G M; Henriksen-Lacey, Malou; Franken, Kees; Ottenhoff, Tom H M; Perrie, Yvonne; Bouwstra, Joke A; Ossendorp, Ferry; Jiskoot, Wim

    2011-06-24

    The formulation of plasmid DNA (pDNA) in cationic liposomes is a promising strategy to improve the potency of DNA vaccines. In this respect, physicochemical parameters such as liposome size may be important for their efficacy. The aim of the current study was to investigate the effect of vesicle size on the in vivo performance of liposomal pDNA vaccines after subcutaneous vaccination in mice. The tissue distribution of cationic liposomes of two sizes, 500 nm (PDI 0.6) and 140 nm (PDI 0.15), composed of egg PC, DOPE and DOTAP, with encapsulated OVA-encoding pDNA, was studied by using dual radiolabeled pDNA-liposomes. Their potency to elicit cellular and humoral immune responses was investigated upon application in a homologous and heterologous vaccination schedule with 3 week intervals. It was shown that encapsulation of pDNA into cationic lipsomes resulted in deposition at the site of injection, and strongest retention was observed at large vesicle size. The vaccination studies demonstrated a more robust induction of OVA-specific, functional CD8+ T-cells and higher antibody levels upon vaccination with small monodisperse pDNA-liposomes, as compared to large heterodisperse liposomes or naked pDNA. The introduction of a PEG-coating on the small cationic liposomes resulted in enhanced lymphatic drainage, but immune responses were not improved when compared to non-PEGylated liposomes. In conclusion, it was shown that the physicochemical properties of the liposomes are of crucial importance for their performance as pDNA vaccine carrier, and cationic charge and small size are favorable properties for subcutaneous DNA vaccination. PMID:21565240

  7. DNA strand exchange stimulated by spontaneous complex formation with cationic comb-type copolymer.

    PubMed

    Kim, Won Jong; Akaike, Toshihiro; Maruyama, Atsushi

    2002-10-30

    Cationic comb-type copolymers (CCCs) composed of a polycation backbone and water-soluble side chains accelerate by 4-5 orders the DNA strand exchange reaction (SER) between double helical DNA and its homologous single-strand DNA. The accelerating effect is considered due to alleviation of counterion association during transitional intermediate formation in sequential displacement pathway. CCCs stabilize not only matured hybrids but also the nucleation complex to accelerate hybridization. PMID:12392411

  8. Chromomycin dimer-DNA oligomer complexes. Sequence selectivity and divalent cation specificity.

    PubMed

    Gao, X L; Patel, D J

    1990-12-11

    This paper reports on a solution NMR characterization of the sequence selectivity and metal ion specificity in chromomycin-DNA oligomer complexes in the presence of divalent cations. The sequence selectivity studies have focused on chromomycin complexes with the self-complementary d(A1-A2-G3-G4-C5-C6-T7-T8) duplex containing a pair of adjacent (G3-G4).(C5-C6) steps and the self-complementary d(A1-G2-G3-A4-T5-C6-C7-T8) duplex containing a pair of separated (G2-G3).(C6-C7) steps in aqueous solution. The antitumor agent (chromomycin) and nucleic acid protons have been assigned following analysis of distance connectivities in NOESY spectra and coupling connectivities in DQF-COSY spectra for both complexes in H2O and D2O solution. The observed intermolecular NOEs establish that chromomycin binds as a Mg(II)-coordinated dimer [1 Mg(II) per complex] and contacts the minor-groove edge with retention of 2-fold symmetry centered about the (G3-G4-C5-C6).(G3-G4-C5-C6) segment of the d(A2G2C2T2) duplex. By contrast, complex formation is centered about the (G2-G3-A4-T5).(A4-T5-C6-C7) segment and results in removal of the two fold symmetry of the d(AG2ATC2T) duplex. Thus, the binding of one subunit of the chromomycin dimer at its preferred (G-G).(C-C) site assists in the binding of the second subunit to the less preferred adjacent (A-T).(A-T) site. These observations suggest a hierarchy of chromomycin binding sites, with a strong site detected at the (G-G) step due to the hydrogen-bonding potential of acceptor N3 and donor NH2 groups of guanosine that line the minor groove. The divalent cation specificity has been investigated by studies on the symmetric chromomycin-d(A2G2C2T2) complex in the presence of diamagnetic Mg(II), Zn(II), and Cd(II) cations and paramagnetic Ni(II) and Co(II) cations. A comparative NOESY study of the Mg(II) and Ni(II) symmetric complexes suggests that a single tightly bound divalent cation aligns the two chromomycins in the dimer through coordination to

  9. Cationic lipophilic complexes of /sup 99/ /SUP m/ Tc and their use for myocardial and hepatobiliary imaging

    SciTech Connect

    Deutsch, E. A.; Glavan, K. A.

    1984-12-18

    A method of imaging organs with /sup 99/ /SUP m/ Tc radiopharmaceuticals, especially of hepatobiliary imaging and negative myocardial infarct imaging in a mammal which comprises administering to the mammal a hepatobiliary or myocardial imaging amount of a cationic lipophilic complex of Tc-99m and detecting the Tc-99m complex in the mammal. A method for the preparation of cationic lipophilic complexes of Tc-99m.

  10. The complexes of some s-triazine herbicides with metal cations studied by ESI mass spectrometry and theoretical calculations

    NASA Astrophysics Data System (ADS)

    Lyapchenko, Nataliya; Eitner, Krystian; Schroeder, Grzegorz; Brzezinski, Bogumił

    2004-03-01

    The complex formation of s-triazine herbicides (prometon, ametryn, terbutryn and simazin) with monovalent and divalent cations as well as the structure of the complexes was studied by the electrospray ionization mass spectrometry and PM5 semiempirical methods. It is demonstrated that the herbicides studied form stable complexes with monovalent and heavy metal cations, which is of very great importance for agriculture especially in the aspect of the environment protection.

  11. Interaction of cationic liposomes and their DNA complexes with monocytic leukemia cells.

    PubMed

    Pires, P; Simões, S; Nir, S; Gaspar, R; Düzgünes, N; Pedroso de Lima, M C

    1999-04-14

    Cationic liposomes complexed with DNA have been used extensively as non-viral vectors for the intracellular delivery of reporter or therapeutic genes in culture and in vivo. We examined the relationship between the characteristics of the lipoplexes, their mode of interaction with monocytic THP-1 cells and their ability to transfect these cells. We determined the size and zeta potential of cationic liposomes (composed of 1,2-dioleoyl-3-(trimethylammonium) propane (DOTAP) and its mixtures with neutral lipids), and lipoplexes at different (+/-) charge ratios. As the (+/-) charge ratio of the lipoplexes decreased to (1/1), a significant reduction in zeta potential and an increase in size was observed. The increase in size resulted from fusion between liposomes promoted by DNA, as demonstrated by a lipid mixing assay, and from aggregation of the complexes. Interaction of liposomes and lipoplexes with THP-1 cells was assessed by monitoring lipid mixing ('fusion') as well as binding and cell association. While no lipid mixing was observed with the 1/2 (+/-) lipid/DNA complexes, lipoplexes with higher (+/-) charge ratios underwent significant fusion in conjunction with extensive cell binding. Liposome binding to cells was dependent on the positive charge of the liposomes, and their fusion could be modulated by the co-lipid. DOTAP/phosphatidylethanolamine (1:1) liposomes fused with THP-1 cells, unlike DOTAP/phosphatidylcholine (1:1) liposomes, although both liposome types bound to the cells to a similar extent. The use of inhibitors of endocytosis indicated that fusion of the cationic liposomes with cells occurred mainly at the plasma membrane level. The presence of serum increased the size of the cationic liposomes, but not that of the lipoplexes. Low concentrations of serum (3%) completely inhibited the fusion of cationic liposomes with cells, while inhibiting binding by only 20%. Our results suggest that binding of cationic liposomes and lipoplexes to cells is governed

  12. Complexation of cationic-neutral block polyelectrolyte with insulin and in vitro release studies.

    PubMed

    Pippa, Natassa; Karayianni, Maria; Pispas, Stergios; Demetzos, Costas

    2015-08-01

    Insulin (INS) was incorporated into complexes with the block polyelectrolyte quaternized poly[3,5-bis(dimethylaminomethylene)hydroxystyrene]-b-poly(ethylene oxide) (QNPHOSEO), which is a cationic-neutral block polyelectrolyte. Light scattering techniques are used in order to examine the size, the size distribution and the ζ-potential of the nanocarriers in aqueous and biological media, which are found to depend on the ratio of the components and the physicochemical parameters during and after complex preparation. Circular dichroism and infrared spectroscopy, employed to investigate the structure of the complexed INS, show no alteration of protein structure after complexation. In vitro release profiles of the entrapped protein are found to depend on the ratio of the components and the solution conditions used during preparation of the complexes. PMID:26101970

  13. Molecular mechanics (MM3) calculations on benzocrown ether complexes of the alkali and alkaline earth cations

    SciTech Connect

    Yang, Linrong R.; Hay, B.P.

    1997-12-31

    The new metal-ligand feature of MM3 has been extended to benzocrown ether complexes of alkali and alkaline earth cations. Over 50 complexes were compared with the crystal structures retrieved from Cambridge Crystal Database. The results agree with experimental data. The averages of absolute deviations between experimental and calculated structural features are: metal-oxygen bond length, 0.03 {angstrom}; Metal-oxygen-carbon angles, 4.1{degrees}; and Metal-oxygen-carbon-carbon angles: 5.1{degrees}. Development of structure-function relationships is in progress.

  14. Aza-crown ether complex cation ionic liquids: preparation and applications in organic reactions.

    PubMed

    Song, Yingying; Cheng, Chen; Jing, Huanwang

    2014-09-26

    Aza-crown ether complex cation ionic liquids (aCECILs) were devised, fabricated, and characterized by using NMR spectroscopy, MS, thermogravimetric differential thermal analysis (TG-DTA), elemental analysis and physical properties. These new and room-temperature ILs were utilized as catalysts in various organic reactions, such as the cycloaddition reaction of CO2 to epoxides, esterification of acetic acid and alcohols, the condensation reaction of aniline and propylene carbonate, and Friedel-Crafts alkylation of indole with aldehydes were investigated carefully. In these reactions, the ionic liquid exhibited cooperative catalytic activity between the anion and cation. In addition, the aza-[18-C-6HK][HSO4]2 was the best acidic catalyst in the reactions of esterification and Friedel-Crafts alkylation under mild reaction conditions. PMID:25154312

  15. Hydrodynamic size of DNA/cationic gemini surfactant complex as a function of surfactant structure.

    PubMed

    Devínsky, Ferdinand; Pisárcik, Martin; Lacko, Ivan

    2009-06-01

    The present study deals with the determination of hydrodynamic size of DNA/cationic gemini surfactant complex in sodium bromide solution using the dynamic light scattering method. Cationic gemini surfactants with polymethylene spacer of variable length were used for the interaction with DNA. The scattering experiments were performed at constant DNA and sodium bromide concentrations and variable surfactant concentration in the premicellar and micellar regions as a function of surfactant spacer length. It was found that the DNA conformation strongly depends on the polymethylene spacer length as well as on the surfactant concentration relative to the surfactant critical micelle concentration. Gemini surfactant molecules with 4 methylene groups in the spacer were found to be the least efficient DNA compacting agent in the region above the surfactant cmc. Gemini molecules with the shortest spacer length (2 methylene groups) and the longest spacer length (8 methylene groups) investigated showed the most efficient DNA compaction ability. PMID:19592712

  16. Substituent and Solvent Effects on the Absorption Spectra of CationComplexes of Benzene and Borazine: A Theoretical Study.

    PubMed

    Sarmah, Nabajit; Bhattacharyya, Pradip Kr; Bania, Kusum K

    2014-05-14

    Time-dependent density functional theory (TDDFT) has been used to predict the absorption spectra of cationcomplexes of benzene and borazine. Both polarized continuum model (PCM) and discrete solvation model (DSM) and a combined effect of PCM and DSM on the absorption spectra have been elucidated. With decrease in size of the cation, the π → π* transitions of benzene and borazine are found to undergo blue and red shift, respectively. A number of different substituents (both electron-withdrawing and electron-donating) and a range of solvents (nonpolar to polar) have been considered to understand the effect of substituent and solvents on the absorption spectra of the cationcomplexes of benzene and borazine. Red shift in the absorption spectra of benzene cationcomplexes are observed with both electron-donating groups (EDGs) and electron-withdrawing groups (EWGs). The same trend has not been observed in the case of substituted borazine cationcomplexes. The wavelength of the electronic transitions corresponding to cationcomplexes correlates well with the Hammet constants (σp and σm). This correlation indicates that the shifting of spectral lines of the cationcomplexes on substitution is due to both resonance and inductive effect. On incorporation of solvent phases, significant red or blue shifting in the absorption spectra of the complexes has been observed. Kamlet-Taft multiparametric equation has been used to explain the effect of solvent on the absorption spectra of complexes. Polarity and polarizability are observed to play an important role in the solvatochromism of the cationcomplexes. PMID:24801959

  17. A Mesoionic Carbene as Neutral Ligand for Phosphorescent Cationic Ir(III) Complexes.

    PubMed

    Baschieri, Andrea; Monti, Filippo; Matteucci, Elia; Mazzanti, Andrea; Barbieri, Andrea; Armaroli, Nicola; Sambri, Letizia

    2016-08-15

    Two phosphorescent Ir(III) complexes bearing a mesoionic carbene ligand based on 1,2,3-triazolylidene are obtained for the first time. A silver-iridium transmetalation of the in situ-generated mesoionic carbene affords the cationic dichloro complex [Ir(trizpy)2Cl2](+) (3, trizpy = 1-benzyl-3-methyl-4-(pyridin-2-yl)-1H-1,2,3-triazolylidene) that reacts with a bis-tetrazolate (b-trz) dianionic ligand to give [Ir(trizpy)2(b-trz)](+) (5). The new compounds are fully characterized by NMR spectroscopy and mass spectrometry, and the X-ray structure of 3 is determined. The electrochemical behavior is somewhat different compared to most standard cationic iridium complexes. The first oxidation process is shifted to substantially higher potential in both 3 and 5, due to peculiar and different ligand-induced effects in the two cases, which stabilize the highest occupied molecular orbital; reduction processes are centered on the mesoionic carbene ligands. Both compounds exhibit a mostly ligand-centered luminescence band in the blue-green spectral region, substantially stronger in the case of 5 versus 3, both in CH3CN solution and in poly(methyl methacrylate) matrix at room temperature. Optimized geometries, orbital energies, spin densities, and electronic transitions are determined via density functional theory calculations, which support a full rationalization of the electrochemical and photophysical behavior. This work paves the way for the development of Ir-based emitters with neutral mesoionic carbene ligands and anionic ancillary ligands, a new concept in the area of cationic Ir(III) complexes. PMID:27483041

  18. Zeaxanthin Radical Cation Formation in Minor Light-Harvesting Complexes of Higher Plant Antenna

    SciTech Connect

    Avenson, Thomas H.; Ahn, Tae Kyu; Zigmantas, Donatas; Niyogi, Krishna K.; Li, Zhirong; Ballottari, Matteo; Bassi, Roberto; Fleming, Graham R.

    2008-01-31

    Previous work on intact thylakoid membranes showed that transient formation of a zeaxanthin radical cation was correlated with regulation of photosynthetic light-harvesting via energy-dependent quenching. A molecular mechanism for such quenching was proposed to involve charge transfer within a chlorophyll-zeaxanthin heterodimer. Using near infrared (880-1100 nm) transient absorption spectroscopy, we demonstrate that carotenoid (mainly zeaxanthin) radical cation generation occurs solely in isolated minor light-harvesting complexes that bind zeaxanthin, consistent with the engagement of charge transfer quenching therein. We estimated that less than 0.5percent of the isolated minor complexes undergo charge transfer quenching in vitro, whereas the fraction of minor complexes estimated to be engaged in charge transfer quenching in isolated thylakoids was more than 80 times higher. We conclude that minor complexes which bind zeaxanthin are sites of charge transfer quenching in vivo and that they can assume Non-quenching and Quenching conformations, the equilibrium LHC(N)<--> LHC(Q) of which is modulated by the transthylakoid pH gradient, the PsbS protein, and protein-protein interactions.

  19. Characterization of cationic lipid DNA transfection complexes differing in susceptability to serum inhibition

    PubMed Central

    2002-01-01

    Background Cationic lipid DNA complexes based on DOTAP (1,2-dioleoyl-3-(trimethyammonium) propane) and mixtures of DOTAP and cholesterol (DC) have been previously optimized for transfection efficiency in the absence of serum and used as a non-viral gene delivery system. To determine whether DOTAP and DC lipid DNA complexes could be obtained with increased transfection effciency in the presence of high serum concentrations, the composition of the complexes was varied systematically and a total of 162 different complexes were analyzed for transfection efficiency in the presence and absence of high serum concentrations. Results Increasing the ratio of DOTAP or DC to DNA led to a dose dependent enhancement of transfection efficiency in the presence of high serum concentrations up to a ratio of approximately 128 nmol lipid/μg DNA. Transfection efficiency could be further increased for all ratios of DOTAP and DC to DNA by addition of the DNA condensing agent protamine sulfate (PS). For DOTAP DNA complexes with ratios of ≤ 32 nmol/μg DNA, peak transfection efficiencies were obtained with 4 μg PS/μg DNA. In contrast, increasing the amount of PS of DC complexes above 0.5 μg PS /μg DNA did not lead to significant further increases in transfection efficiency in the presence of high serum concentrations. Four complexes, which had a similar high transfection efficiency in cell culture in the presence of low serum concentrations but which differed largely in the lipid to DNA ratio and the amount of PS were selected for further analysis. Intravenous injection of the selected complexes led to 22-fold differences in transduction efficiency, which correlated with transfection efficiency in the presence of high serum concentrations. The complex with the highest transfection efficiency in vivo consisted of 64 nmol DC/ 16 μg PS/ μg DNA. Physical analysis revealed a predicted size of 440 nm and the highest zeta potential of the complexes analyzed. Conclusions Optimization of

  20. Aza-macrocyclic complexes of the Group 1 cations - synthesis, structures and density functional theory study.

    PubMed

    Dyke, John; Levason, William; Light, Mark E; Pugh, David; Reid, Gillian; Bhakhoa, Hanusha; Ramasami, Ponnadurai; Rhyman, Lydia

    2015-08-21

    The Group 1 complexes, [M(Me6[18]aneN6)][BAr(F)] (M = Li-Cs; Me6[18]aneN6 = 1,4,7,10,13,16-hexamethyl-1,4,7,10,13,16-hexaazacyclooctadecane; BAr(F) = tetrakis{3,5-bis(trifluoromethyl)-phenyl}borate), are obtained in high yield by reaction of the macrocycle with M[BAr(F)] in anhydrous CH2Cl2 solution, and characterised spectroscopically ((1)H, (13)C{(1)H}, (7)Li, (23)Na, and (133)Cs NMR), by microanalysis and, for M = Li, K, and Rb, by single crystal X-ray analysis. The structures show N6-coordination to the metal ion; the small ionic radius for Li(+) leads to a puckered conformation. In contrast, the K(+) ion fits well into the N6 plane, with the [BAr(F)](-) anions above and below, leading to two K(+) species in the asymmetric unit (a hexagonal planar [K(Me6[18]aneN6)](+) cation and a '[K(Me6[18]aneN6)(κ(1)-BAr(F))2](-) anion', with long axial KF interactions). The Rb(+) ion sits above the N6 plane, with two long axial RbF interactions in one cation and two long, mutually cis RbF interactions in the other. The unusual sandwich cations, [M(Me3tacn)2](+) (M = Na, K; distorted octahedral, N6 donor set) and half-sandwich cations [Li(Me3tacn)(thf)](+) (distorted tetrahedron, N3O donor set), [Li(Me4cyclen)(OH2)](+), and [Na(Me4cyclen)(thf)](+) (both distorted square pyramids with N4O donor sets) were also prepared (Me3tacn = 1,4,7-trimethyl-1,4,7-triazacyclononane, Me4cyclen = 1,4,7,10-tetramethyl-1,4,7,10-tetraazacyclododecane). Density functional theory (DFT) calculations, using the BP86 and B3LYP functionals, show that the accessibility of the [M(Me3tacn)2](+) sandwich cations depends strongly on the M(+) ionic radius, such that it is sufficiently large to avoid steric clashing between the Me groups of the two rings, and small enough to avoid very acute N-M-N chelate angles. The calculations also show that coordination to the Group 1 cation involves significant donation of electron density from the p-orbitals on the N atoms of the macrocycle, rather than purely

  1. Effect of monovalent cations on the kinetics of hypoxic conformational change of mitochondrial complex I

    PubMed Central

    Stepanova, Anna; Valls, Alba; Galkin, Alexander

    2015-01-01

    Mitochondrial complex I is a large, membrane-bound enzyme central to energy metabolism, and its dysfunction is implicated in cardiovascular and neurodegenerative diseases. An interesting feature of mammalian complex I is the so-called A/D transition, when the idle enzyme spontaneously converts from the active (A) to the de-active, dormant (D) form. The A/D transition plays an important role in tissue response to ischemia and rate of the conversion can be a crucial factor determining outcome of ischemia/reperfusion. Here, we describe the effects of alkali cations on the rate of the D-to-A transition to define whether A/D conversion may be regulated by sodium. At neutral pH (7–7.5) sodium resulted in a clear increase of rates of activation (D-to-A conversion) while other cations had minor effects. The stimulating effect of sodium in this pH range was not caused by an increase in ionic strength. EIPA, an inhibitor of Na+/H+ antiporters, decreased the rate of D-to-A conversion and sodium partially eliminated this effect of EIPA. At higher pH (> 8.0), acceleration of the D-to-A conversion by sodium was abolished, and all tested cations decreased the rate of activation, probably due to the effect of ionic strength. The implications of this finding for the mechanism of complex I energy transduction and possible physiological importance of sodium stimulation of the D-to-A conversion at pathophysiological conditions in vivo are discussed. PMID:26009015

  2. Zinc (II) complex with a cationic Schiff base ligand: Synthesis, characterization, and biological studies

    NASA Astrophysics Data System (ADS)

    Lee, Sze Koon; Tan, Kong Wai; Ng, Seik Weng; Ooi, Kah Kooi; Ang, Kok Pian; Abdah, Md Akim

    2014-03-01

    A cationic Schiff base ligand, TSB (L) and its Zn (II) complex (1) were synthesized and characterized by using CHN, 1H-NMR, FT-IR, UV, LC-MS, and X-ray methods. Their ability to inhibit topoisomerase I, DNA cleavage activities, and cytotoxicity were studied. X-ray diffraction study shows that the mononuclear complex 1 is four coordinated with distorted tetrahedral geometry. The singly deprotonated Schiff base ligand L acts as a bidentate ON-donor ligand. Complexation of L increases the inhibitory strength on topoisomerase I activity. Complex 1 could fully inhibit topoisomerase I activity at 250 μM, while L did not show any inhibitory effect on topoisomerase I activity. In addition, L and complex 1 could cleave pBR322 DNA in a concentration and time dependent profile. Surprisingly, L has better DNA cleavage activity than complex 1. The cleavage of DNA by complex 1 is altered in the presence of hydrogen peroxide. Furthermore, L and complex 1 are mildly cytotoxic towards human ovarian cancer A2780 and hepatocellular carcinoma HepG2.

  3. Complexes between high charge density cationic polyelectrolytes and anionic single- and double-tail surfactants.

    PubMed

    Mantzaridis, C; Mountrichas, G; Pispas, S

    2009-05-21

    Polyelectrolyte/surfactant complexes formed between well-defined linear flexible polyelectrolytes, namely, quaternized poly[3,5-bis(dimethylaminomethylene)hydroxystyrene] (Q-N-PHOS), bearing two cationic sites on each repeating unit, and two different anionic surfactants, namely, sodium dodecyl sulfate (SDS) with one hydrocarbon tail and sodium bis(2-ethylhexyl) sulfosuccinate (AOT) with two hydrocarbon chains, are studied by means of fluorescence spectroscopy, electrophoretic, dynamic and static light scattering, and atomic force microscopy. Depending on the surfactant state in initial solutions (i.e., below or above nominal critical micelle concentration, cmc) and final (-/+) charge ratio, self-assembly in nanoparticles of variable size, stability, and effective charge is possible. Spherical, rather polydispserse complexes are formed in all cases. Critical aggregation concentrations (cac) depend on the surfactant type, while hydrophobicity of the main polyelectrolyte chain plays a role in colloidal stability of the complex nanoparticles. PMID:19388679

  4. Cesium complexes of naphthalimide substituted carboxylate ligands: Unusual geometries and extensive cation-π interactions

    NASA Astrophysics Data System (ADS)

    Reger, Daniel L.; Leitner, Andrew; Smith, Mark D.

    2015-07-01

    The reactions of (1,8-naphthalimido)ethanoic acid (HLgly), and (S)-2-(1,8-naphthalimido)-3-hydroxypropanoic acid (HLser), protonated forms of ligands that contain a carboxylate donor group and a 1,8-naphthalimide π⋯π stacking supramolecular tecton, with cesium hydroxide followed by solvothermal treatment in ethanol led to the formation of crystalline Cs(Lgly) (1) and Cs(Lene) (2), where the Lene- ligand, 2-(1,8-naphthalimido)acrylate, is formed from the dehydration of the HLser starting material. The X-ray studies show that 1 crystallizes in the monoclinic space group C2/c with unit cell dimensions a = 30.430(7) Å, b = 4.9820(12) Å, c = 16.566(4) Å, β = 101.951(4)° and 2 in the monoclinic space group P21/n with unit cell dimensions a = 13.6049(15) Å, b = 6.8100(8) Å, c = 14.4187(16) Å, β = 105.345(2)°. The solid state structure of 1 contains two types of 6-coordinate cesium cations linked into sheets by bridging carboxylate oxygen atoms. One cation has a distorted octahedral environment, while the other is in an unusual planar, hexagonal O6-coordination geometry. The latter geometry is stabilized on both sides of the plane by η2-coordination of naphthalimide rings. The 1,8-naphthalimide rings are involved in intra-sheet π⋯π stacking interactions. The O6 coordination sphere of complex 2 is distorted and only half-filled with the oxygen atoms, which link the cations into rods that are further linked into sheets by bridging interactions of naphthalimide carbonyls with cesium cations from adjacent rods. The open face on the cation has unique η2:η1 interactions with two methylene groups in the ligands. These sheets are linked into a 3D supramolecular structure by interdigitated 1,8-naphthalimide rings involved in strong π⋯π interactions. Both complexes show naphthalimide based fluorescence.

  5. Bell Curve for Transfection by Lamellar Cationic Lipid--DNA Complexes

    NASA Astrophysics Data System (ADS)

    Ahmad, A.; Evans, Heather M.; Ewert, K.; George, C. X.; Samuel, C. E.; Safinya, C. R.

    2004-03-01

    Cationic liposomes (CL) present a viable alternative to viral delivery of therapeutic DNA to cells. We combine CL with DNA in order to form complexes that can deliver foreign DNA (genes) to cells. In trying to improve the transfection efficiency (TE) of lamellar CL-DNA complexes, we have identified universal trends depending on the headgroup size and charge of the cationic lipid. By using new multivalent lipids ranging from 2+ to 16+ (e.g. Ewert et al, J. Med. Chem. 2002; 45: 5023) we are able to access a wide range of membrane charge density values, or σ _M. TE plots vs. σ M for multivalent lipids merge onto a universal curve with a Gaussian shape. The optimal σ M depends on the overall CL/DNA charge. The universal TE curve shows three regimes related to cellular obstacles: at low σ _M, TE is limited by endosomal escape of CL-DNA, while at high σ M TE is limited by complex dissociation and DNA release into the cytoplasm. Funded by NIH GM-59288 and NSF DMR-0203755.

  6. Involvement of divalent cations in the complex between the platelet glycoproteins IIb and IIIa.

    PubMed

    Hangen, I; Bjerrum, O J; Gogstad, G; Korsmo, R; Solum, N O

    1982-02-01

    The major immunoprecipitate (No. 16) seen on crossed immunoelectrophoresis of Triton X-100-solubilized platelet proteins against whole platelet antibodies represents a complex containing the membrane glycoproteins IIb and IIIa. When EDTA is present during the solubilization, immunoprecipitate 16 as such is not observed, and two new arcs, termed 16a and 16b, appear. As with 16 these immunoprecipitates become radioactively labelled on lactoperoxidase-catalyzed iodination of platelets. Immunoprecipitate 16a showed partial immunochemical identity with 16, and was precipitated by an antibody raised against immunoprecipitate 16. The areas covered by immunoprecipitates 16, 16a and 16b were strongly reduced compared to normal with platelets from a patient with Glanzmann's thrombasthenia type II. Such platelets are known to contain reduced amounts of glycoproteins IIb and IIIa. The new arcs appearing when divalent cations are chelated by EDTA thus represent proteins derived from the immunoprecipitate 16 proteins, and divalent cations seem to be necessary to preserve the protein complex containing glycoprotein IIb and IIIa. The different complex formations between the components of immunoprecipitate 16 may reflect biochemical alterations of functional importance. PMID:6173070

  7. Time-resolved FRET and PCT in cationic conjugated polymer/dye-labeled DNA complex

    NASA Astrophysics Data System (ADS)

    Kim, Inhong; Kim, Jihoon; Kim, Bumjin; Kang, Mijeong; Woo, Han Young; Kyhm, Kwangseuk

    2011-12-01

    The energy transfer mechanism between cationic conjugated polyelectrolytes and a single stranded DNA labeled with fluorescein was investigated in terms of Förster resonance energy transfer (FRET) and photo-induced charge transfer (PCT) by time-resolved fluorescence. Both FRET and PCT rate efficiencies were obtained by phenomenological coupled rate equations, which are in excellent agreement with experiments. We found the total energy transfer in the complex is maximized as a consequence of FRET and PCT at an optimum distance 32.7Å.

  8. Functional Mn–Mg{sub k} cation complexes in GaN featured by Raman spectroscopy

    SciTech Connect

    Devillers, T. Bonanni, A.; Leite, D. M. G.; Dias da Silva, J. H.

    2013-11-18

    The evolution of the optical branch in the Raman spectra of (Ga,Mn)N:Mg epitaxial layers as a function of the Mn and Mg concentrations, reveals the interplay between the two dopants. We demonstrate that the various Mn-Mg-induced vibrational modes can be understood in the picture of functional Mn–Mg{sub k} complexes formed when substitutional Mn cations are bound to k substitutional Mg through nitrogen atoms, the number of ligands k being driven by the ratio between the Mg and the Mn concentrations.

  9. Recent Applications of Acyclic (Diene)iron Complexes and (Dienyl)iron Cations in Organic Synthesis

    PubMed Central

    Chaudhury, Subhabrata

    2009-01-01

    Complexation of (tricarbonyl)iron to an acyclic diene serves to protect the ligand against oxidation, reduction and cycloaddition reactions while the steric bulk of this adjunct serves to direct the approach reagents to unsaturated groups attached to the diene onto the face opposite to iron. Furthermore, the Fe(CO)3 moiety can serve to stabilize carbocation centers adjacent to the diene (i.e. pentadienyl-iron cations). Recent applications of these reactivities to the synthesis of polyene, cyclopropane, cycloheptadiene and cyclohexenone containing natural products or analogs will be presented. PMID:21709767

  10. Adsorption of Cationic Laser Dye onto Polymer/Surfactant Complex Film

    NASA Astrophysics Data System (ADS)

    Paul, Pabitra Kumar; Arshad Hussain, Syed; Bhattacharjee, Debajyoti; Pal, Mrinal

    2011-06-01

    Fabrication of complex molecular films of organic materials is one of the most important issues in modern nanoscience and nanotechnology. Soft materials with flexible properties have been given much attention and can be obtained through bottom up processing from functional molecules, where self-assembly based on supramolecular chemistry and designed assembly have become crucial processes and technologies. In this work, we report the successful incorporation of cationic laser dye rhodamine 6G abbreviated as R6G into the pre-assembled polyelectrolyte/surfactant complex film onto quartz substrate by electrostatic adsorption technique. Poly(allylamine hydrochloride) (PAH) was used as polycation and sodium dodecyl sulphate (SDS) was used as anionic surfactant. UV-Vis absorption spectroscopic characterization reveals the formation of only H-type aggregates of R6G in their aqueous solution and both H- and J-type aggregates in PAH/SDS/R6G complex layer-by-layber films as well as the adsorption kinetics of R6G onto the complex films. The ratio of the absorbance intensity of two aggregated bands in PAH/SDS/R6G complex films is merely independent of the concentration range of the SDS solution used to fabricate PAH/SDS complex self-assembled films. Atomic force microscopy reveals the formation of R6G aggregates in PAH/SDS/R6G complex films.

  11. Competition between pi and non-pi cation-binding sites in aromatic amino acids: a theoretical study of alkali metal cation (Li+, Na+, K+)-phenylalanine complexes.

    PubMed

    Siu, Fung Ming; Ma, Ngai Ling; Tsang, Chun Wai

    2004-04-19

    To understand the cation-pi interaction in aromatic amino acids and peptides, the binding of M(+) (where M(+) = Li(+), Na(+), and K(+)) to phenylalanine (Phe) is studied at the best level of density functional theory reported so far. The different modes of M(+) binding show the same order of binding affinity (Li(+)>Na(+)>K(+)), in the approximate ratio of 2.2:1.5:1.0. The most stable binding mode is one in which the M(+) is stabilized by a tridentate interaction between the cation and the carbonyl oxygen (O[double bond]C), amino nitrogen (--NH(2)), and aromatic pi ring; the absolute Li(+), Na(+), and K(+) affinities are estimated theoretically to be 275, 201, and 141 kJ mol(-1), respectively. Factors affecting the relative stabilities of various M(+)-Phe binding modes and conformers have been identified, with ion-dipole interaction playing an important role. We found that the trend of pi and non-pi cation bonding distances (Na(+)-pi>Na(+)-N>Na(+)-O and K(+)-pi>K(+)-N>K(+)-O) in our theoretical Na(+)/K(+)-Phe structures are in agreement with the reported X-ray crystal structures of model synthetic receptors (sodium and potassium bound lariat ether complexes), even though the average alkali metal cation-pi distance found in the crystal structures is longer. This difference between the solid and the gas-phase structures can be reconciled by taking the higher coordination number of the cations in the lariat ether complexes into account. PMID:15079836

  12. Cationic liposome–nucleic acid complexes for gene delivery and gene silencing

    PubMed Central

    Ewert, Kai K.; Majzoub, Ramsey N.; Leal, Cecília

    2014-01-01

    Cationic liposomes (CLs) are studied worldwide as carriers of DNA and short interfering RNA (siRNA) for gene delivery and gene silencing, and related clinical trials are ongoing. Optimization of transfection efficiency and silencing efficiency by cationic liposome carriers requires a comprehensive understanding of the structures of CL–nucleic acid complexes and the nature of their interactions with cell membranes as well as events leading to release of active nucleic acids within the cytoplasm. Synchrotron x-ray scattering has revealed that CL–nucleic acid complexes spontaneously assemble into distinct liquid crystalline phases including the lamellar, inverse hexagonal, hexagonal, and gyroid cubic phases, and fluorescence microscopy has revealed CL–DNA pathways and interactions with cells. The combining of custom synthesis with characterization techniques and gene expression and silencing assays has begun to unveil structure–function relations in vitro. As a recent example, this review will briefly describe experiments with surface-functionalized PEGylated CL–DNA nanoparticles. The functionalization, which is achieved through custom synthesis, is intended to address and overcome cell targeting and endosomal escape barriers to nucleic acid delivery faced by PEGylated nanoparticles designed for in vivo applications. PMID:25587216

  13. Synthesis and chemistry of cationic d sup 0 metal alkyl complexes

    SciTech Connect

    Jordan, R.F.

    1991-01-01

    The objective of this project is to develop new types of electrophilic metal alkyl complexes for catalytic C-H activation and olefin polymerization chemistry, and associated fundamental mechanistic studies. We have focused our efforts on four classes of early metal alkyl complexes: (1) cationic group 4 Cp{sub 2}M(R){sup +} complexes (1) which are active species in Cp{sub 2}MX{sub 2}-based Ziegler-Natta olefin polymerization catalyst systems and which catalyze productive C-H activation reactions of heterocycles, (2) neutral (dicarbollide)(Cp*)M(R) complexes (2) which are structurally are electronically very similar to 1, (3) half-sandwich complexes CpM(R){sub 2}(L){sub n}{sup +} which are highly coordinatively and electronically unsaturated, and (4) new group 5 (dicarbollide)(Cp)MR{sub 2} and (dicarbollide){sub 2} MR complexes which are more unsaturated than group 5 Cp{sub 2}M systems due to incorporation of the dicarbollide ligand.

  14. Exposing elusive cationic magnesium-chloro aggregates in aluminate complexes through donor control.

    PubMed

    Brouillet, Etienne V; Kennedy, Alan R; Koszinowski, Konrad; McLellan, Ross; Mulvey, Robert E; Robertson, Stuart D

    2016-04-01

    The cationic magnesium moiety of magnesium organohaloaluminate complexes, relevant to rechargeable Mg battery electrolytes, typically takes the thermodynamically favourable dinuclear [Mg2Cl3](+) form in the solid-state. We now report that judicious choice of Lewis donor allows the deliberate synthesis and isolation of the hitherto only postulated mononuclear [MgCl](+) and trinuclear [Mg3Cl5](+) modifications, forming a comparable series with a common aluminate anion [(Dipp)(Me3Si)NAlCl3](-). By pre-forming the Al-N bond prior to introduction of the Mg source, a consistently reproducible protocol is reported. Usage of the green solvent 2-methyltetrahydrofuran in place of THF in the context of Mg/Al battery electrolyte type complexes is also promoted. PMID:26916737

  15. Cationic technetium-99m complexes of N-substituted pyridoxal derivatives as renal function agents

    SciTech Connect

    Karube, Yoshiharu; Iwamoto, Koji; Takata, Jiro

    1994-10-01

    New cationic technetium-chelating agents containing a pyridinium group have been synthesized and evaluated as potential renal radiopharmaceuticals. The pyridinium compounds used in the study are N-methyl pyridoxal chloride, N-ethyl pyridoxal chloride, N-propyl pyridoxal chloride, 1-methyl-3-hydroxy-4-formylpyridinium chloride, 1-methyl-2-formyl-3-hydroxpyridinium chloride and the Schiff`s bases of N-methyl pyridoxal chloride with amino acid, amino acid ester and amino acid amide. Complexes of these chelating agents with {sup 22m}Tc were prepared using a Na{sub 2}S{sub 2}O{sub 4} or a SnCl{sub 2} solution as a reducing agent. The purity of the {sup 99m}Tc complexes was determined by paper electrophoresis in 0.1 Mtris buffer. Electrophoresis indicates slightly positive-charged species. The log P values of these complexes showed a hydrophilic nature. Urinary excretion of the {sup 99m}Tc N-alkylated pyridoxal derivatives, {sup 99m}Tc-diethylenetriaminepentaacetic acid, {sup 99m}Tc-mercaptoacetylglycylglycylglycine (MAG3) and {sup 131}I-o-iodohippurate were determined in mice and rats at different time intervals. In a rat model, the pyridoxal-derived {sup 99m}Tc complexes are rapidly excreted in urine and provide clear renal scintigrams. Hepatobiliary excretion was negligible, reducing scan interference from the intestines. Total clearances were lower than that of {sup 131}I-hippurate and {sup 99m}Tc-MAG3. The rate of urinary clearance of the new tracers was not significantly faster than {sup 99m}Tc diethylenetriaminepentaacetic acid and the inhibitor N{sup 1}-methylnicotinamide had only a minimal effect on the renal behavior. Though the new tracers have cationic properties, the pyridinium group did not contribute largely to the excretion of active transport. 21 refs., 4 figs., 4 tabs.

  16. Cooperativity or phase transition? Unfolding transition of DNA cationic surfactant complex

    NASA Astrophysics Data System (ADS)

    Mel'nikov, Sergey M.; Sergeyev, Vladimir G.; Yoshikawa, Kenichi; Takahashi, Hiroshi; Hatta, Ichiro

    1997-11-01

    We recently reported that single duplex DNA, with the size above the order of several tens kilobase pairs, undergoes a large discrete transition from an elongated coil into a collapsed globule with the addition of a cationic surfactant. In the present article, we describe the manner of the unfolding transition of compact long DNA, or globule DNA, complexed with cationic surfactants, cetyltrimethylammonium bromide (CTAB) and distearyldimethylammonium bromide (D18DAB), as is induced by the addition of sodium bromide. The conformational dynamics of individual single duplex T4DNA molecules was directly observed with the use of fluorescence microscopy. We found that on the level of individual DNAs, the salt-induced unfolding transition of the globules is largely discrete, or first-order phase transition for the both complexes with CTAB and D18DAB. On the other hand, for the ensemble average of the DNAs, the transition is discrete with CTAB but is continuous (sigmoidal) with D18DAB. The discreteness for the coil-globule transition in the ensemble of DNAs complexed with CTAB is attributed to the existence of the phase transition in whole over the bulk solution: the sphere-rod transition in surfactant micelles. On the other hand, for D18DAB such phase transition on the micelle structure in the bulk solution seems to be absent. In correspondence to such a large difference on the manner of the transition, x-ray diffraction analysis indicates marked difference on the structure of DNA complexes with CTAB and with D18DAB.

  17. Two dinuclear Ru(II) polypyridyl complexes with different photophysical and cation recognition properties

    NASA Astrophysics Data System (ADS)

    Cheng, Feixiang; He, Chixian; Ren, Mingli; Wang, Fan; Yang, Yuting

    2015-02-01

    Two dinuclear Ru(II) polypyridyl complexes functionalized with vacant coordination sites have been designed and synthesized. Their photophysical properties and interactions with various metal ions have been investigated at room temperature. The two complexes exhibit different UV/Vis absorption and emission intensities. When titrated with various metal ions, complex [{Ru(bpy)2}2(μ2-L1)]4+ exhibits a notable fluorescence quenching in the presence of Cu2+ in H2O-CH3CN media (1:1, v/v); its analogous complex [{Ru(bpy)2}2(μ2-L2)]4+ exhibits no cation selectivity, the fluorescence intensity of complex [{Ru(bpy)2}2(μ2-L2)]4+ has been enhanced by several transition metal ions due to prevention of the photo-induced electron transfer process. The fluorescence titration spectra and Benesi-Hildebrand expression reveal the formation of a 1:1 bonding mode between [{Ru(bpy)2}2(μ2-L1)]4+ and Cu2+ ion with the association constant of 5.50 × 104 M-1.

  18. Optical tweezers reveal a dynamic mechanical response of cationic peptide-DNA complexes

    NASA Astrophysics Data System (ADS)

    Lee, Amy; Zheng, Tai; Sucayan, Sarah; Chou, Szu-Ting; Tricoli, Lucas; Hustedt, Jason; Kahn, Jason; Mixson, A. James; Seog, Joonil

    2013-03-01

    Nonviral carriers have been developed to deliver nucleic acids by forming nanoscale complexes; however, there has been limited success in achieving high transfection efficiency. Our hypothesis is that a factor affecting gene delivery efficiency is the mechanical response of the condensed complex. To begin to test this hypothesis, we directly measured the mechanical properties of DNA-carrier complexes using optical tweezers. Histidine-lysine (HK) polymer, Asparagine-lysine (NK) polymer and poly-L-lysine were used to form complexes with a single DNA molecule. As carriers were introduced, a sudden decrease in DNA extension occurrs at a force level which is defined as critical force (Fc). Fc is carrier and concentration dependent. Pulling revealed reduction in DNA extension length for HK-DNA complexes. The characteristics of force profiles vary by agent and can be dynamically manipulated by changes in environmental conditions such as ionic strength of the buffer as well as pH. Heparin can remove cationic reagents which are otherwise irreversibly bound to DNA. The implications for optimizing molecular interactions to enhance transfection efficiency will be discussed.

  19. Circular Dichroism is Sensitive to Monovalent Cation Binding in Monensin Complexes.

    PubMed

    Nedzhib, Ahmed; Kessler, Jiří; Bouř, Petr; Gyurcsik, Béla; Pantcheva, Ivayla

    2016-05-01

    Monensin is a natural antibiotic that exhibits high affinity to certain metal ions. In order to explore its potential in coordination chemistry, circular dichroism (CD) spectra of monensic acid A (MonH) and its derivatives containing monovalent cations (Li(+) , Na(+) , K(+) , Rb(+) , Ag(+) , and Et4 N(+) ) in methanolic solutions were measured and compared to computational models. Whereas the conventional CD spectroscopy allowed recording of the transitions down to 192 nm, synchrotron radiation circular dichroism (SRCD) revealed other bands in the 178-192 nm wavelength range. CD signs and intensities significantly varied in the studied compounds, in spite of their similar crystal structure. Computational modeling based on the Density Functional Theory (DFT) and continuum solvent model suggests that the solid state monensin structure is largely conserved in the solutions as well. Time-dependent Density Functional Theory (TDDFT) simulations did not allow band-to-band comparison with experimental spectra due to their limited precision, but indicated that the spectral changes were caused by a combination of minor conformational changes upon the monovalent cation binding and a direct involvement of the metal electrons in monensin electronic transitions. Both the experiment and simulations thus show that the CD spectra of monensin complexes are very sensitive to the captured ions and can be used for their discrimination. Chirality 28:420-428, 2016. © 2016 Wiley Periodicals, Inc. PMID:27062535

  20. Synthesis and structures of neutral and cationic rac-(ethylenebis(tetrahydroindenyl))zirconium(IV) benzyl complexes

    SciTech Connect

    Jordan, R.F.; LaPointe, R.E.; Baenziger, N.; Hinch, G.D. )

    1990-05-01

    Reaction of rac-(ethylenebis(tetrahydroindenyl))ZrCl{sub 2} (1) with 2 equiv of K(CH{sub 2}Ph) produces the dibenzyl complex (ethylenebis(tetrahydroindenyl))Zr(CH{sub 2}Ph){sub 2} (2). Reaction of 2 with ((C{sub 5}H{sub 4}Me){sub 2}Fe)(BPh{sub 4}) yields the cationic complex ((ethylenebis(tetrahydroindenyl))Zr(CH{sub 2}Ph)(THF))(BPh{sub 4}) (3). In CH{sub 3}CN solvent, 3 undergoes ligand substitution to yield ((ethylenebis(tetrahydroindenyl))Zr({eta}{sup 2}-CH{sub 2}Ph)(CH{sub 3}CN))(BPh{sub 4}) (4). The structures of 2 and 4 have been determined by X-ray diffraction. Complex 2 crystallizes in space group Pbcn with a = 10.008 (3) {angstrom}, b = 14.895 (4) {angstrom}, c = 17.532 (6) {angstrom}, V = 2,613.5 (2.4) {angstrom}{sup 3}, and Z = 4. Complex 4 crystallizes in space group P1 with a = 12.300 (2) {angstrom}, b = 12.493 (2) {angstrom}, c = 16.633 (3) {angstrom}, {alpha} = 84.61 (1){degree}, {beta} = 71.18 (1){degree}, {gamma} = 69.42 (1){degree}, V = 2,264.1 (9) {angstrom}{sup 3}, and Z = 2.

  1. Cationic and anionic polyelectrolyte complexes of xylan and chitosan. Interaction with lignocellulosic surfaces.

    PubMed

    Mocchiutti, Paulina; Schnell, Carla N; Rossi, Gerardo D; Peresin, María S; Zanuttini, Miguel A; Galván, María V

    2016-10-01

    Cationic (CatPECs) and anionic (AnPECs) polyelectrolyte complexes from xylan and chitosan were formed, characterized and adsorbed onto unbleached fibers for improving the papermaking properties. They were prepared at a level of 30% of neutralization charge ratio by modifying the order of addition of polyelectrolytes and the ionic strength (0.01N and 0.1N NaCl). The charge density, colloidal stability and particle size of polyelectrolyte complexes (PECs) was measured using polyelectrolyte titration method, Turbiscan and Zetasizer Nano equipments, respectively. All the complexes were stable even after seven days from PEC formation. DRIFT spectra of complexes were also analyzed. The adsorption behavior of them onto cellulose nanofibrils model surfaces was studied using quartz crystal microbalance with dissipation monitoring, and surface plasmon resonance. It was found that the PEC layers were viscoelastic and highly hydrated. Finally, it is shown that the adsorbed PECs onto cellulosic fibers markedly improved the tensile and crushing strengths of paper. PMID:27312617

  2. Modulation of pyridinium cationic lipid-DNA complex properties by pyridinium gemini surfactants and its impact on lipoplex transfection properties.

    PubMed

    Sharma, Vishnu Dutt; Lees, Julia; Hoffman, Nicholas E; Brailoiu, Eugen; Madesh, Muniswamy; Wunder, Stephanie L; Ilies, Marc A

    2014-02-01

    The study presents the effects of blending a cationic gemini surfactant into cationic lipid bilayers and its impact on the plasmid DNA compaction and delivery process. Using nanoDSC, dynamic light scattering, zeta potential, and electrophoretic mobility measurements, together with transfection (2D- and 3D-) and viability assays, we identified the main physicochemical parameters of the lipid bilayers, liposomes, and lipoplexes that are affected by the gemini surfactant addition. We also correlated the cationic bilayer composition with the dynamics of the DNA compaction process and with transfection efficiency, cytotoxicity, and the internalization mechanism of the resultant nucleic acid complexes. We found that the blending of gemini surfactant into the cationic bilayers fluidized the supramolecular assemblies, reduced the amount of positive charge required to fully compact the plasmid DNA and, in certain cases, changed the internalization mechanism of the lipoplexes. The transfection efficiency of select ternary lipoplexes derived from cationic gemini surfactants and lipids was several times superior to the transfection efficiency of corresponding binary lipoplexes, also surpassing standard transfection systems. The overall impact of gemini surfactants into the formation and dynamic of cationic bilayers was found to depend heavily on the presence of colipids, their nature, and amount present in lipoplexes. The study confirmed the possibility of combining the specific properties of pyridinium gemini surfactants and cationic lipids synergistically to obtain efficient synthetic transfection systems with negligible cytotoxicity useful for therapeutic gene delivery. PMID:24377350

  3. Modulation of pyridinium cationic lipid-DNA complex properties by pyridinium gemini surfactants and its impact on lipoplex transfection properties

    PubMed Central

    Sharma, Vishnu Dutt; Lees, Julia; Hoffman, Nicholas E.; Brailoiu, Eugen; Madesh, Muniswamy; Wunder, Stephanie L.; Ilies, Marc A.

    2014-01-01

    The study presents the effects of blending a cationic gemini surfactant into cationic lipid bilayers and its impact towards plasmid DNA compaction and delivery process. Using nanoDSC, dynamic light scattering, zeta potential and electrophoretic mobility measurements, together with transfection (2D- and 3D-) and viability assays, we identified the main physicochemical parameters of the lipid bilayers, liposomes and lipoplexes that are affected by the gemini surfactant addition. We also correlated the cationic bilayer composition with the dynamics of the DNA compaction process, and with transfection efficiency, cytotoxicity and internalization mechanism of the resultant nucleic acid complexes. We found that blending of gemini surfactant into the cationic bilayers fluidized the supramolecular assemblies, reduced the amount of positive charge required to fully compact the plasmid DNA and, in certain cases, changed the internalization mechanism of the lipoplexes. Transfection efficiency of select ternary lipoplexes derived from cationic gemini surfactants and lipids was several times superior to transfection efficiency of corresponding binary lipoplexes, also surpassing standard transfection systems. The overall impact of gemini surfactants into the formation and dynamic of cationic bilayers was found to depend heavily on the presence of co-lipids, their nature and amount present into lipoplexes. The study confirmed the possibility of combining the specific properties of pyridinium gemini surfactants and cationic lipids synergistically for obtaining efficient synthetic transfection systems with negligible cytotoxicity useful for therapeutic gene delivery. PMID:24377350

  4. Gene Delivery from Supercharged Coiled-coil Protein and Cationic Lipid Hybrid Complex

    PubMed Central

    More, Haresh T.; Frezzo, Joseph A.; Dai, Jisen; Yamano, Seiichi; Montclare, Jin K.

    2014-01-01

    A lipoproteoplex comprised of an engineered supercharged coiled-coil protein (CSP) bearing multiple arginines and the cationic lipid formulation FuGENE HD (FG) was developed for effective condensation and delivery of nucleic acids. The CSP was able to maintain helical structure and self-assembly properties while exhibiting binding to plasmid DNA. The ternary CSP•DNA(8:1)•FG lipoproteoplex complex demonstrated enhanced transfection of β-galactosidase DNA into MC3T3-E1 mouse preosteoblasts. The lipoproteoplexes showed significant increases in transfection efficiency when compared to conventional FG and an mTat•FG lipopolyplex with a 6- and 2.5-fold increase in transfection, respectively. The CSP•DNA(8:1)•FG lipoproteoplex assembled into spherical particles with a net positive surface charge, enabling efficient gene delivery. These results support the application of lipoproteoplexes with protein engineered CSP for non-viral gene delivery. PMID:24875765

  5. Unexpected Actinyl Cation-Directed Structural Variation in Neptunyl(VI) A-Type Tri-lacunary Heteropolyoxotungstate Complexes.

    PubMed

    Berg, John M; Gaunt, Andrew J; May, Iain; Pugmire, Alison L; Reilly, Sean D; Scott, Brian L; Wilkerson, Marianne P

    2015-05-01

    A-type tri-lacunary heteropolyoxotungstate anions (e.g., [PW9O34](9-), [AsW9O34](9-), [SiW9O34](10-), and [GeW9O34](10-)) are multidentate oxygen donor ligands that readily form sandwich complexes with actinyl cations ({UO2}(2+), {NpO2}(+), {NpO2}(2+), and {PuO2}(2+)) in near-neutral/slightly alkaline aqueous solutions. Two or three actinyl cations are sandwiched between two tri-lacunary anions, with additional cations (Na(+), K(+), or NH4(+)) also often held within the cluster. Studies thus far have indicated that it is these additional +1 cations, rather than the specific actinyl cation, that direct the structural variation in the complexes formed. We now report the structural characterization of the neptunyl(VI) cluster complex (NH4)13[Na(NpO2)2(A-α-PW9O34)2]·12H2O. The anion in this complex, [Na(NpO2)2(PW9O34)2](13-), contains one Na(+) cation and two {NpO2}(2+) cations held between two [PW9O34](9-) anions, with an additional partial occupancy NH4(+) or {NpO2}(2+) cation also present. In the analogous uranium(VI) system, under similar reaction conditions that include an excess of NH4Cl in the parent solution, it was previously shown that [(NH4)2(U(VI)O2)2(A-PW9O34)2](12-) is the dominant species in both solution and the crystallized salt. Spectroscopic studies provide further proof of differences in the observed chemistry for the {NpO2}(2+)/[PW9O34](9-) and {UO2}(2+)/[PW9O34](9-) systems, both in solution and in solid state complexes crystallized from comparable salt solutions. This work reveals that varying the actinide element (Np vs U) can indeed measurably impact structure and complex stability in the cluster chemistry of actinyl(VI) cations with A-type tri-lacunary heteropolyoxotungstate anions. PMID:25901900

  6. Unexpected Actinyl Cation-Directed Structural Variation in Neptunyl(VI) A-Type Tri-lacunary Heteropolyoxotungstate Complexes

    DOE PAGESBeta

    Berg, John M.; Gaunt, Andrew J.; May, Iain; Pugmire, Alison L.; Reilly, Sean D.; Scott, Brian L.; Wilkerson, Marianne P.

    2015-04-22

    A-type tri-lacunary heteropolyoxotungstate anions (e.g., [PW9O34]9-, [AsW9O34]9-, [SiW9O34]10- and [GeW9O34]10-) are multi-dentate oxygen donor ligands that readily form sandwich complexes with actinyl cations ({UO2}2+, {NpO2}+, {NpO2}2+ & {PuO2}2+) in near neutral/slightly alkaline aqueous solutions. Two or three actinyl cations are sandwiched between two trilacunary anions, with additional cations (Na+, K+ or NH4 +) also often held within the cluster. Studies thus far have indicated that it is these additional +I cations, rather than the specific actinyl cation, that direct the structural variation in the complexes formed. We now report the structural characterization of the neptunyl (VI) cluster complex (NH4)13 [Na(NpO2)2(A-α-more » PW9O34)2]·12H2O. The anion in this complex, [Na(NpO2)2(PW9O34)2]13-, contains one Na+ cation and two {NpO2}2+ cations held between two [PW9O34]9- anions – with an additional partial occupancy NH4 + or {NpO2}2+ cation also present. In the analogous uranium (VI) system, under similar reaction conditions that includes an excess of NH4Cl in the parent solution, it was previously shown that [(NH4)2(UVIO2)2(A-PW9O34)2]12- is the dominant species in both solution and the crystallized salt. Spectroscopic studies provide further proof of differences in the observed chemistry for the {NpO2}2+/[PW9O34]9- and {UO2}2+/[PW9O34]9- systems, both in solution and in solid state complexes crystallized from comparable salt solutions. The work revealed that varying the actinide element (Np vs. U) can indeed measurably impact structure and complex stability in the cluster chemistry of actinyl (VI) cations with A-type tri-lacunary heteropolyoxotungstate anions.« less

  7. Cationic bis-N-heterocyclic carbene (NHC) ruthenium complex: structure and application as latent catalyst in olefin metathesis.

    PubMed

    Rouen, Mathieu; Queval, Pierre; Falivene, Laura; Allard, Jessica; Toupet, Loïc; Crévisy, Christophe; Caijo, Frédéric; Baslé, Olivier; Cavallo, Luigi; Mauduit, Marc

    2014-10-13

    An unexpected cationic bis-N-heterocyclic carbene (NHC) benzylidene ether based ruthenium complex (2 a) was prepared through the double incorporation of an unsymmetrical unsaturated N-heterocyclic carbene (U2 -NHC) ligand that bore an N-substituted cyclododecyl side chain. The isolation and full characterization (including X-ray diffraction studies) of key synthetic intermediates along with theoretical calculations allowed us to understand the mechanism of the overall cationization process. Finally, the newly developed complex 2 a displayed interesting latent behavior during ring-closing metathesis, which could be "switched on" under acidic conditions. PMID:25212827

  8. Computational study on the complexation behavior of tetrapropyl diglycolamide with Ln3+ (Ln = Nd, Pm, Sm, and Eu) cation series

    NASA Astrophysics Data System (ADS)

    Hosseinnejad, Tayebeh; Nikoo, Sepideh

    2015-09-01

    In the present study, we have focused mainly on the survey of interactions in Ln3+ (Ln = Nd, Pm, Sm, Eu) complexes with tetrapropyl diglycolamide (TPDGA) by means of density functional theory (DFT) methods. In the first step, the interaction of TPDGA ligand with Ln3+ cation series has been assessed thermodynamically in the gas phase and in presence of three solvents: n-hexane, chloroform and toluene, via polarized continuum model (PCM) calculations. The trend of metal-ligand interaction strength has been investigated and compared with the trend of ionic hardness within the series of lanthanide cations. Our results for the gas and solution phases demonstrate a consistency between the increasing trend in the hardness of Ln3+ cation series with the increasing in thermodynamical stability of [Ln(TPDGA)]3+ complex series. Moreover, our PCM calculations show that using n-hexane as a solvent is more favorable thermodynamically than chloroform and toluene for the complexation reaction of all [Ln(TPDGA)]3+ complex series. It should be stated that this issue has been observed in many experimental calculations. Finally the assessment of calculated deformation energies and also the variation in bond order of some selected key bonds in [Ln(TPDGA)]3+ complex series shows a similar trend with increasing in the hardness of Ln3+ cation series.

  9. Spin-coupling in ferric metalloporphyrin radical cation complexes: Mössbauer and susceptibility studies

    NASA Astrophysics Data System (ADS)

    Lang, George; Boso, Brian; Erler, Brian S.; Reed, Christopher A.

    1986-03-01

    The ferric metalloporphyrin π-radical cation complexes Fe(III) (OClO3)2 (TPP.) and [Fe(III) Cl (TPP.)] [SbCl6] were examined in microcrystalline form by Mössbauer spectroscopy and magnetic susceptometry over a range of temperatures and applied fields. All measurements on the six-coordinate Fe(OClO3)2 (TPP.) were consistent with isolated molecules having an S=5/2 iron site with zero field splitting (12 cm-1) S2z that is ferromagnetically coupled to the S=1/2 porphyrin radical by an energy term (-110 cm-1) Sṡs. Thus the ground state is overall spin-3. In the five-coordinate [FeCl (TPP.)] [SbCl6] the susceptibility is in reasonable agreement with the results of a calculation based on zero field splitting (12 cm-1) S2z for the S=5/2 iron and antiferromagnetic coupling (200 cm-1) Sṡs with the radical to give an overall spin-2 ground state. However, the Mössbauer measurements require a more complicated model having the same large intramolecular iron-radical coupling, a smaller zero field splitting (3 cm-1) S2z, and weak intermolecular antiferromagnetic coupling between heme pairs given by (32 cm-1) s1ṡs2 or, equivalently, (0.65 cm-1) S1ṡS2. A slightly improved correspondence with the measured susceptibility results. The intermolecular antiferromagnetic coupling probably results from crystallization of the [FeCl (TPP.)]+ cations in face-to-face dimers as observed in other closely related five-coordinate iron (III) porphyrins.

  10. Cationic drug-based self-assembled polyelectrolyte complex micelles: Physicochemical, pharmacokinetic, and anticancer activity analysis.

    PubMed

    Ramasamy, Thiruganesh; Poudel, Bijay Kumar; Ruttala, Himabindu; Choi, Ju Yeon; Hieu, Truong Duy; Umadevi, Kandasamy; Youn, Yu Seok; Choi, Han-Gon; Yong, Chul Soon; Kim, Jong Oh

    2016-10-01

    Nanofabrication of polymeric micelles through self-assembly of an ionic block copolymer and oppositely charged small molecules has recently emerged as a promising method of formulating delivery systems. The present study therefore aimed to investigate the interaction of cationic drugs doxorubicin (DOX) and mitoxantrone (MTX) with the anionic block polymer poly(ethylene oxide)-block-poly(acrylic acid) (PEO-b-PAA) and to study the influence of these interactions on the pharmacokinetic stability and antitumor potential of the formulated micelles in clinically relevant animal models. To this end, individual DOX and MTX-loaded polyelectrolyte complex micelles (PCM) were prepared, and their physicochemical properties and pH-responsive release profiles were studied. MTX-PCM and DOX-PCM exhibited a different release profile under all pH conditions tested. MTX-PCM exhibited a monophasic release profile with no initial burst, while DOX-PCM exhibited a biphasic release. DOX-PCM showed a higher cellular uptake than that shown by MTX-PCM in A-549 cancer cells. Furthermore, DOX-PCM induced higher apoptosis of cancer cells than that induced by MTX-PCM. Importantly, both MTX-PCM and DOX-PCM showed prolonged blood circulation. MTX-PCM improved the AUCall of MTX 4-fold compared to a 3-fold increase by DOX-PCM for DOX. While a definite difference in blood circulation was observed between MTX-PCM and DOX-PCM in the pharmacokinetic study, both MTX-PCM and DOX-PCM suppressed tumor growth to the same level as the respective free drugs, indicating the potential of PEGylated polymeric micelles as effective delivery systems. Taken together, our results show that the nature of interactions of cationic drugs with the polyionic copolymer can have a tremendous influence on the biological performance of a delivery system. PMID:27318960

  11. Methodology for the calculation of the potential of mean force for a cation-pi complex in water.

    PubMed

    Ghoufi, Aziz; Archirel, Pierre; Morel, Jean-Pierre; Morel-Desrosiers, Nicole; Boutin, Anne; Malfreyt, Patrice

    2007-08-01

    We report potential of mean force (PMF) calculations on the interaction between the p-sulfonatocalix[4]arene and a monovalent cation (Cs(+)). It has been recently shown from microcalorimetry and (133)Cs NMR experiments that the association with Cs(+) is governed by favourable cation-pi interactions and is characterized by the insertion of the cation into the cavity of the macrocycle. We show that the PMF calculation based upon a classical model is not able to reproduce both the thermodynamic properties of association and the insertion of the cation. In order to take into account the different contributions of the cation-pi interactions, we develop a new methodology consisting of changing the standard PMF by an additional contribution resulting from quantum calculations. The calculated thermodynamic properties of association are thus in line with the microcalorimetry and (133)Cs NMR experiments and the structure of the complex at the Gibbs free-energy minimum shows the insertion of the cation into the cavity of the calixarene. PMID:17583904

  12. Influence of phospholipid composition on cationic emulsions/DNA complexes: physicochemical properties, cytotoxicity, and transfection on Hep G2 cells

    PubMed Central

    Fraga, Michelle; Bruxel, Fernanda; Lagranha, Valeska Lizzi; Teixeira, Helder Ferreira; Matte, Ursula

    2011-01-01

    Background Cationic nanoemulsions have been recently considered as potential delivery systems for nucleic acids. This study reports the influence of phospholipids on the properties of cationic nanoemulsions/DNA plasmid complexes. Methods Nanoemulsions composed of medium-chain triglycerides, stearylamine, egg lecithin or isolated phospholipids, ie, DSPC, DOPC, DSPE, or DOPE, glycerol, and water were prepared by spontaneous emulsification. Gene transfer to Hep G2 cells was analyzed using real-time polymerase chain reaction. Results The procedure resulted in monodispersed nanoemulsions with a droplet size and zeta potential of approximately 250 nm and +50 mV, respectively. The complexation of cationic nanoemulsions with DNA plasmid, analyzed by agarose gel retardation assay, was complete when the complex was obtained at a charge ratio of ≥1.0. In these conditions, the complexes were protected from enzymatic degradation by DNase I. The cytotoxicity of the complexes in Hep G2 cells, evaluated by MTT assay, showed that an increasing number of complexes led to progressive toxicity. Higher amounts of reporter DNA were detected for the formulation obtained with the DSPC phospholipid. Complexes containing DSPC and DSPE phospholipids, which have high phase transition temperatures, were less toxic in comparison with the formulations obtained with lecithin, DOPC, and DOPE. Conclusion The results show the effect of the DNA/nanoemulsion complexes composition on the toxicity and transfection results. PMID:22114484

  13. Self-assembled DNA-cationic-lipid complexes: Two-dimensional smectic ordering, correlations, and interactions

    NASA Astrophysics Data System (ADS)

    Salditt, T.; Koltover, I.; Rädler, J. O.; Safinya, C. R.

    1998-07-01

    We report a synchrotron small-angle x-ray scattering (SAXS) study of the mutilayered, self-assembled structure (complex) that is formed by mixing DNA with cationic liposomes. In these complexes the DNA is confined between charged lipid bilayers and orders as a two-dimensional (2D) smectic liquid crystal. The power-law bilayer-bilayer correlations of the 3D multilayer smectic liquid crystal, which are coupled to the 2D lattice of DNA chains, are found to deviate significantly from those described by the standard Caillé model of smectic-A phases. To model the DNA ordering, the 2D smectic correlation function and the corresponding structure factor are derived from the smectic Hamiltonian in harmonic approximation. The resulting line shape is then fitted to the DNA correlation peak. It is found that for samples of higher d, short-range correlations between the DNA in adjacent sheets have to be assumed to explain the data. From the least-square fitting, the 2D DNA interchain compressibility modulus B is extracted as a function of d and discussed in view of different possible microscopic interactions responsible for the ordering.

  14. Genetic factors influence level of proteinuria in cationic antigen-induced immune complex glomerulonephritis in the rat.

    PubMed Central

    Kato, A; Thaiss, F; Oite, T; Günther, E; Batsford, S; Vogt, A

    1985-01-01

    The influence of genetic factors on the susceptibility of the rat to cationic antigen-induced in situ immune complex glomerulonephritis was investigated. The levels of proteinuria developing in 11 inbred strains of rats differing in MHC and in genetic background varied markedly. Susceptibility was not MHC associated but resided in the genetic background. PMID:3159528

  15. A study of molecular adsorption of a cationic surfactant on complex surfaces with atomic force microscopy.

    PubMed

    Sokolov, I; Zorn, G; Nichols, J M

    2016-02-01

    The study of molecular adsorption on solid surfaces is of broad interest. However, so far the study has been restricted to idealized flat smooth rigid surfaces which are rarely the case in real world applications. Here we describe a study of molecular adsorption on a complex surface of the submicron fibers of a fibrous membrane of regenerated cellulose in aqueous media. We use a cationic surfactant, cetyltrimethylammonium chloride (CTAC), as the adsorbing molecule. We study the equilibrium adsorption of CTAC molecules on the same area of the fibers by sequentially immersing the membrane in pure water, 1 mM and then a 20 mM solution of CTAC. Atomic force microscopy (AFM) is applied to study the adsorption. The force-volume mode is used to record the force-deformation curves of the adsorbed molecules on the fiber surface. We suggest a model to separate the forces due to the adsorbed molecules from the elastic deformation of the fiber. Interestingly, knowledge of the surface geometry is not required in this model provided the surface is made of elastically homogeneous material. Different models are investigated to estimate the amount of the adsorbed molecules based on the obtained force curves. The exponential steric repulsion model fits the force data the best. The amount of the adsorbed surfactant molecules and its dependence on the concentration are found to be reasonable compared to the data previously measured by means of Raman scattering done on a flat surface of silica. PMID:26730682

  16. Investigation of complexes formed by interaction of cationic gemini surfactants with deoxyribonucleic acid.

    PubMed

    Wang, Chuanzhong; Li, Xingfu; Wettig, Shawn D; Badea, Ildiko; Foldvari, Marianna; Verrall, Ronald E

    2007-04-01

    Cationic gemini surfactants, N,N-bis(dimethylalkyl)-alpha,omega-alkanediammonium dibromide [C(m)H(2m+1)(CH(3))(2)N(+)(CH(2))(s)N(+)(CH(3))(2)C(m)H(2m+1) x 2 Br(-), or m-s-m], have proven to be effective synthetic vectors for gene delivery (transfection). Complexes (lipoplexes) of gemini compounds, where m = 12, s = 3, 12 and m = 18 : 1(oleyl), s = 2, 3, 6, with DNA have been investigated using isothermal titration calorimetry (ITC), dynamic light scattering (DLS), zeta potential, atomic force microscopy (AFM) and circular dichroism (CD) techniques. The results show that lipoplex properties depend on the structural properties of the gemini surfactants, the presence of the helper lipid dioleoylphosphatidylethanolamine (DOPE), and the titration sequence. ITC data show that the interaction between DNA and gemini surfactants is endothermic and the observed enthalpy vs. charge ratio profile depends upon the titration sequence. Isoelectric points (IP) of lipoplex formation were estimated from the zeta potential measurements and show good agreement with the reaction endpoints (RP) obtained from ITC. DLS data indicate that DNA is condensed in the lipoplex. AFM images suggest that the lipoplex morphology changes from isolated globular-like aggregated particles to larger-size aggregates with great diversity in morphology. This change is further accentuated by the presence of DOPE in the lipoplexes. The results are interpreted in terms of some current models of lipoplex formation. PMID:17429555

  17. DNA and its cationic lipid complexes induce CpG motif-dependent activation of murine dendritic cells

    PubMed Central

    Yoshinaga, Takaharu; Yasuda, Kei; Ogawa, Yoshiyuki; Nishikawa, Makiya; Takakura, Yoshinobu

    2007-01-01

    Unmethylated CpG motifs in bacterial DNA, but not in vertebrate DNA, are known to trigger an inflammatory response of antigen-presenting cells (APC). In this study, we investigated the cytokine release from murine dendritic cells (DC) by the addition of various types of DNA in the free or complexed form with cationic lipids. Naked plasmid DNA and Escherichia coli DNA with immunostimulatory unmethylated CpG motifs induced pro-inflammatory cytokine secretion from granulocyte–macrophage colony-stimulating factor (GM-CSF)-cultured bone marrow-derived DC and the DC cell-line, DC2.4 cells, though vertebrate calf thymus DNA (CT DNA) with less CpG motifs did not. These characteristics differed from mouse peritoneal resident macrophages that do not respond to any naked DNA. The amount of cytokines released from the DC was significantly increased by complex formation with cationic lipids when CpG-motif positive DNAs were used. Unlike murine macrophages or Flt-3 L cultured DC, GM-CSF DC did not release inflammatory cytokines in response to the addition of CT DNA/cationic lipid complex, suggesting that the activation is completely dependent on CpG motifs. Taken together, the results of the present study demonstrate that murine DC produce pro-inflammatory cytokines upon stimulation with CpG-containing DNAs and the responses are enhanced by cationic lipids. These results also suggest that DC are the major cells that respond to naked CpG DNA in vivo, although both DC and macrophages will release inflammatory cytokines after the administration of a DNA/cationic lipid complex. PMID:17199803

  18. Coordinatively saturated cationic ruthenium(II) complexes. Preparation, characterization, and reaction with potassium superoxide

    SciTech Connect

    Oshima, N.; Suzuki, H.; Moro-oka, Y.

    1986-09-10

    Coordinatively saturated cationic ruthenium(II) complexes, (eta/sup 5/-C/sub 5/H/sub 5/)(eta/sup 6/-C/sub 6/H/sub 6/)Ru/sup II/)(BF/sub 4/) (1), (eta/sup 5/-C/sub 5/Me/sub 5/)(eta/sup 6/-C/sub 66/)Ru/sup II/)(BF/sub 4/) (2), ((1-5-eta/sup 5/-C/sub 6/H/sub 7/)(eta/sup 6/-C/sub 6/H/sub 6/)Ru/sup II/)(BF/sub 4/) (3), ((1-5-eta/sup 5/-C/sub 7/H/sub 9/)(eta/sup 6/-C/sub 6/H/sub 7/)Ru/sup II/)(BF/sub 4/) (4), ((1-3:5,6-eta/sup 5/-C/sub 8/H/sub 1/exclamation)(eta/sup 6/-C/sub 6/H/sub 6/)Ru/sup II/)(BG/sub 4/)(5), and ((6-EtO-1-5-eta /sup 5/-C/sub 7/H/sub 8/)(eta/sup 6/-C/sub 6/H/sub 6/)Ru/sup II/)(BF/sub 4/) (7), are prepared by the reaction of (eta/sup 6/-C/sub 6/H/sub 6/)RuCl/sub 2/)/sub 2/ with cyclopentadiene, pentamethylcyclopentadiene, 1,3-cyclohexadiene, 1,3-cycloheptadiene, 1,5-cyclooctadiene, and 1,3,5-cycloheptatriene, respectively, in ethanol in the presence of AgBF/sub 4/. Superoxide anion attacks at the terminal position of the dienyl moiety of 3-5 to yield ruthenium(0) complexes 8-10, containing cyclic dienone ligand. 25 references, 4 figures, 4 tables.

  19. Novel amphiphilic cationic porphyrin and its Ag(II) complex as potential anticancer agents

    PubMed Central

    Tovmasyan, Artak; Babayan, Nelli; Poghosyan, David; Margaryan, Kristine; Harutyunyan, Boris; Grigoryan, Rusanna; Sarkisyan, Natalia; Spasojevic, Ivan; Mamyan, Suren; Sahakyan, Lida; Aroutiounian, Rouben; Ghazaryan, Robert; Gasparyan, Gennadi

    2015-01-01

    In the present study we have synthesized a novel amphiphilic porphyrin and its Ag(II) complex through modification of water-soluble porphyrinic structure in order to increase its lipophilicity and in turn pharmacological potency. New cationic non-symmetrical meso-substituted porphyrins were characterized by UV–visible, electrospray ionization mass spectrometry (ESI-MS), 1H NMR techniques, lipophilicity (thin-layer chromatographic retention factor, Rf), and elemental analysis. The key toxicological profile (i.e. cytotoxicity and cell line-(cancer type-) specificity; genotoxicity; cell cycle effects) of amphiphilic Ag porphyrin was studied in human normal and cancer cell lines of various tissue origins and compared with its water-soluble analog. Structural modification of the molecule from water-soluble to amphiphilic resulted in a certain increase in the cytotoxicity and a decrease in cell line-specificity. Importantly, Ag(II) porphyrin showed less toxicity to normal cells and greater toxicity to their cancerous counterparts as compared to cisplatin. The amphiphilic complex was also not genotoxic and demonstrated a slight cytostatic effect via the cell cycle delay due to the prolongation of S-phase. As expected, the performed structural modification affected also the photocytotoxic activity of metal-free amphiphilic porphyrin. The ligand tested on cancer cell line revealed a dramatic (more than 70-fold) amplification of its phototoxic activity as compared to its water-soluble tetracationic metal-free analog. The compound combines low dark cytotoxicity with 5 fold stronger phototoxicity relative to Chlorin e6 and could be considered as a potential photosensitizer for further development in photodynamic therapy. PMID:25086237

  20. Reactions of heteroatom and carbon nucleophiles with the cationic bridging methylidyne complex

    SciTech Connect

    Casey, C.P.; Crocker, M.; Vosejpka, P.C.; Fagan, P.J.; Marder, S.R.; Gohdes, M.A.

    1988-03-01

    The reaction of the ..mu..-methylidyne complex /((C/sub 5/H/sub 5/)(CO)Fe)/sub 2/(..mu..-CO)(..mu..-CH)//sup +/PF/sub 6//sup -/ (1) with NMe/sub 3/ and (C/sub 6/H/sub 5/)/sub 2/C=NH gave the cationic 1:1 adducts /((C/sub 5/H/sub 5/)(CO)Fe)/sub 2/(..mu..-CO)(..mu..-CHNMe/sub 3/)//sup +/PF/sub 6//sup -/ (3) and /((C/sub 5/H/sub 5/)(CO)Fe)/sub 2/(..mu..-CHNH=C(C/sub 6/H/sub 5/)/sub 2/)//sup +/PF/sub 6//sup -/ (9), respectively, arising from attack of nitrogen on the methylidyne carbon. The reaction of 1 with KOC(CH/sub 3/)/sub 3/ gave the neutral ..mu..-carbene complex ((C/sub 5/H/sub 5/)(CO)Fe)/sub 2/(..mu..-CO)(..mu..-CHOC(CH/sub 3/)P/sub 3/) (4). Reaction of 1 with water afforded a 1:1 mixture of ..mu..methylene complex ((C/sub 5/H/sub 5/)(CO)Fe)/sub 2/(..mu..-CO)(..mu..-CH/sub 2/) (2) and ((C/sub 5/H/sub 5/)(CO)Fe)/sub 2/(..mu..-CO)/sub 2/; these products are proposed to arise from disproportionation of an initially formed hydroxy carbene species. Reaction of 1 with Et/sub 4/N/sup +/Br/sup -/ gave the unstable /sup +/-carbene complex ((C/sub 5/H/sub 5/)(CO)Fe)/sub 2/(..mu..-CO)(..mu..-CHBr) (6). Reaction of 1 with the carbon nucleophiles CH/sub 3/Li and Li(C/sub 6/H/sub 5/CuCN) gave the ..mu..-carbene complexes ((C/sub 5/H/sub 5/)(CO)Fe/sub 2/(..mu..-CO)(..mu..-CHCH/sub 3/) (11) and ((C/sub 5/H/sub 5/)(CO)Fe)/sub 2/(..mu..-CO)(..mu..-CHC/sub 6/H/sub 5/ (12), while reaction of 1 with HFe(CO)/sub 4//sup -/ afforded 2. 1 reacted with acetone via nucleophilic addition of the enol affording the neutral ..mu..-carbene complex (C/sub 5/H/sub 5/)-(CO)Fe)/sub 2/(..mu..-CO)(..mu..-CHCH/sub 2/COCH/sub 3/)) (13). 1 also reacted with cyclohexanone, 2-butanone, 4-methyl-2-pentanone, 2,4-pentanedione, 5,5-dimethyl-1,3-cyclohexanedione, ethyl acetoacetate, and the sodium salt of diethyl malonate to give similar ..mu..-carbene products.

  1. The electronic structure of vanadium monochloride cation (VCl(+)): tackling the complexities of transition metal species.

    PubMed

    DeYonker, Nathan J; Halfen, DeWayne T; Allen, Wesley D; Ziurys, Lucy M

    2014-11-28

    Six electronic states (X (4)Σ(-), A (4)Π, B (4)Δ, (2)Φ, (2)Δ, (2)Σ(+)) of the vanadium monochloride cation (VCl(+)) are described using large basis set coupled cluster theory. For the two lowest quartet states (X (4)Σ(-) and A (4)Π), a focal point analysis (FPA) approach was used that conjoined a correlation-consistent family of basis sets up to aug-cc-pwCV5Z-DK with high-order coupled cluster theory through pentuple (CCSDTQP) excitations. FPA adiabatic excitation energies (T0) and spectroscopic constants (re, r0, Be, B0, D¯e, He, ωe, v0, αe, ωexe) were extrapolated to the valence complete basis set Douglas-Kroll (DK) aug-cc-pV∞Z-DK CCSDT level of theory, and additional treatments accounted for higher-order valence electron correlation, core correlation, and spin-orbit coupling. Due to the delicate interplay between dynamical and static electronic correlation, single reference coupled cluster theory is able to provide the correct ground electronic state (X (4)Σ(-)), while multireference configuration interaction theory cannot. Perturbations from the first- and second-order spin orbit coupling of low-lying states with quartet spin multiplicity reveal an immensely complex rotational spectrum relative to the isovalent species VO, VS, and TiCl. Computational data on the doublet manifold suggest that the lowest-lying doublet state ((2)Γ) has a Te of ∼11 200 cm(-1). Overall, this study shows that laboratory and theoretical rotational spectroscopists must work more closely in tandem to better understand the bonding and structure of molecules containing transition metals. PMID:25429937

  2. The electronic structure of vanadium monochloride cation (VCl+): Tackling the complexities of transition metal species

    NASA Astrophysics Data System (ADS)

    DeYonker, Nathan J.; Halfen, DeWayne T.; Allen, Wesley D.; Ziurys, Lucy M.

    2014-11-01

    Six electronic states (X 4Σ-, A 4Π, B 4Δ, 2Φ, 2Δ, 2Σ+) of the vanadium monochloride cation (VCl+) are described using large basis set coupled cluster theory. For the two lowest quartet states (X 4Σ- and A 4Π), a focal point analysis (FPA) approach was used that conjoined a correlation-consistent family of basis sets up to aug-cc-pwCV5Z-DK with high-order coupled cluster theory through pentuple (CCSDTQP) excitations. FPA adiabatic excitation energies (T0) and spectroscopic constants (re, r0, Be, B0, bar De, He, ωe, v0, αe, ωexe) were extrapolated to the valence complete basis set Douglas-Kroll (DK) aug-cc-pV∞Z-DK CCSDT level of theory, and additional treatments accounted for higher-order valence electron correlation, core correlation, and spin-orbit coupling. Due to the delicate interplay between dynamical and static electronic correlation, single reference coupled cluster theory is able to provide the correct ground electronic state (X 4Σ-), while multireference configuration interaction theory cannot. Perturbations from the first- and second-order spin orbit coupling of low-lying states with quartet spin multiplicity reveal an immensely complex rotational spectrum relative to the isovalent species VO, VS, and TiCl. Computational data on the doublet manifold suggest that the lowest-lying doublet state (2Γ) has a Te of ˜11 200 cm-1. Overall, this study shows that laboratory and theoretical rotational spectroscopists must work more closely in tandem to better understand the bonding and structure of molecules containing transition metals.

  3. Thermodynamic study of the complexation of trivalent actinide and lanthanide cations by ADPTZ, a tridentate N-donor ligand.

    PubMed

    Miguirditchian, Manuel; Guillaneux, Denis; Guillaumont, Dominique; Moisy, Philippe; Madic, Charles; Jensen, Mark P; Nash, Kenneth L

    2005-03-01

    To better understand the bonding in complexes of f-elements by polydentate N-donor ligands, the complexation of americium(III) and lanthanide(III) cations by 2-amino-4,6-di-(pyridin-2-yl)-1,3,5-triazine (ADPTZ) was studied using a thermodynamic approach. The stability constants of the 1:1 complexes in a methanol/water mixture (75/25 vol %) were determined by UV-visible spectrophotometry for every lanthanide(III) ion (except promethium), and yttrium(III) and americium(III) cations. The thermodynamic parameters (DeltaH degrees , DeltaS degrees) of complexation were determined from the temperature dependence of the stability constants and by microcalorimetry. The trends of the variations of DeltaG degrees , DeltaH degrees , and DeltaS degrees across the lanthanide series are compared with published results for other tridentate ligands and confirm strongly ionic bonding in the lanthanide-ADPTZ complexes. Comparison of the thermodynamic properties between the Am- and Ln-ADPTZ complexes highlights an increase in stability of the complexes by a factor of 20 in favor of the americium cation. This difference arises from a more exothermic reaction enthalpy in the case of Am, which is correlated with a greater degree of covalency in the americium-nitrogen bonds. Quantum chemistry calculations performed on a series of trivalent actinide and lanthanide-ADPTZ complexes support the experimental results, showing a slightly greater covalence in the actinide-ligand bonds that originates from a charge transfer from the ligand sigma orbitals to the 5f and 6d orbitals of the actinide ion. PMID:15732980

  4. Unexpected Actinyl Cation-Directed Structural Variation in Neptunyl(VI) A-Type Tri-lacunary Heteropolyoxotungstate Complexes

    SciTech Connect

    Berg, John M.; Gaunt, Andrew J.; May, Iain; Pugmire, Alison L.; Reilly, Sean D.; Scott, Brian L.; Wilkerson, Marianne P.

    2015-04-22

    A-type tri-lacunary heteropolyoxotungstate anions (e.g., [PW9O34]9-, [AsW9O34]9-, [SiW9O34]10- and [GeW9O34]10-) are multi-dentate oxygen donor ligands that readily form sandwich complexes with actinyl cations ({UO2}2+, {NpO2}+, {NpO2}2+ & {PuO2}2+) in near neutral/slightly alkaline aqueous solutions. Two or three actinyl cations are sandwiched between two trilacunary anions, with additional cations (Na+, K+ or NH4 +) also often held within the cluster. Studies thus far have indicated that it is these additional +I cations, rather than the specific actinyl cation, that direct the structural variation in the complexes formed. We now report the structural characterization of the neptunyl (VI) cluster complex (NH4)13 [Na(NpO2)2(A-α- PW9O34)2]·12H2O. The anion in this complex, [Na(NpO2)2(PW9O34)2]13-, contains one Na+ cation and two {NpO2}2+ cations held between two [PW9O34]9- anions – with an additional partial occupancy NH4 + or {NpO2}2+ cation also present. In the analogous uranium (VI) system, under similar reaction conditions that includes an excess of NH4Cl in the parent solution, it was previously shown that [(NH4)2(UVIO2)2(A-PW9O34)2]12- is the dominant species in both solution and the crystallized salt. Spectroscopic studies provide further proof of differences in the observed chemistry for the {NpO2}2+

  5. Fluorescent metal ion chemosensors via cation exchange reactions of complexes, quantum dots, and metal-organic frameworks.

    PubMed

    Cheng, Jinghui; Zhou, Xiangge; Xiang, Haifeng

    2015-11-01

    Due to their wide range of applications and biological significance, fluorescent sensors have been an active research area in the past few years. In the present review, recent research developments on fluorescent chemosensors that detect metal ions via cation exchange reactions (transmetalation, metal displacement, or metal exchange reactions) of complexes, quantum dots, and metal-organic frameworks are described. These complex-based chemosensors might have a much better selectivity than the corresponding free ligands/receptors because of the shielding function of the filled-in metal ions. Moreover, not only the chemical structure of the ligands/receptors but also the identity of the central metal ions have a tremendous impact on the sensing performances. Therefore, sensing via cation exchange reactions potentially provides a new, simple, and powerful way to design fluorescent chemosensors. PMID:26375420

  6. Suppressing the dendritic growth of zinc in an ionic liquid containing cationic and anionic zinc complexes for battery applications.

    PubMed

    Liu, Zhen; Pulletikurthi, Giridhar; Lahiri, Abhishek; Cui, Tong; Endres, Frank

    2016-05-10

    Metallic zinc is a promising negative electrode for high energy rechargeable batteries due to its abundance, low-cost and non-toxic nature. However, the formation of dendritic zinc and low Columbic efficiency in aqueous alkaline solutions during charge/discharge processes remain a great challenge. Here we demonstrate that the dendritic growth of zinc can be effectively suppressed in an ionic liquid electrolyte containing highly concentrated cationic and anionic zinc complexes obtained by dissolving zinc oxide and zinc trifluoromethylsulfonate in a protic ionic liquid, 1-ethylimidazolium trifluoromethylsulfonate. The presence of both cationic and anionic zinc complexes alters the interfacial structure at the electrode/electrolyte interface and influences the nucleation and growth of zinc, leading to compact, homogeneous and dendrite-free zinc coatings. This study also provides insights into the development of highly concentrated metal salts in ionic liquids as electrolytes to deposit dendrite-free zinc as an anode material for energy storage applications. PMID:27080261

  7. Thermal treatment effects imposed on solid DNA cationic lipid complex with hexadecyltrimethylammonium chloride, observed by variable angle spectroscopic ellipsometry

    SciTech Connect

    Nizioł, Jacek

    2014-12-21

    DNA cationic lipid complexes are materials of properties required for applications in organic electronics and optoelectronics. Often, their thermal stability demonstrated by thermogravimetry is cited in the literature as important issue. However, little is known about processes occurring in heated solid DNA cationic lipid complexes. In frame of this work, thin films of Deoxyribonucleic acid-hexadecyltrimethylammonium chloride (DNA-CTMA) were deposited on silicon wafers. Samples were thermally annealed, and simultaneously, their optical functions were measured by spectroscopic ellipsometry. At lower temperatures, thermal expansion coefficient of solid DNA-CTMA was negative, but at higher temperatures positive. Thermally induced modification of absorption spectrum in UV-vis was observed. It occurred at a range of temperatures higher than this of DNA denaturation in solution. The observed phenomenon was irreversible, at least in time scale of the experiment (one day)

  8. Non-photochemical Fluorescence Quenching in Photosystem II Antenna Complexes by the Reaction Center Cation Radical.

    PubMed

    Paschenko, V Z; Gorokhov, V V; Grishanova, N P; Korvatovskii, B N; Ivanov, M V; Maksimov, E G; Mamedov, M D

    2016-06-01

    In direct experiments, rate constants of photochemical (kP) and non-photochemical (kP(+)) fluorescence quenching were determined in membrane fragments of photosystem II (PSII), in oxygen-evolving PSII core particles, as well as in core particles deprived of the oxygen-evolving complex. For this purpose, a new approach to the pulse fluorometry method was implemented. In the "dark" reaction center (RC) state, antenna fluorescence decay kinetics were measured under low-intensity excitation (532 nm, pulse repetition rate 1 Hz), and the emission was registered by a streak camera. To create a "closed" [P680(+)QA(-)] RC state, a high-intensity pre-excitation pulse (pump pulse, 532 nm) of the sample was used. The time advance of the pump pulse against the measuring pulse was 8 ns. In this experimental configuration, under the pump pulse, the [P680(+)QA(-)] state was formed in RC, whereupon antenna fluorescence kinetics was measured using a weak testing picosecond pulsed excitation light applied to the sample 8 ns after the pump pulse. The data were fitted by a two-exponential approximation. Efficiency of antenna fluorescence quenching by the photoactive RC pigment in its oxidized (P680(+)) state was found to be ~1.5 times higher than that of the neutral (P680) RC state. To verify the data obtained with a streak camera, control measurements of PSII complex fluorescence decay kinetics by the single-photon counting technique were carried out. The results support the conclusions drawn from the measurements registered with the streak camera. In this case, the fitting of fluorescence kinetics was performed in three-exponential approximation, using the value of τ1 obtained by analyzing data registered by the streak camera. An additional third component obtained by modeling the data of single photon counting describes the P680(+)Pheo(-) charge recombination. Thus, for the first time the ratio of kP(+)/kP = 1.5 was determined in a direct experiment. The mechanisms of higher

  9. The different roles of a cationic gold(i) complex in catalysing hydroarylation of alkynes and alkenes with a heterocycle.

    PubMed

    Mehrabi, Tahmineh; Ariafard, Alireza

    2016-08-01

    The mechanism of twofold hydroarylation of terminal alkynes with pyrrole catalyzed by a cationic gold(i) complex was investigated using DFT. It was found that while both the hydroarylation reactions proceed via a Friedel-Crafts-type mechanism, the first hydroarylation is directly promoted by gold(i) but the second hydroarylation by a proton released through interaction of the alkene product with gold-bound acidic organic species such as acetic acid and terminal alkynes. PMID:27377712

  10. To jump or not to jump? Cα hydrogen atom transfer in post-cleavage radical-cation complexes.

    PubMed

    Bythell, Benjamin J

    2013-02-14

    Conventionally, electron capture or transfer to a polyprotonated peptide ion produces an initial radical-cation intermediate which dissociates "directly" to generate complementary c(n)' and z(m)(•) sequence ions (or ions and neutrals). Alternatively, or in addition, the initial radical-cation intermediate can undergo H(•) migration to produce c(n)(•) (or c(n) - H(•)) and z(m)' (or z(m)(•) + H(•)) species prior to complex separation ("nondirect"). This reaction significantly complicates spectral interpretation, creates ambiguity in peak assignment, impairs effective algorithmic processing (reduction of the spectrum to solely (12)C m/z values), and reduces sequence ion signal-to-noise. Experimental evidence indicates that the products of hydrogen atom transfer reactions are substantially less prevalent for higher charge state precursors. This effect is generally rationalized on the basis of decreased complex lifetime. Here, we present a theoretical study of these reactions in post N-C(α) bond cleavage radical-cation complexes as a function of size and precursor charge state. This approach provides a computational estimate of the barriers associated with these processes for highly charged peptides with little charge solvation. The data indicate that the H(•) migration is an exothermic process and that the barrier governing this reaction rises steeply with precursor ion charge state. There is also some evidence for immediate product separation following N-C(α) bond cleavage at higher charge state. PMID:22809411

  11. The role of multivalent metal cations and organic complexing agents in bitumen-mineral interactions in aqueous solutions

    NASA Astrophysics Data System (ADS)

    Gan, Weibing

    A systematic investigation was carried out to study the interactions between bitumen (or hexadecane) and minerals (quartz, kaolinite and illite) in aqueous solutions containing multivalent metal cations Ca2+, Mg2+ and Fe2+/Fe3+, in the absence and presence of organic complexing agents (oxalic acid, EDTA and citric acid). A range of experimental techniques, including coagulation measurement, visualization of bitumen-mineral attachment, metal ion adsorption measurement, zeta potential measurement, Fourier-transform infrared spectroscopy and X-ray photoelectron spectroscopic analyses, were employed in the investigation. Free energy changes of adsorption of metal cations on the minerals and bitumen were evaluated using the James & Healy thermodynamic model. Total interaction energies between the minerals and bitumen were calculated using classical DLVO theory. It was observed that while the tested minerals showed varying degrees of mutual-coagulation with bitumen (or hexadecane), the presence of the multivalent metal cations could prominently increase the mutual coagulation. It was also found that such enhancement of the mutual coagulation was only significant when the metal cations formed first-order hydroxyl complexes (such as CaOH +, MgOH+, etc.) or metal hydroxides (such as Fe(OH) 3, Mg(OH)2, etc.). Therefore, the increase of the bitumen-mineral mutual coagulation by the metal cations was strongly pH dependent. Organic complexing agents (oxalic acid, citric acid and EDTA) used in this study, citric acid in particular, significantly reduced or virtually eliminated the mutual coagulation between bitumen (or hexadecane) and minerals caused by metal cations Ca2+, Mg2+, Fe 2+ and Fe3+. Due to its ability to substantially lower the mutual coagulation between bitumen and mineral particles, citric acid was found the most effective in improving bitumen-mineral liberation in solutions containing the multivalent metal cations at pH 8--10. In small scale flotation experiments

  12. Release of cationic polymer-DNA complexes from the endosome: A theoretical investigation of the proton sponge hypothesis.

    PubMed

    Yang, Shuang; May, Sylvio

    2008-11-14

    Polyplexes are complexes composed of DNA and cationic polymers; they are promising transport vehicles for nonviral gene delivery. Cationic polymers that contain protonatable groups, such as polyethylenimine, have been suggested to trigger endosomal escape of polyplexes according to the "proton sponge hypothesis." Here, osmotic swelling is induced by a decrease in the endosomal pH value, leading to an accumulation of polymer charge accompanied by the influx of Cl(-) ions to maintain overall electroneutrality. We study a theoretical model of the proton sponge mechanism. The model is based on the familiar Poisson-Boltzmann approach, modified so as to account for the presence of ionizable polyelectrolytes within self-consistent field theory with assumed ground state dominance. We consider polyplexes, composed of fixed amounts of DNA and cationic polymer, to coexist with uncomplexed cationic polymer in an enclosing vesicle of fixed volume. For such a system, we calculate the increase in osmotic pressure upon moderately decreasing the pH value and relate that pressure to the rupture tension of the enclosing membrane. Our model predicts membrane rupture upon pH decrease only within a certain range of free polymer content in the vesicle. That range narrows with increasing amount of DNA. Consequently, there exists a maximal amount of DNA that can be incorporated into a vesicle while maintaining the ability of content release through the proton sponge mechanism. PMID:19045433

  13. Colorimetric Humidity and Solvent Recognition Based on a Cation-Exchange Clay Mineral Incorporating Nickel(II)-Chelate Complexes.

    PubMed

    Hosokawa, Hitoshi; Mochida, Tomoyuki

    2015-12-01

    Solvatochromic nickel(II) complexes with diketonato and diamine ligands were incorporated into a saponite clay by ion exchange, and their colorimetric humidity- and solvent-recognition properties were investigated. These powders exhibit color change from red to blue-green depending on humidity, and the detection range can be controlled by modifying the metal complex. The humidity response takes advantage of the humidity-dependent water content in clay and the coordination of water molecules to the metal complex in equilibrium. The addition of organic solvents to the powders causes a color change to occur, varying from red to blue-green depending on the donor number of the solvent, thereby enabling solvent recognition. In the clay, the affinity of less sterically hindered complexes to water or solvent molecules is decreased compared with that in solution because the cationic complexes interact with the anionic layers in the clay. Incorporating diethylene glycol into the materials produced thermochromic powders. PMID:26542108

  14. Photostable ester-substituted bis-cyclometalated cationic iridium(III) complexes for continuous monitoring of oxygen.

    PubMed

    Liu, Chun; Yu, Hongcui; Xing, Yang; Gao, Zhanming; Jin, Zilin

    2016-01-14

    Three bis-cyclometalated cationic Ir(iii) complexes , and with an ester substituent at the 4-position of the phenyl ring on the 2-phenylpyridine (ppy) have been synthesized and fully characterized. The emission maxima of ester-substituted Ir(iii) complexes show a notable blue-shift compared to the parent complex [Ir(ppy)2(phen)](+)PF6(-) (phen = 1,10-phenanthroline). The influence of an ester group on the photoelectric properties of the Ir(iii) complexes has been investigated systematically. The oxygen sensing films prepared from ethyl cellulose immobilized with Ir(iii) complexes exhibit excellent operational stability, high photostability and a quick response to oxygen. show extended luminescence lifetimes relative to , and display better sensitivity to changes in oxygen partial pressure. PMID:26630292

  15. Peptide-lanthanide cation equilibria in aqueous phase. I. Bound shifts for L-carnosine-praseodymium complexes

    NASA Astrophysics Data System (ADS)

    Mossoyan, J.; Asso, M.; Benlian, D.

    L-Carnosine complexes of Pr 3+ were characterized in aqueous solution by 1H NMR and potentiometric titration. A rigorous treatment of chemical shifts and pH variation data with lanthanide concentration is presented. Two different forms of the peptide ligand, forming simultaneously two complexes, were taken into account. At low pH values the cation is only coordinated at the carboxylate site of the ligand in a weak complex ( β2 = 6) whereas in neutral solution a stronger complex ( β1 = 37) is present as a consequence of the deprotonation of the imidazole ring. The computation of induced bound shifts † 2 and Δ1 for resonating nuclei of the peptide in both forms yields consistent figures. These provide the experimental basis for a conformational model which is usually not obtainable for labile complexes with low stability constants.

  16. Broad Scope Aminocyclization of Enynes with Cationic JohnPhos–Gold(I) Complex as the Catalyst

    PubMed Central

    2016-01-01

    A practical aminocyclization of 1,6-enynes with a wide variety of substituted anilines, including N-alkyl anilines, has been achived by using cationic [JohnPhosAu(MeCN)]SbF6 as a general purpose catalyst. The resulting adducts can be easily converted into polycyclic compounds by palladium- and gold-catalyzed reactions. PMID:26839084

  17. Control of intramolecular π-π stacking interaction in cationic iridium complexes via fluorination of pendant phenyl rings.

    PubMed

    He, Lei; Ma, Dongxin; Duan, Lian; Wei, Yongge; Qiao, Juan; Zhang, Deqiang; Dong, Guifang; Wang, Liduo; Qiu, Yong

    2012-04-16

    Intramolecular π-π stacking interaction in one kind of phosphorescent cationic iridium complexes has been controlled through fluorination of the pendant phenyl rings on the ancillary ligands. Two blue-green-emitting cationic iridium complexes, [Ir(ppy)(2)(F2phpzpy)]PF(6) (2) and [Ir(ppy)(2)(F5phpzpy)]PF(6) (3), with the pendant phenyl rings on the ancillary ligands substituted with two and five fluorine atoms, respectively, have been synthesized and compared to the parent complex, [Ir(ppy)(2)(phpzpy)]PF(6) (1). Here Hppy is 2-phenylpyridine, F2phpzpy is 2-(1-(3,5-difluorophenyl)-1H-pyrazol-3-yl)pyridine, F5phpzpy is 2-(1-pentafluorophenyl-1H-pyrazol-3-yl)-pyridine, and phpzpy is 2-(1-phenyl-1H-pyrazol-3-yl)pyridine. Single crystal structures reveal that the pendant phenyl rings on the ancillary ligands stack to the phenyl rings of the ppy ligands, with dihedral angles of 21°, 18°, and 5.0° between least-squares planes for complexes 1, 2, and 3, respectively, and centroid-centroid distances of 3.75, 3.65, and 3.52 Å for complexes 1, 2, and 3, respectively, indicating progressively reinforced intramolecular π-π stacking interactions from complexes 1 to 2 and 3. Compared to complex 1, complex 3 with a significantly reinforced intramolecular face-to-face π-π stacking interaction exhibits a significantly enhanced (by 1 order of magnitude) photoluminescent efficiency in solution. Theoretical calculations reveal that in complex 3 it is unfavorable in energy for the pentafluorophenyl ring to swing by a large degree and the intramolecular π-π stacking interaction remains on the lowest triplet state. PMID:22462475

  18. The Conducting Spin-Crossover Compound Combining Fe(II) Cation Complex with TCNQ in a Fractional Reduction State.

    PubMed

    Shvachko, Yuri N; Starichenko, Denis V; Korolyov, Aleksander V; Yagubskii, Eduard B; Kotov, Alexander I; Buravov, Lev I; Lyssenko, Konstantin A; Zverev, Vladimir N; Simonov, Sergey V; Zorina, Leokadiya V; Shakirova, Olga G; Lavrenova, Lyudmila G

    2016-09-01

    The radical anion salt [Fe{HC(pz)3}2](TCNQ)3 demonstrates conductivity and spin-crossover (SCO) transition associated with Fe(II) complex cation subsystem. It was synthesized and structurally characterized at temperatures 100, 300, 400, and 450 K. The compound demonstrates unusual for 7,7,8,8,-tetracyanoquinodimethane (TCNQ)-based salts quasi-two-dimensional conductivity. Pronounced changes of the in-plane direct-current resistivity and intensity of the electron paramagnetic resonance (EPR) signal, originated from TCNQ subsystem, precede the SCO transition at the midpoint T* = 445 K. The boltzmannian growth of the total magnetic response and structural changes in the vicinity of T* uniquely show that half [Fe{HC(pz)3}2] cations exist in high-spin state. Robust broadening of the EPR signal triggered by the SCO transition is interpreted in terms of cross relaxation between the TCNQ and Fe(II) spin subsystems. PMID:27541570

  19. Cationic terminal gallylene complexes by halide abstraction: coordination chemistry of a valence isoelectronic analogue of CO and N2.

    PubMed

    Coombs, Natalie D; Vidovic, Dragoslav; Day, Joanna K; Thompson, Amber L; Le Pevelen, Delphine D; Stasch, Andreas; Clegg, William; Russo, Luca; Male, Louise; Hursthouse, Michael B; Willock, David J; Aldridge, Simon

    2008-11-26

    While N(2) and CO have played central roles in developing models of electronic structure, and their interactions with transition metals have been widely investigated, the valence isoelectronic diatomic molecules EX (E = group 13 element, X = group 17 element) have yet to be isolated under ambient conditions, either as the "free" molecule or as a ligand in a simple metal complex. As part of a program designed to address this deficiency, together with wider issues of the chemistry of cationic systems [L(n)M(ER)](+) (E = B, Al, Ga; R = aryl, amido, halide), we have targeted complexes of the type [L(n)M(GaX)](+). Halide abstraction is shown to be a viable method for the generation of mononuclear cationic complexes containing gallium donor ligands. The ability to isolate tractable two-coordinate products, however, is strongly dependent on the steric and electronic properties of the metal/ligand fragment. In the case of complexes containing ancillary pi-acceptor ligands such as CO, cationic complexes can only be isolated as base-trapped adducts, even with bulky aryl substituents at gallium. Base-free gallylene species such as [Cp*Fe(CO)(2)(GaMes)](+) can be identified only in the vapor phase by electrospray mass spectrometry experiments. With bis(phosphine) donor sets at the metal, the more favorable steric/electronic environment allows for the isolation of two-coordinate ligand systems, even with halide substituents at gallium. Thus, [Cp*Fe(dppe)(GaI)](+)[BAr(f)(4)](-) (9) can be synthesized and shown crystallographically to feature a terminally bound GaI ligand; 9 represents the first experimental realization of a complex containing a valence isoelectronic group 13/group 17 analogue of CO and N(2). DFT calculations reveal a relatively weakly bound GaI ligand, which is confirmed experimentally by the reaction of 9 with CO to give [Cp*Fe(dppe)(CO)](+)[BAr(f)(4)](-). In the absence of such reagents, 9 is stable for weeks in fluorobenzene solution, presumably reflecting (i

  20. Thiophene complexes of the platinum group metals. 2. Preparation and characterization of cationic thiophene complexes of [(cyclooctadiene)Ir][BF[sub 4

    SciTech Connect

    Polam, J.R.; Porter, L.C. )

    1993-09-01

    Cleavage of chloro-bridged rhodium and iridium dimers, [(NBD)RhCl][sub 2] and [(COD)IrCl][sub 2], in methanol leads to the formation of cationic (COD)[sub 2]Ir[sup +] and (NBD)Rh[sup +] monomers, respectively. Reaction of these cationic species with 2-methylthiophene and 2,5-dimethylthiophene results in the formation of complexes in which the thiophene coordinates in an [eta][sup 5] manner. With benzothiophene and dibenzothiophene, complexes bearing a 1:1 metal:ligand stoichiometry are obtained with the ligand coordinating in an [eta][sup 6] fashion using the six carbon atoms of the arene ring. Good yields of these Rh and Ir products are obtained with the exception of those of reactions involving thiophene, where only small amounts of product were obtained. A crystal structure determination of the cationic (cyclooctadiene)rhodium 2,5-dimethylthiophene complex shows that the thiophene ligand binds to the transition metal center in an [eta][sup 5] manner. The S atom is displaced 0.1888 A from the least-squares plane defined by the four carbon ring atoms and displays C-S bond lengths similar to those found in free thiophene. 17 refs., 2 figs., 3 tabs.

  1. Photophysical and antibacterial properties of complex systems based on smectite, a cationic surfactant and methylene blue.

    PubMed

    Donauerová, Alena; Bujdák, Juraj; Smolinská, Miroslava; Bujdáková, Helena

    2015-10-01

    Solid or colloidal materials with embedded photosensitizers are promising agents from the medical or environmental perspective, where the direct use of photoactive solutions appears to be problematic. Colloids based on layered silicates of the saponite (Sap) and montmorillonite (Mon) type, including those modified with dodecylammonium cations (C12) and photosensitizer--methylene blue (MB) were studied. Two representatives of bacteria, namely Enterobacter cloacae and Escherichia coli, were selected for this work. A spectral study showed that MB solutions and also colloids with Sap including C12 exhibited the highest photoactivities. The antimicrobial properties of the smectite colloids were not directly linked to the photoactivity of the adsorbed MB cations. They were also influenced by other parameters, such as light vs. dark conditions, the spectrum, power and duration of the light used for the irradiation; growth phases, and the pre-treatment of microorganisms. Both the photoactivity and antimicrobial properties of the colloids were improved upon pre-modification with C12. Significantly higher antimicrobial properties were observed for the colloids based on Mon with MB in the form of molecular aggregates without significant photoactivities. The MB/Mon colloids, both modified and non-modified with C12 cations, exhibited higher antimicrobial effects than pure MB solution. Besides the direct effect of photosensitization, the surface properties of the silicate particles likely played a crucial role in the interactions with microorganisms. PMID:26248233

  2. A heterobimetallic superoxide complex formed through O2 activation between chromium(II) and a lithium cation.

    PubMed

    Schax, Fabian; Suhr, Simon; Bill, Eckhard; Braun, Beatrice; Herwig, Christian; Limberg, Christian

    2015-01-19

    The reaction of 1,1,3,3-tetraphenyl-1,3-disiloxandiol (LH2) with n-butyllithium and CrCl2 results in a mononuclear chromium(II) complex (1) that further reacts with O2 at low temperatures to yield a mononuclear chromium(III) superoxide complex [L2CrO2(THF)][Li2(THF)3] (2). The crystal structure revealed that the chromium superoxido entity is stabilized by the coordination to an adjacent lithium cation. Complex 2 thus contains an unprecedented heterobimetallic [Cr(III)(μ-O2)Li(+)] core; beyond this it is the first chromium superoxide for which a temperature-dependent magnetic characterization could be achieved, and the first structurally characterized representative with chromium in an exclusive O-donor environment. PMID:25477030

  3. Two coordination modes around the Cu(II) cations in complexes with benzo[b]furancarboxylic acids

    NASA Astrophysics Data System (ADS)

    Drzewiecka, Aleksandra; Koziol, Anna E.; Klepka, Marcin T.; Wolska, Anna; Jimenez-Pulido, Sonia B.; Lis, Tadeusz; Ostrowska, Kinga; Struga, Marta

    2013-02-01

    Three Cu(II) complexes with derivatives of the benzo[b]furancarboxylic acid have been synthesized and characterized by the elemental and thermal analyses, and IR spectroscopy. The geometry of metal-ligand interaction for all compounds has been described using X-ray absorption spectroscopy and for one of them by X-ray crystallography. Two mononuclear Cu(II) complexes, with 7-acetyl-5-bromo-6-hydroxy-3-methylbenzo[b]furan-2-carboxylic and 6-acetyl-5-hydroxy-2-methylbenzo[b]furan-3-carboxylic acids, exhibit a tetra-fold coordination, CuO4. The Cu(II) cation in crystals with 7-acetyl-6-methoxy-3-methyl-benzo[b]furan-2-carboxylic acid is penta-coordinated; the bridging COO- groups and ethanol molecule stabilize the dinuclear center Cu2O10. The powdered form of this complex is based on the Cu2O8 units, indicating the absence of the ethanol molecules.

  4. Diblock Polyelectrolytic Copolymers Containing Cationic Iron and Cobalt Sandwich Complexes: Living ROMP Synthesis and Redox Properties.

    PubMed

    Gu, Haibin; Ciganda, Roberto; Hernandez, Ricardo; Castel, Patricia; Zhao, Pengxiang; Ruiz, Jaime; Astruc, Didier

    2016-04-01

    Diblock metallopolymer polyelectrolytes containing the two redox-robust cationic sandwich units [CoCp'Cp](+) and [FeCp'(η(6)-C6 Me6)](+) (Cp = η(5)-C5 H5; Cp' = η(5)-C5H4-) as hexafluorophosphate ([PF6](-)) salts are synthesized by ring-opening metathesis polymerization using Grubbs' third generation catalyst. Their electrochemical properties show full chemical and electrochemical reversibilities allowing fine determination of the copolymer molecular weight using Bard-Anson's electrochemical method by cyclic voltammetry. PMID:26841204

  5. Novel cationic polyene glycol phospholipids as DNA transfer reagents--lack of a structure-activity relationship due to uncontrolled self-assembling processes.

    PubMed

    Øpstad, Christer L; Zeeshan, Muhammad; Zaidi, Asma; Sliwka, Hans-Richard; Partali, Vassilia; Nicholson, David G; Surve, Chinmay; Izower, Mitchell A; Bilchuk, Natalia; Lou, Howard H; Leopold, Philip L; Larsen, Helge; Liberska, Alexandra; Khalique, Nada Abdul; Raju, Liji; Flinterman, Marcella; Jubeli, Emile; Pungente, Michael D

    2014-10-01

    Cationic glycol phospholipids were synthesized introducing chromophoric, rigid polyenoic C20:5 and C30:9 chains next to saturated flexible alkyl chains of variable lengths C6-20:0. Surface properties and liposome formation of the amphiphilic compounds were determined, the properties of liposome/DNA complexes (lipoplexes) were established using three formulations (no co-lipid, DOPE as a co-lipid, or cholesterol as a co-lipid), and the microstructure of the best transfecting compounds inspected using small angle X-ray diffraction to explore details of the partially ordered structures of the systems that constitute the series. Transfection and cytotoxicity of the lipoplexes were evaluated by DNA delivery to Chinese hamster ovary (CHO-K1) cells using the cationic glycerol phospholipid 1,2-dioleoyl-sn-glycero-3-ethylphosphocholine (EPC) as a reference compound. The uncontrollable self-association of the molecules in water resulted in aggregates and liposomes of quite different sizes without a structure-property relationship. Likewise, adding DNA to the liposomes gave rise to unpredictable sized lipoplexes, which, again, transfected without a structure-activity relationship. Nevertheless, one compound among the novel lipids (C30:9 chain paired with a C20:0 chain) exhibited comparable transfection efficiency and toxicity to the control cationic lipid EPC. Thus, the presence of a rigid polyene chain in this best performing achiral glycol lipid did not have an influence on transfection compared with the chiral glycerolipid reference ethyl phosphocholine EPC with two flexible saturated C14 chains. PMID:24814958

  6. Dynamics of Nucleic Acid/Cationic Polymer Complexation and Disassembly under Biologically Simulated Conditions Using In Situ Atomic Force Microscopy

    PubMed Central

    Shim, Min Suk; Wang, Xi; Ragan, Regina; Kwon, Young Jik

    2010-01-01

    Elucidating dynamic morphological changes of gene-carrying vectors and their nucleic acid release under varying intracellular conditions has been a technical challenge. Atomic force microscopy (AFM) was employed to observe nucleic acid/polymer polyplexes under endosomal and reducible cytosolic conditions. Both ketalized (acid-degradable) and unmodified (non-degradable) polyethylenimine (PEI) in linear and branched forms were used to prepare plasmid DNA- or siRNA-complexing polyplexes. Then, the polyplexes’ complexation and disassembly were observed by in situ AFM in various differentially changing buffers that represent intracellular conditions. Results demonstrated obvious morphological destruction of DNA/ketalized linear PEI (KL-PEI) polyplexes under mildly acidic endosomal conditions, while no morphological changes were observed by DNA/ketalized branched PEI (KB-PEI) under the same conditions. In addition, siRNA was more efficiently dissociated from KL-PEI than KB-PEI under the same conditions. Non-degradable PEI did not show any evidence that DNA or siRNA was released. Anionic biomacromolecules (e.g., heparan sulfate), which was hypothesized to dissociate nucleic acids from cationic polymers, did not successfully disassemble polyplexes but appeared to be adsorbed on cationic polymers. The in situ AFM results combined with in vitro cellular transfection and gene silencing indicated that efficient endosomal escape of plasmid DNA in a compact polyplex form is required for efficient gene expression. On the contrary, rapid dissociation of siRNA from its cationic carrier is crucial for efficient gene silencing. The findings of this study may provide new insightful information for designing stimuli-responsive nonviral gene vectors as well as expanding tools for investigating nonviral vectors in nano scales under biologically inspired conditions. PMID:20803694

  7. A ferric-cyanide-bridged one-dimensional dirhodium complex with (18-crown-6)potassium cations.

    PubMed

    Kim, Y; Kim, S J; Nam, W

    2001-03-01

    The crystal structure of the title compound, catena-poly[bis[aqua(18-crown-6)potassium] diaqua(18-crown-6)potassium [[tetra-mu-benzoato-2:3 kappa(8)O:O'-mu-cyano-1:2 kappa(2)C:N-tetracyano-1 kappa C-irondirhodium(Rh-Rh)]-mu-cyano-1 kappa C:3' kappa N] octahydrate], [K(18-crown-6)(H(2)O)](2)[K(18-crown-6)(H(2)O)(2)][FeRh(2)(C(7)H(5)O(2))(4)(CN)(6)] x 8H(2)O, where (18-crown-6) is 1,4,7,10,13,16-hexaoxacyclooctadecane (C(12)H(24)O(6)), has been determined. Ferric cyanides connect the dirhodium units to form a one-dimensional chain compound. [K(18-crown-6-ether)(H(2)O)(2)] cations (with inversion symmetry) and [K(18-crown-6-ether)(H(2)O)] cations (in general positions) are located between the chains. PMID:11250572

  8. Cationic mono and dicarbonyl pincer complexes of rhodium and iridium to assess the donor properties of PCcarbeneP ligands.

    PubMed

    Smith, Joel D; Logan, Jessamyn R; Doyle, Lauren E; Burford, Richard J; Sugawara, Shun; Ohnita, Chiho; Yamamoto, Yohsuke; Piers, Warren E; Spasyuk, Denis M; Borau-Garcia, Javier

    2016-08-01

    The donor properties of five different PCcarbeneP ligands are assessed by evaluation of the CO stretching frequencies in iridium(i) and rhodium(i) carbonyl cations. The ligands feature dialkyl phosphine units (R = (i)Pr or (t)Bu) linked to the central benzylic carbon by either an ortho-phenylene bridge, or a 2,3-benzo[b]thiophene linker; in the former, substituent patterns on the phenyl linker are varied. The carbonyl complexes are synthesized from the (PCcarbeneP)M-Cl starting materials via abstraction of the chlorides in the presence of CO gas. In addition to the expected mono carbonyl cations, products with two carbonyl ligands are produced, and for the rhodium example, a novel product in which the second carbonyl ligand adds reversibly across the Rh[double bond, length as m-dash]C bond to give an η(2) ketene moiety was characterized. The IR data for the complexes shows the 2,3-benzo[b]thiophene linked system to be the poorest overall donor, while the phenyl bridged ligands incorporating electron donating dialkyl amino groups para to the anchoring carbene are very strongly donating pincer arrays. PMID:27465584

  9. Quaternary ammonium groups exposed at the surface of silica nanoparticles suitable for DNA complexation in the presence of cationic lipids.

    PubMed

    Reinhardt, Nora; Adumeau, Laurent; Lambert, Olivier; Ravaine, Serge; Mornet, Stéphane

    2015-05-28

    The production of silica nanoparticles (NPs) exposing quaternary ammonium groups (NPQ(+)) has been achieved using an optimized chemical surface functionalization protocol. The procedures of surface modification and quaternization of amino groups were validated by diffuse reflectance infrared Fourier transform (DRIFT) and (1)H NMR spectroscopies. Compared to nonquaternized aminated NP, the colloidal stability of NPQ(+) was improved for various pH and salt conditions as assessed by ζ potential and light scattering measurements. In the context of their use for nucleic acid delivery, DNA efficiently bound to NPQ(+) analyzed by cosedimentation assays for a large pH range and various NaCl concentrations and exhibited a better efficacy at basic pH than nonquaternized NP. The study of NPQ(+)/DNA/cationic lipids ternary complexes was carried out with 1,2-dioleoyl-3-trimethylammonium propane (DOTAP) and analyzed by cryo-electron microscopy (cryo-EM). Cryo-EM images showed ternary assemblies where condensed DNA strands are sandwiched between the NPQ(+) surface and the cationic lipid bilayer. Because of an unusual electrostatic colloidal stability of NPQ(+) and a high propensity to bind DNA molecules particularly at high salt concentrations, a novel type of ternary assembly has been formed that might impact the delivery properties of these complexes including their stability in biological environment. PMID:25950202

  10. Tuning the Emission of Cationic Iridium (III) Complexes Towards the Red Through Methoxy Substitution of the Cyclometalating Ligand

    PubMed Central

    Hasan, Kamrul; Bansal, Ashu K.; Samuel, Ifor D.W.; Roldán-Carmona, Cristina; Bolink, Henk J.; Zysman-Colman, Eli

    2015-01-01

    The synthesis, characterization and evaluation in solid-state devices of a series of 8 cationic iridium complexes bearing different numbers of methoxy groups on the cyclometallating ligands are reported. The optoelectronic characterization showed a dramatic red shift in the absorption and the emission and a reduction of the electrochemical gap of the complexes when a methoxy group was introduced para to the Ir-C bond. The addition of a second or third methoxy group did not lead to a significant further red shift in these spectra. Emission maxima over the series ranged from 595 to 730 nm. All complexes possessing a motif with a methoxy group at the 3-position of the cyclometalating ligands showed very short emission lifetimes and poor photoluminescence quantum yields whereas complexes having a methoxy group at the 4-position were slightly blue shifted compared to the unsubstituted parent complexes, resulting from the inductively electron withdrawing nature of this directing group on the Ir-C bond. Light-emitting electrochemical cells were fabricated and evaluated. These deep red emitters generally showed poor performance with electroluminescence mirroring photoluminescence. DFT calculations accurately modelled the observed photophysical and electrochemical behavior of the complexes and point to an emission from a mixed charge transfer state. PMID:26179641

  11. Synthesis and chemistry of cationic d{sup 0} metal alkyl complexes. Progress report, July 1988--May 1991

    SciTech Connect

    Jordan, R.F.

    1991-12-31

    The objective of this project is to develop new types of electrophilic metal alkyl complexes for catalytic C-H activation and olefin polymerization chemistry, and associated fundamental mechanistic studies. We have focused our efforts on four classes of early metal alkyl complexes: (1) cationic group 4 Cp{sub 2}M(R){sup +} complexes (1) which are active species in Cp{sub 2}MX{sub 2}-based Ziegler-Natta olefin polymerization catalyst systems and which catalyze productive C-H activation reactions of heterocycles, (2) neutral (dicarbollide)(Cp*)M(R) complexes (2) which are structurally are electronically very similar to 1, (3) half-sandwich complexes CpM(R){sub 2}(L){sub n}{sup +} which are highly coordinatively and electronically unsaturated, and (4) new group 5 (dicarbollide)(Cp)MR{sub 2} and (dicarbollide){sub 2} MR complexes which are more unsaturated than group 5 Cp{sub 2}M systems due to incorporation of the dicarbollide ligand.

  12. A spectroscopic and computational study of Al(III) complexes in cryolite melts: Effect of cation nature

    NASA Astrophysics Data System (ADS)

    Nazmutdinov, Renat R.; Zinkicheva, Tamara T.; Vassiliev, Sergey Yu.; Glukhov, Dmitrii V.; Tsirlina, Galina A.; Probst, Michael

    2013-02-01

    Lithium, sodium and potassium cryolite melts are probed by Raman spectroscopy in a wide range of the melt composition. The experimental data demonstrate a slight red shift of main peaks and a decrease of their half-widths in the row Li+, Na+, K+. Quantum chemical modelling of the systems is performed at the density functional theory level. The ionic environment is found to play a crucial role in the energy of fluoroaluminates. Potential energy surfaces describing the formation/dissociation of certain complex species, as well as model Raman spectra are constructed and compared with those obtained recently for sodium containing cryolite melts (R.R. Nazmutdinov, et al., Spectrochim, Acta A 75 (2010) 1244.). The calculations show that the cation nature affects the geometry of the ionic associates as well as the equilibrium and kinetics of the complexation processes. This enables to interpret both original experimental data and those reported in literature.

  13. A spectroscopic and computational study of Al(III) complexes in cryolite melts: Effect of cation nature

    PubMed Central

    Nazmutdinov, Renat R.; Zinkicheva, Tamara T.; Vassiliev, Sergey Yu.; Glukhov, Dmitrii V.; Tsirlina, Galina A.; Probst, Michael

    2013-01-01

    Lithium, sodium and potassium cryolite melts are probed by Raman spectroscopy in a wide range of the melt composition. The experimental data demonstrate a slight red shift of main peaks and a decrease of their half-widths in the row Li+, Na+, K+. Quantum chemical modelling of the systems is performed at the density functional theory level. The ionic environment is found to play a crucial role in the energy of fluoroaluminates. Potential energy surfaces describing the formation/dissociation of certain complex species, as well as model Raman spectra are constructed and compared with those obtained recently for sodium containing cryolite melts (R.R. Nazmutdinov, et al., Spectrochim, Acta A 75 (2010) 1244.). The calculations show that the cation nature affects the geometry of the ionic associates as well as the equilibrium and kinetics of the complexation processes. This enables to interpret both original experimental data and those reported in literature. PMID:23408115

  14. A spectroscopic and computational study of Al(III) complexes in cryolite melts: Effect of cation nature.

    PubMed

    Nazmutdinov, Renat R; Zinkicheva, Tamara T; Vassiliev, Sergey Yu; Glukhov, Dmitrii V; Tsirlina, Galina A; Probst, Michael

    2013-02-01

    Lithium, sodium and potassium cryolite melts are probed by Raman spectroscopy in a wide range of the melt composition. The experimental data demonstrate a slight red shift of main peaks and a decrease of their half-widths in the row Li(+), Na(+), K(+). Quantum chemical modelling of the systems is performed at the density functional theory level. The ionic environment is found to play a crucial role in the energy of fluoroaluminates. Potential energy surfaces describing the formation/dissociation of certain complex species, as well as model Raman spectra are constructed and compared with those obtained recently for sodium containing cryolite melts (R.R. Nazmutdinov, et al., Spectrochim, Acta A 75 (2010) 1244.). The calculations show that the cation nature affects the geometry of the ionic associates as well as the equilibrium and kinetics of the complexation processes. This enables to interpret both original experimental data and those reported in literature. PMID:23408115

  15. Features of the complexation of 3,3'-dimethoxy-4,4'-dihydroxy-5,5'-bis(di(n-carboxymethyl)aminomethyl)benzophenone with some cations and oxo cations of metals

    SciTech Connect

    Sinitsyna, T.A.; Ivakin, A.A.

    1988-02-01

    The complexation of 3,3'-dimethoxy-4,4'-dihydroxy-5,5'-bis(di(N-carboxymethyl)amino-methyl)benzophenone with Ca/sup 2 +/, Zn/sup 2 +/, Y/sup 3 +/, VO/sup 2 +/, and VO/sub 2//sup +/ cations has been investigated by the methods of IR and PMR spectroscopy. Hypotheses regarding the coordination capacity of the chelating agent in the complexes studied have been advanced on the basis of the data obtained.

  16. Role of cholesterol on the transfection barriers of cationic lipid/DNA complexes

    NASA Astrophysics Data System (ADS)

    Pozzi, Daniela; Cardarelli, Francesco; Salomone, Fabrizio; Marchini, Cristina; Amenitsch, Heinz; Barbera, Giorgia La; Caracciolo, Giulio

    2014-08-01

    Most lipid formulations need cholesterol for efficient transfection, but the precise motivation remains unclear. Here, we have investigated the effect of cholesterol on the transfection efficiency (TE) of cationic liposomes made of 1,2-dioleoyl-3-trimethylammonium-propane and dioleoylphosphocholine in Chinese hamster ovary cells. The transfection mechanisms of cholesterol-containing lipoplexes have been investigated by TE, synchrotron small angle X-ray scattering, and laser scanning confocal microscopy experiments. We prove that cholesterol-containing lipoplexes enter the cells using different endocytosis pathways. Formulations with high cholesterol content efficiently escape from endosomes and exhibit a lamellar-nonlamellar phase transition in mixture with biomembrane mimicking lipid formulations. This might explain both the DNA release ability and the high transfection efficiency. These studies highlight the enrichment in cholesterol as a decisive factor for transfection and will contribute to the rational design of lipid nanocarriers with superior TE.

  17. Aqueous complexation of trivalent lanthanide and actinide cations by N,N,N'{sub 2},N'-tetrakis(2-pyridylmethyl)ethylenediamine.

    SciTech Connect

    Beitz, J. V.; Ensor, D. D.; Jensen, M. P.; Morss, L. R.

    1999-06-16

    The aqueous complexation reactions of trivalent lanthanide and actinide cations with the hexadentate ligand N,N,N{prime},N{prime}-tetrakis(2-pyridylmethyl)ethylenediamine (TPEN), have been characterized using potentiometric and spectroscopic techniques in 0.1 M NaClO{sub 4} At 25 C, the stability constant of Am(TPEN){sup 3+} is two orders of magnitude larger than that of Sm(TPEN){sup 3+}, reflecting the stronger interactions of the trivalent actinide cations with softer ligands as compared to lanthanide cations.

  18. Cyanide anion binding by a triarylborane at the outer rim of a cyclometalated ruthenium(II) cationic complex.

    PubMed

    Wade, Casey R; Gabbaï, François P

    2010-01-18

    As part of our ongoing interest in the design of boron-based cyanide anion receptors, we have synthesized a triaryl borane decorated by a cationic Ru(II) complex and have investigated its anion binding properties. This new borane, [(2,2'-bpy)Ru(kappa-C,N-2-(dimesitylborylphenyl)pyridinato)]OTf ([2]OTf), binds both fluoride and cyanide anions in organic solvents to afford 2-F and 2-CN whose crystal structures have been determined. UV-vis titrations in 9/1 CHCl(3)/DMF (vol.) afforded K((F(-))) = 1.1(+/-0.1) x 10(4) M(-1) and K((CN(-))) = 3.0(+/-1.0) x 10(6) M(-1) indicating that [2](+) has a higher affinity for cyanide than for fluoride in this solvent mixture. These elevated binding constants show that the cationic Ru(II) complex increases the anion affinity of these complexes via Coulombic and inductive effects. The UV-vis spectral changes which accompany either fluoride or cyanide binding to the boron center are similar and include a 30 nm bathochromic shift of the metal-to-ligand charge transfer band. This shift is attributed to an increase in the donor ability of the boron-substituted phenylpyridine ligand upon anion binding to the boron center. Accordingly, cyclic voltammetry revealed that the Ru(II/III) redox couple of [2]OTf (E(1/2) = +0.051 V vs Fc/Fc(+)) undergoes a cathodic shift upon F(-) (DeltaE(1/2) = -0.242 V vs Fc/Fc(+)) or CN(-) (DeltaE(1/2) = -0.198 V vs Fc/Fc(+)) binding. PMID:20000628

  19. Cationic cluster formation versus disproportionation of low-valent indium and gallium complexes of 2,2'-bipyridine

    PubMed Central

    Lichtenthaler, Martin R.; Stahl, Florian; Kratzert, Daniel; Heidinger, Lorenz; Schleicher, Erik; Hamann, Julian; Himmel, Daniel; Weber, Stefan; Krossing, Ingo

    2015-01-01

    Group 13 MI compounds often disproportionate into M0 and MIII. Here, however, we show that the reaction of the MI salt of the weakly coordinating alkoxyaluminate [GaI(C6H5F)2]+[Al(ORF)4]− (RF=C(CF3)3) with 2,2'-bipyridine (bipy) yields the paramagnetic and distorted octahedral [Ga(bipy)3]2+•{[Al(ORF)4]−}2 complex salt. While the latter appears to be a GaII compound, both, EPR and DFT investigations assign a ligand-centred [GaIII{(bipy)3}•]2+ radical dication. Surprisingly, the application of the heavier homologue [InI(C6H5F)2]+[Al(ORF)4]− leads to aggregation and formation of the homonuclear cationic triangular and rhombic [In3(bipy)6]3+, [In3(bipy)5]3+ and [In4(bipy)6]4+ metal atom clusters. Typically, such clusters are formed under strongly reductive conditions. Analysing the unexpected redox-neutral cationic cluster formation, DFT studies suggest a stepwise formation of the clusters, possibly via their triplet state and further investigations attribute the overall driving force of the reactions to the strong In−In bonds and the high lattice enthalpies of the resultant ligand stabilized [M3]3+{[Al(ORF)4]−}3 and [M4]4+{[Al(ORF)4]−}4 salts. PMID:26478464

  20. Spectroscopic studies of the interaction between methylene blue-naphthol orange complex and anionic and cationic surfactants

    NASA Astrophysics Data System (ADS)

    Yamamoto, Shunzo; Kobashi, Serina; Tsutsui, Ken-ichiro; Sueishi, Yoshimi

    2007-02-01

    Initially, the absorbance of MB at 665 nm decreased rapidly with increasing sodium dodecyl sulfate (SDS) concentration, but increased gradually above about 2.3 × 10 -3 M. However, the absorbance of MB was almost independent of the cetyltrimethylammonium bromide (CTAB) concentration. On the other hand, the absorbance of NpO was affected by addition of CTAB in a similar manner to the change in MB-SDS system, but not by addition of SDS. The absorption band of MB showed a small red-shift and a decrease in intensity upon addition of NpO, while that of NpO showed only the decrease in the intensity upon the addition of MB. These spectral changes were attributed to the formation of complexes between these dyes. The effects of anionic and cationic surfactants on the absorption spectra of mixtures of MB and NpO were also examined. Contrary to the effects on the absorption spectrum of MB and NpO, respectively, the absorbances of MB and NpO in the mixtures were changed with the additions of both anionic and cationic surfactants. The spectral changes were explained by changes in the forms of MB and NpO in the solutions with increasing surfactant concentrations.

  1. Alkali metal cation complexation by 1,3-alternate, mono-ionisable calix[4]arene-benzocrown-6 compounds

    DOE PAGESBeta

    Surowiec, Malgorzata A.; Custelcean, Radu; Surowiec, Kazimierz; Bartsch, Richard A.

    2014-04-23

    Alkali metal cation extraction behavior for two series of 1,3-alternate, mono-ionizable calix[4]arene-benzocrown-6 compounds is examined. In Series 1, the proton-ionizable group is a substituent on the benzo group of the polyether ring that directs it away from the crown ether cavity. In Series 2, the proton-ionizable group is attached to one para position in the calixarene framework, thus positioning it over the crown ether ring. Competitive solvent extraction of alkali metal cations from aqueous solutions into chloroform shows high Cs+ efficiency and selectivity. Single-species extraction pH profiles of Cs+ for Series 1 and 2 ligands with the same proton-ionizable groupmore » are very similar. Thus, association of Cs+ with the calixcrown ring is more important than the the proton-ionizable group’s position in relation to the crown ether cavity. Solid-state structures are presented for two unionized ligands from Series 2, as is a crystal containing two different ionized ligand–Cs+ complexes.« less

  2. Alkali metal cation complexation by 1,3-alternate, mono-ionisable calix[4]arene-benzocrown-6 compounds

    SciTech Connect

    Surowiec, Malgorzata A.; Custelcean, Radu; Surowiec, Kazimierz; Bartsch, Richard A.

    2014-04-23

    Alkali metal cation extraction behavior for two series of 1,3-alternate, mono-ionizable calix[4]arene-benzocrown-6 compounds is examined. In Series 1, the proton-ionizable group is a substituent on the benzo group of the polyether ring that directs it away from the crown ether cavity. In Series 2, the proton-ionizable group is attached to one para position in the calixarene framework, thus positioning it over the crown ether ring. Competitive solvent extraction of alkali metal cations from aqueous solutions into chloroform shows high Cs+ efficiency and selectivity. Single-species extraction pH profiles of Cs+ for Series 1 and 2 ligands with the same proton-ionizable group are very similar. Thus, association of Cs+ with the calixcrown ring is more important than the the proton-ionizable group’s position in relation to the crown ether cavity. Solid-state structures are presented for two unionized ligands from Series 2, as is a crystal containing two different ionized ligand–Cs+ complexes.

  3. Computational study of structural properties of lithium cation complexes with carbamate-modified disiloxanes.

    PubMed

    Jeschke, Steffen; Wiemhöfer, Hans-Dieter; Mück-Lichtenfeld, Christian

    2014-07-21

    Lithium cation solvation structures [Li(S)(n=1-4)](+) with ligands of cyclic or noncyclic carbamate-modified disiloxanes are optimized at B3LYP level of theory and compared to their corresponding simplified carbamates and to the organic carbonates ethylene carbonate (EC) and dimethyl carbonate (DMC). The electrostatic potentials (ESP) of these investigated carbonyl-containing solvents are mapped on the electron density surface. The maximum ESP is located at the C=O-oxygen, whereas the disiloxane functionality represents an unpolar residue. Natural Bond Orbitals (NBO) analysis reveals strong n(N) →π(C[double bond, length as m-dash]O) donor-acceptor interactions in carbamates which outrun dipolar properties. As a result, higher total binding energies (ΔE(B)) for solvation of Li(+) in carbamates (-148 kcal mol(-1)) are found than for carbonates (-137 kcal mol(-1)). Furthermore, the disiloxane moiety with its Si-O bond is stabilized by n(O) →σ*(Si-C) hyperconjugation that provides additional electron density to a nearby SiCH3 methyl group thus supporting an additional SiCH2-H...Li(+) coordination. The formation of all investigated solvation structures is exothermic. Owing to steric hindrance of noncyclic carbonyl-containing ligands and the bulky disiloxane functionality, the solvation structure [Li(S)3](+) is the preferred structure according to Gibbs free energy ΔG(B) results. PMID:24914737

  4. Gel-derived cation-π stacking films of carbon nanotube-graphene complexes as oxygen cathodes.

    PubMed

    Zhang, Tao; Matsuda, Hirofumi; Zhou, Haoshen

    2014-10-01

    A key challenge in processing carbon nanotubes and their composites for large-scale applications is aggregation. Cation-π stacking interactions have been discovered to disperse heavily entangled single-walled carbon nanotube (SWNT) bundles in ionic liquids (ILs). In this work, we found that a dispersible, silky single-layer graphene (SLG) can be readily gathered together to form a crosslinked gel after entrapping sufficient IL molecular via the likely noncovalent interaction. By incorporating the dispersed SWNTs into the gathered SLG gel synchronously, we prepared solid, finely crosslinked SWNTs-SLG films, assisted by an avenue of 2-step extraction to remove the IL completely. The gel-derived SWNTs-SLG complex film was applied as a support material of oxygen cathodes for Li-O2 batteries. It exhibited a remarkable improved cycleability in comparison to made of SWNTs and SLG alone due to the finely crosslinked feature. Decorated SWNTs and SLG can also form gel-derived complexes via the same process to construct support-catalyst complexes. A SWNTs-SLG film loaded with Ru nanoparticles exhibited not only catalytic effects, but also the ability to suppress the side reactions, and hence stabilized the whole Li-O2 battery. Our research introduces a gel-derived, high-dispersed processing of carbon nanotube-graphene complexes and demonstrates their favorable applications on Li-O2 batteries. PMID:25164151

  5. Cationic Lipid-Nucleic Acid Complexes for Gene Delivery And Silencing: Pathways And Mechanisms for Plasmid Dna And Sirna

    SciTech Connect

    Ewert, K.K.; Zidovska, A.; Ahmad, A.; Bouxsein, N.F.; Evans, H.M.; McAllister, C.S.; Samuel, C.E.; Safinya, C.R.; /SLAC

    2012-07-17

    Motivated by the promises of gene therapy, there is great interest in developing non-viral lipid-based vectors for therapeutic applications due to their low immunogenicity, low toxicity, ease of production, and the potential of transferring large pieces of DNA into cells. In fact, cationic liposome (CL) based vectors are among the prevalent synthetic carriers of nucleic acids (NAs) currently used in gene therapy clinical trials worldwide. These vectors are studied both for gene delivery with CL-DNA complexes and gene silencing with CL-siRNA (short interfering RNA) complexes. However, their transfection efficiencies and silencing efficiencies remain low compared to those of engineered viral vectors. This reflects the currently poor understanding of transfection-related mechanisms at the molecular and self-assembled levels, including a lack of knowledge about interactions between membranes and double stranded NAs and between CL-NA complexes and cellular components. In this review we describe our recent efforts to improve the mechanistic understanding of transfection by CL-NA complexes, which will help to design optimal lipid-based carriers of DNA and siRNA for therapeutic gene delivery and gene silencing.

  6. Electronic structure and luminescence of tellurium (IV) halide complexes with guanidine and caesium cations

    NASA Astrophysics Data System (ADS)

    Dotsenko, A. A.; Shcheka, O. L.; Vovna, V. I.; Korochentsev, V. V.; Mirochnik, A. G.; Sedakova, T. V.

    2016-04-01

    The present paper continues a series of publications on the investigation of complex compounds of s2 ions and their properties. The structure of the valence levels of Cs2TeX6, (HGu)2TeCl6 complexes (where X = Cl, Br; HGu+ - guanidinium) is examined, the orbital nature of luminescence excitation is established, and the relationship of properties with the electronic structure is determined by means of X-ray photoelectron spectroscopy (XPS) and density functional theory (DFT).

  7. Complexation of Donor-Acceptor Substituted Aza-Crowns with Alkali and Alkaline Earth Metal Cations. Charge Transfer and Recoordination in Excited State.

    PubMed

    Volchkov, Valery V; Gostev, Fedor E; Shelaev, Ivan V; Nadtochenko, Viktor A; Dmitrieva, Svetlana N; Gromov, Sergey P; Alfimov, Mikhail V; Melnikov, Mikhail Ya

    2016-03-01

    Complexation between two aza-15-crown-5 ethers bearing electron donor and acceptor fragments and alkali and alkaline earth perchlorates has been studied using absorption, steady-state fluorescence and femtosecond transient absorption spectroscopy. The spectral-luminescent parameters, the stability and dissociation constants of the complexes were calculated. The intramolecular charge transfer reaction takes place both in the excited state of the crowns and their complexes 1:1; the latter is subjected to photorecoordination resulting in a weakening or a complete disruption of coordination bond between nitrogen atom and metal cation, disposed within a cavity of the crown. The compounds investigated can be viewed as novel optical molecular sensors for alkali and alkaline-earth metal cations. The photoejection of a metal cation into the bulk was not observed. PMID:26670689

  8. Protein binding studies of technetium-99m-labeled phosphine and isocyanide cationic complexes

    SciTech Connect

    Zanelli, G.D.; Cook, N.; Lahiri, A.; Ellison, D.; Webbon, P.; Woolley, G.

    1988-01-01

    Most /sup 99m/Tc/phosphine/isocyanide complexes synthesized to date show preferential uptake by the myocardium of many animal species but not in man. A new complex has been synthesized, (/sup 99m/Tc(DEPE)2(CNR)2), +(DEPIC), where R = t - butyl isocyanide, which in three animal species images the myocardium very well, but in humans it remains primarily in the blood pool. One reason for the difference in the behavior of these complexes in different species could be the characteristics of their binding to plasma proteins. The protein binding characteristics of DEPIC and two other well-known complexes have therefore been studied. Whereas the other complexes bind nonspecifically to many proteins both in animal and human plasma, DEPIC binds almost exclusively to prealbumin in humans but nonspecifically to other proteins in the rabbit. The binding sites in human plasma appear to be those normally occupied by thyroxine on the prealbumin tetramer and these can be blocked by sodium salicylate.

  9. Electrocatalytic carbon dioxide reduction by using cationic pentamethylcyclopentadienyl-iridium complexes with unsymmetrically substituted bipyridine ligands.

    PubMed

    Sypaseuth, Fanni D; Matlachowski, Corinna; Weber, Manuela; Schwalbe, Matthias; Tzschucke, C Christoph

    2015-04-20

    Eight [Ir(bpy)Cp*Cl](+) -type complexes (bpy= bipyridine, Cp*=1,2,3,4,5-pentamethylcyclopentadienyl) containing differently substituted bipyridine ligands were synthesized and characterized. Cyclic voltammetry (CV) of the complexes in Ar-saturated acetonitrile solutions showed that the redox behavior of the complexes could be fine tuned by the electronic properties of the substituted bipyridine ligands. Further CV in CO2 -saturated MeCN/H2 O (9:1, v/v) solutions showed catalytic currents for CO2 reduction. In controlled potential electrolysis experiments (MeCN/MeOH (1:1, v/v), Eapp =-1.80 V vs Ag/AgCl), all of the complexes showed moderate activity in the electrocatalytic reduction of CO2 with good stability over at least 15 hours. This electrocatalytic process was selective toward formic acid, with only traces of dihydrogen or carbon monoxide and occasionally formaldehyde as byproducts. However, the turnover frequencies and current efficiencies were quite low. No direct correlation between the redox potentials of the complexes and their catalytic activity was observed. PMID:25756194

  10. Cationized bovine serum albumin as gene carrier: Influence of specific secondary structure on DNA complexibility and gene transfection.

    PubMed

    Du, Jianwei; Li, Bangbang; Zhang, Peng; Wang, Youxiang

    2016-07-01

    In this research, BSA, one of the natural rigid globular proteins with ca. 51% of α-helix secondary structure, was utilized to prepare cationized BSA (cBSA) as gene carrier. Tetraethylenepentamine (TEPA) or polyethylenimine (PEI1800) was grafted to BSA with different grafting levels. Based on the circular dichoism (CD) spectra, all cBSA remained α-helical structure to some degree. This was exciting to endow cBSA with quite different DNA complexibility and cellular biology behavior from the random coiled and flexible polycations such as PEI and poly-l-lysine (PLL). Strangely, the DNA condensability decreased with the increment of TEPA or PEI1800 grafting level. Also, the cBSA could condense DNA effectively to form irregular nanoparticles around 50-200nm above N/P ratio of 10. On account of the excellent hydration of BSA, the cBSA/DNA complexes revealed good colloidal stability under physiological salt condition. Cell culture experiments indicated this BSA-based gene carrier possessed good cellular compatibility. Surprisingly, cBSA/DNA complexes could be uptaken excellently by up to 90% cells. This might be owing to the agitation effect of α-helical structure and the positive potential of these complexes. BSA-PEI1800/DNA complexes with quick endosome escape even had transfection efficiency as high as PEI25k/DNA complexes. Overall, this paper provided us the potential of cBSA as gene carrier and might have some instructions in the design of protein-based gene delivery system. PMID:26998865

  11. Efficient in vivo gene delivery by the negatively charged complexes of cationic liposomes and plasmid DNA.

    PubMed

    Son, K K; Tkach, D; Hall, K J

    2000-09-29

    We examined changes in zeta potential (the surface charge density, zeta) of the complexes of liposome (nmol)/DNA (microg) (L/D) formed in water at three different ratios (L/D=1, 10 and 20) by changing the ionic strength or pH to find an optimum formulation for in vivo gene delivery. At high DNA concentrations, zeta of the complexes formed in water at L/D=10 was significantly lowered by adding NaCl (zeta=+8.44+/-3.1 to -27.6+/-3.5 mV) or increasing pH from 5 (zeta=+15.3+/-1.0) to 9 (zeta=-22.5+/-2.5 mV). However, the positively charged complexes formed at L/D=20 (zeta=+6.2+/-3.5 mV) became negative as NaCl was added at alkaline pH as observed in medium (zeta=-19.7+/-9.9 mV). Thus, the complexes formed in water under the optimum condition were stable and largely negatively charged at L/D=1 (zeta=-58.1+/-3.9 mV), unstable and slightly positively charged at L/D=10 (zeta=+8.44+/-3.7 mV), and unstable and largely positively charged at L/D=20 (zeta=+24.3+/-3.6 mV). The negatively charged complexes efficiently delivered DNA into both solid and ascitic tumor cells. However, the positively charged complexes were very poor in delivering DNA into solid tumors, yet were efficient in delivering DNA into ascitic tumors grown in the peritoneum regardless of complex size. This slightly lower gene transfer efficiency of the negatively charged complexes can be as efficient as the positively charged ones when an injection is repeated (at least two injections), which is the most common case for therapy regimes. The results indicate that optimum in vivo lipofection may depend on the site of tumor growth. PMID:11018645

  12. Ab Initio Characterization of the Electrostatic Complexes Formed by H2 Molecule and Cr(+), Mn(+), Cu(+), and Zn(+) Cations.

    PubMed

    Artiukhin, Denis G; Bieske, Evan J; Buchachenko, Alexei A

    2016-07-14

    Equilibrium structures, dissociation energies, and rovibrational energy levels of the electrostatic complexes formed by molecular hydrogen and first-row S-state transition metal cations Cr(+), Mn(+), Cu(+), and Zn(+) are investigated ab initio. Extensive testing of the CCSD(T)-based approaches for equilibrium structures provides an optimal scheme for the potential energy surface calculations. These surfaces are calculated in two dimensions by keeping the H-H internuclear distance fixed at its equilibrium value in the complex. Subsequent variational calculations of the rovibrational energy levels permits direct comparison with data obtained from equilibrium thermochemical and spectroscopic measurements. Overall accuracy within 2-3% is achieved. Theoretical results are used to examine trends in hydrogen activation, vibrational anharmonicity, and rotational structure along the sequence of four electrostatic complexes covering the range from a relatively floppy van der Waals system (Mn(+)···H2) to an almost a rigid molecular ion (Cu(+)···H2). PMID:26914616

  13. Analysis of Native-Like Proteins and Protein Complexes Using Cation to Anion Proton Transfer Reactions (CAPTR)

    NASA Astrophysics Data System (ADS)

    Laszlo, Kenneth J.; Bush, Matthew F.

    2015-12-01

    Mass spectra of native-like protein complexes often exhibit narrow charge-state distributions, broad peaks, and contributions from multiple, coexisting species. These factors can make it challenging to interpret those spectra, particularly for mixtures with significant heterogeneity. Here we demonstrate the use of ion/ion proton transfer reactions to reduce the charge states of m/ z-selected, native-like ions of proteins and protein complexes, a technique that we refer to as cation to anion proton transfer reactions (CAPTR). We then demonstrate that CAPTR can increase the accuracy of charge state assignments and the resolution of interfering species in native mass spectrometry. The CAPTR product ion spectra for pyruvate kinase exhibit ~30 peaks and enable unambiguous determination of the charge state of each peak, whereas the corresponding precursor spectra exhibit ~6 peaks and the assigned charge states have an uncertainty of ±3%. 15+ bovine serum albumin and 21+ yeast enolase dimer both appear near m/ z 4450 and are completely unresolved in a mixture. After a single CAPTR event, the resulting product ions are baseline resolved. The separation of the product ions increases dramatically after each subsequent CAPTR event; 12 events resulted in a 3000-fold improvement in separation relative to the precursor ions. Finally, we introduce a framework for interpreting and predicting the figures of merit for CAPTR experiments. More generally, these results suggest that CAPTR strongly complements other mass spectrometry tools for analyzing proteins and protein complexes, particularly those in mixtures.

  14. Synthesis and antimicrobial activity of polysaccharide alginate derived cationic surfactant-metal(II) complexes.

    PubMed

    Tawfik, Salah M; Hefni, Hassan H

    2016-01-01

    New natural polysaccharide carbohydrate derivatives of sodium alginate surfactant and its cobalt, copper and zinc complexes were synthesized. Structures of the synthesized compounds are reported using FTIR, (1)H NMR and UV-vis. The critical micelle concentration (CMC) value of the alginate surfactant and its metal complexes in aqueous solution was found out from surface tension measurements. Surface tension data at different temperatures served for the evaluation of the temperature-dependent CMC and the thermodynamics of micellization (ΔGmic, ΔHmic, ΔSmic) and adsorption (ΔGads, ΔGads, ΔSads). The surface activities of the synthesized polymeric surfactant and its metal complexes were influenced by their chemical structures and the type of the transition metals. These compounds were evaluated against Gram-positive bacteria (Bacillus subtilis and Staphylococcus aureus), Gram-negative bacteria (Escherichia coli and Pseudomonas aeruginosa) and fungi (Candida albicans and Asperigllus niger). The antibacterial and antifungal screening tests of the alginate surfactant metal complexes have shown good results compared to its precursor alginate surfactant. PMID:26478092

  15. Stability constants and thermodynamic data for complexes of 12-crown-4 with alkali metal and alkaline-earth cations in methanol solutions

    SciTech Connect

    Buschmann, H.

    1987-03-01

    The formation of 1:1- and 2:1-complexes of the crown ether 12C4 with mono- and bivalent cations was studied in methanol solutions by calorimetric, potentiometric and conductometric titrations. It is shown that not all donor atoms of the ligand 12C4 take part in complex formation. The accuracy of the three experimental methods are checked by comparing the results for the complexation of alkali ions with crown ether 18C6.

  16. Methyl-, Ethenyl-, and Ethynyl-Bridged Cationic Digold Complexes Stabilized by Coordination to a Bulky Terphenylphosphine Ligand.

    PubMed

    Espada, María F; Campos, Jesús; López-Serrano, Joaquín; Poveda, Manuel L; Carmona, Ernesto

    2015-12-14

    Reactions of the gold(I) triflimide complex [Au(NTf2 )(PMe2 Ar${{^{{\\rm Dipp}{_{2}}}}}$)] (1) with the gold(I) hydrocarbyl species [AuR(PMe2 Ar${{^{{\\rm Dipp}{_{2}}}}}$)] (2 a-2 c) enable the isolation of hydrocarbyl-bridged cationic digold complexes with the general composition [Au2 (μ-R)(PMe2 Ar${{^{{\\rm Dipp}{_{2}}}}}$)2 ][NTf2 ], where Ar${{^{{\\rm Dipp}{_{2}}}}}$=C6 H3 -2,6-(C6 H3 -2,6-iPr2 )2 and R=Me (3), CHCH2 (4), or CCH (5). Compound 3 is the first alkyl-bridged digold complex to be reported and features a symmetric [Au(μ-CH3 )Au](+) core. Complexes 4 and 5 are the first species of their kind that contain simple, unsubstituted vinyl and acetylide units, respectively. In the series of complexes 3-5, the bridging carbon atom systematically changes its hybridization from sp(3) to sp(2) and sp. Concomitant with this change, and owing to variations in the nature of the bonding within the [Au(μ-R)Au](+) unit, there is a gradual decrease in aurophilicity, that is, the strength of the Au⋅⋅⋅Au bonding interaction decreases. This change is illustrated by a monotonic increase in the Au-Au distance by approximately 0.3 Å from R=CH3 (2.71 Å) to CHCH2 (3.07 Å) and CCH (3.31 Å). PMID:26555404

  17. Charge Localization in Cation-Sulfate Complexes: Implications for Thermodynamic Surface Complexation Models of the Mineral/Water Interface

    SciTech Connect

    Boily, Jean F

    2007-01-25

    The applicability of separating charges of oxyanions across inner- and outer-Helmholtz planes according to the Charge Distribution model was tested by investigating the theoretical charge distribution in a range of metal-sulphate complexes using the methods of Atoms In Molecules and of the Electron Localisation Function. Density Functional Theory gas-phase geometry optimisation calculations revealed that unbound oxygens of the sulphate molecules contracted to relatively constant S-O bond lengths of 1.432 ± 0.019 (3) Å irrespective of the bond strength with the metal ions. The populations of the valence basins of the unbound oxygens also remained relatively constant, showing that even the strongest complexation induces very little charge distribution across the sulphate molecule. Maps of the Laplacian of the electron density and of the Electron Localisation Function revealed that although charge is relatively localised at oxygen centers there is not necessarily a clear charge separation between the inner- and outer-Helmholtz planes. The Proximity and Smit models are presented as alternative surface complexation schemes to provide a molecularly and electronically consistent depiction of the mineral/solution interface. These models are also presented in their capability in accounting for results from large-scale molecular models. It should nonetheless be emphasized that the Charge Distribution model remains a valuable approach and should have the best applicability at low surface loadings and with molecules with sizes similar to those of the compact layer.

  18. Complexation of trivalent cations (Al(III), Cr(III), Fe(III)) with two phosphonic acids in the pH range of fresh waters.

    PubMed

    Lacour, S; Deluchat, V; Bollinger, J C; Bernard Serpaud

    1998-08-01

    The complex formation constants of two phosphonic acids, HEDP and ATMP, with three trivalent metallic cations, Al(III), Cr(III) and Fe(III), have been determined by acid-base titration at 25 degrees C and constant ionic strength (0.1 mol l(-1), KNO(3)), using Martell and Motekaitis' computer programs. Species distribution curves showed that all three cations are in complex form in the pH range of fresh waters (5-9). The study of different cation/ligand ratios proved that both ligands mainly form anionic soluble complexes for systems having an excess of ligand-as protonated and unprotonated forms and especially ternary complexes with HEDP. For higher metal concentrations (excess of cation), weakly soluble species of HEDP and ATMP were formed with Al(III) and Cr(III). Two insoluble complexes with ATMP have been identified by SEM/EDAX as AlH(3)X((s)) and Cr(2)X((s)). Regarding Fe(III) species, Fe(OH)(3(s)) precipitate seems to predominate in solution. PMID:18967224

  19. Effect of Polyelectrolyte Stiffness and Solution pH on the Nanostructure of Complexes Formed by Cationic Amphiphiles and Negatively Charged Polyelectrolytes.

    PubMed

    Ram-On, Maor; Cohen, Yachin; Talmon, Yeshayahu

    2016-07-01

    The interaction between amphiphiles and polyelectrolytes has been widely investigated in recent years due to their potential application in industry and medicine, with special focus on gene therapy. The cationic lipid dioleoyl trimethylammonium propane, DOTAP, and the oppositely charged polyelectrolytes, sodium poly(acrylic acid) and sodium poly(styrenesulfonate), form multilamellar complexes in water. Because of the different molecular stiffness of the two polyelectrolytes, they form different nanostructured complexes. Also, because of the different ionization behavior of the two polyelectrolytes, pH differently affects the complexation of the polyelectrolytes with didodecyldimethylammonium bromide (DDAB), another cationic surfactant. We used cryogenic temperature transmission electron microscopy (cryo-TEM) and small-angle X-ray scattering (SAXS) to compare the nanostructures formed. Our results show that although the basic nanostructures of the complexes are always lamellar (multilamellar or unilamellar) the morphology of the complexes is affected by the polyelectrolyte rigidity and the solution pH. PMID:27049758

  20. Light-scattering study of polyelectrolyte complex formation between anionic and cationic nanogels in an aqueous salt-free system.

    PubMed

    Miyake, Masafumi; Ogawa, Kazuyoshi; Kokufuta, Etsuo

    2006-08-15

    We studied complex formation in an aqueous salt-free system (pH approximately 3 and at 25 degrees C) between nanogel particles having opposite charges. Anionic gel (AG) and cationic gel (CG) particles consist of lightly cross-linked N-isopropylacrylamide (NIPA) copolymers with 2-acrylamido-2-methylpropane sulfonic acid and with 1-vinylimidazole, respectively. The number of charges per particle was -4490 for AG and +20 300 for CG, as estimated from their molar masses (3.33 MD for AG and 11.7 MD for CG) by static light scattering (SLS) and their charge densities (1.35 mmol/g for AG and 1.74 mmol/g for CG) by potentiometric titration. The complexes were formed through the addition of AG to CG and vice versa using a turbidimetric titration technique. At the endpoint of the titration, the aggregate formed was a complex based upon stoichiometric charge neutralization: CG(n)()(+) + xAG(m)()(-) --> CG(n)()(+) (AG(m)()(-))(x)() where x = (n)()/(m)(). At different stages of the titration before the endpoint, the resulting complexes were examined in detail using dynamic light scattering, SLS, and electrophoretic light scattering (ELS). The main results are summarized as follows: (i) When AG with a hydrodynamic radius (R(h)) of 119 nm is added to CG (R(h) approximately 156 nm), the (R(h)) of the complex size decreases from 156 to 80 nm. (ii) In contrast to this (R(h)) change, the molar mass increases from 11.7 MD to 24 MD with increasing amounts of added AG. (iii) Upon addition of CG to AG, the complex formed has the same size ((R(h)) approximately 80 nm) and the same molar mass (55 +/- 2.5 MD) until 55 +/- 5% of AG has been consumed in the complexation. To understand these results, we used the following two models: the random model (RM), in which the added AG particles uniformly bind to all of the CG particles in the system via a strong electrostatic attraction, and the all-or-none model (AONM), in which part of the AG particles in the system preferably bind to the added CG

  1. Reversible Dissociation and Ligand-Glutathione Exchange Reaction in Binuclear Cationic Tetranitrosyl Iron Complex with Penicillamine

    PubMed Central

    Syrtsova, Lidia; Sanina, Natalia; Lyssenko, Konstantin; Kabachkov, Evgeniy; Psikha, Boris; Shkondina, Natal'ja; Pokidova, Olesia; Kotelnikov, Alexander; Aldoshin, Sergey

    2014-01-01

    This paper describes a comparative study of the decomposition of two nitrosyl iron complexes (NICs) with penicillamine thiolic ligands [Fe2(SC5H11NO2)2(NO)4]SO4·5H2O (I) and glutathione- (GSH-) ligands [Fe2(SC10H17N3O6)2(NO)4]SO4·2H2O (II), which spontaneously evolve to NO in aqueous medium. NO formation was measured by a sensor electrode and by spectrophotometric methods by measuring the formation of a hemoglobin- (Hb-) NO complex. The NO evolution reaction rate from (I)  k1 = (4.6 ± 0.1)·10−3 s−1 and the elimination rate constant of the penicillamine ligand k2 = (1.8 ± 0.2)·10−3 s−1 at 25°C in 0.05 M phosphate buffer,  pH 7.0, was calculated using kinetic modeling based on the experimental data. Both reactions are reversible. Spectrophotometry and mass-spectrometry methods have firmly shown that the penicillamine ligand is exchanged for GS− during decomposition of 1.5·10−4 M (I) in the presence of 10−3 M GSH, with 76% yield in 24 h. As has been established, such behaviour is caused by the resistance of (II) to decomposition due to the higher affinity of iron to GSH in the complex. The discovered reaction may impede S-glutathionylation of the essential enzyme systems in the presence of (I) and is important for metabolism of NIC, connected with its antitumor activity. PMID:24790592

  2. Reversible dissociation and ligand-glutathione exchange reaction in binuclear cationic tetranitrosyl iron complex with penicillamine.

    PubMed

    Syrtsova, Lidia; Sanina, Natalia; Lyssenko, Konstantin; Kabachkov, Evgeniy; Psikha, Boris; Shkondina, Natal'ja; Pokidova, Olesia; Kotelnikov, Alexander; Aldoshin, Sergey

    2014-01-01

    This paper describes a comparative study of the decomposition of two nitrosyl iron complexes (NICs) with penicillamine thiolic ligands [Fe2(SC5H11NO2)2(NO)4]SO4 ·5H2O (I) and glutathione- (GSH-) ligands [Fe2(SC10H17N3O6)2(NO)4]SO4 ·2H2O (II), which spontaneously evolve to NO in aqueous medium. NO formation was measured by a sensor electrode and by spectrophotometric methods by measuring the formation of a hemoglobin- (Hb-) NO complex. The NO evolution reaction rate from (I)  k 1 = (4.6 ± 0.1)·10(-3) s(-1) and the elimination rate constant of the penicillamine ligand k 2 = (1.8 ± 0.2)·10(-3) s(-1) at 25°C in 0.05 M phosphate buffer,  pH 7.0, was calculated using kinetic modeling based on the experimental data. Both reactions are reversible. Spectrophotometry and mass-spectrometry methods have firmly shown that the penicillamine ligand is exchanged for GS(-) during decomposition of 1.5·10(-4) M (I) in the presence of 10(-3) M GSH, with 76% yield in 24 h. As has been established, such behaviour is caused by the resistance of (II) to decomposition due to the higher affinity of iron to GSH in the complex. The discovered reaction may impede S-glutathionylation of the essential enzyme systems in the presence of (I) and is important for metabolism of NIC, connected with its antitumor activity. PMID:24790592

  3. Unique solvatochromism of a membrane composed of a cationic porphyrin-clay complex.

    PubMed

    Takagi, Shinsuke; Shimada, Tetsuya; Masui, Dai; Tachibana, Hiroshi; Ishida, Yohei; Tryk, Donald A; Inoue, Haruo

    2010-04-01

    A novel optically transparent membrane composed of porphyrin-clay mineral complexes was developed. Reversible solvatochromism behavior of the membrane was successfully observed, due to an orientation change of porphyrin in the clay interlayer space. The lambda(max) value of porphyrin was 423 nm in acetone, while it was 464 nm in hexane. The color of the membrane changed from pink to green through to brown, when Sn porphyrin was used. The mechanism for solvatochromism in the present system is very unique compared to those for conventionally reported materials. PMID:20229990

  4. Effect of CO on the oxidative addition of arene C-H bonds by cationic rhodium complexes.

    PubMed

    Montag, Michael; Efremenko, Irena; Cohen, Revital; Shimon, Linda J W; Leitus, Gregory; Diskin-Posner, Yael; Ben-David, Yehoshoa; Salem, Hiyam; Martin, Jan M L; Milstein, David

    2010-01-01

    Sequential addition of CO molecules to cationic aryl-hydrido Rh(III) complexes of phosphine-based (PCP) pincer ligands was found to lead first to C-H reductive elimination and then to C-H oxidative addition, thereby demonstrating a dual role of CO. DFT calculations indicate that the oxidative addition reaction is directly promoted by CO, in contrast to the commonly accepted view that CO hinders such reactions. This intriguing effect was traced to repulsive pi interactions along the aryl-Rh-CO axis, which are augmented by the initially added CO ligand (due to antibonding interactions between occupied Rh d(pi) orbitals and occupied pi orbitals of both CO and the arene moiety), but counteracted by the second CO ligand (due to significant pi back-donation). These repulsive interactions were themselves linked to significant weakening of the pi-acceptor character of CO in the positively charged rhodium complexes, which is concurrent with an enhanced sigma-donating capability. Replacement of the phosphine ligands by an analogous phosphinite-based (POCOP) pincer ligand led to significant changes in reactivity, whereby addition of CO did not result in C-H reductive elimination, but yielded relatively stable mono- and dicarbonyl aryl-hydrido POCOP-Rh(III) complexes. DFT calculations showed that the stability of these complexes arises from the higher electrophilicity of the POCOP ligand, relative to PCP, which leads to partial reduction of the excessive pi-electron density along the aryl-Rh-CO axis. Finally, comparison between the effects of CO and acetonitrile on C-H oxidative addition revealed that they exhibit similar reactivity, despite their markedly different electronic properties. However, DFT calculations indicate that the two ligands operate by different mechanisms. PMID:19918810

  5. Toward stereoselective lactide polymerization catalysts: cationic zinc complexes supported by a chiral phosphinimine scaffold.

    PubMed

    Sun, Hongsui; Ritch, Jamie S; Hayes, Paul G

    2011-09-01

    The P-stereogenic phosphinimine ligands (dbf)MePhP═NAr (7: Ar = Dipp; 8: Ar = Mes; dbf = dibenzofuran, Dipp = 2,6-diisopropylphenyl, Mes = 2,4,6-trimethylphenyl) were synthesized as racemates via reactions of the parent phosphines (rac)-(dbf)MePhP (6) with organoazides. The ligands 7 and 8 were protonated by Brønsted acids to afford the aminophosphonium borate salts [(7)-H][BAr(4)] (9: Ar = C(6)F(5); 11: Ar = Ph) and [(8)-H][BAr(4)] (10: Ar = C(6)F(5); 12: Ar = Ph). The protonated ligands 9 and 10 were active toward alkane elimination reactions with diethylzinc and ethyl-[methyl-(S)-lactate]zinc to give the heteroleptic complexes [{(dbf)MePhP═NAr}ZnR][B(C(6)F(5))(4)] (Ar = Dipp, 13: R = Et; 15: R = methyl-(S)-lactate; Ar = Mes, 14: R = Et; 16: R = methyl-(S)-lactate). By contrast, reaction of the tetraphenylborate derivative 11 with diethylzinc yielded a phenyl transfer product, [(dbf)MePhP═NDipp]ZnPh(2) (17). Complex 15 was found to catalyze the ring-opening polymerization of rac-lactide. PMID:21790171

  6. Large Size Color-tunable Electroluminescence from Cationic Iridium Complexes-based Light-emitting Electrochemical Cells.

    PubMed

    Zeng, Qunying; Li, Fushan; Guo, Tailiang; Shan, Guogang; Su, Zhongmin

    2016-01-01

    Solution-processable light-emitting electrochemical cells (LECs) with simple device architecture have become an attractive candidate for application in next generation lighting and flat-panel displays. Herein, single layer LECs employing two cationic Ir(III) complexes showing highly efficient blue-green and yellow electroluminescence with peak current efficiency of 31.6 cd A(-1) and 40.6 cd A(-1), respectively, have been reported. By using both complexes in the device, color-tunable LECs with a single spectral peak in the wavelength range from 499 to 570 nm were obtained by varying their rations. In addition, the fabrication of efficient LECs was demonstrated based on low cost doctor-blade coating technique, which was compatible with the roll to roll fabrication process for the large size production. In this work, for the first time, 4 inch LEC devices by doctor-blade coating were fabricated, which exhibit the efficiencies of 23.4 cd A(-1) and 25.4 cd A(-1) for the blue-green and yellow emission, respectively. The exciting results indicated that highly efficient LECs with controllable color could be realized and find practical application in large size lighting and displays. PMID:27278527

  7. Large Size Color-tunable Electroluminescence from Cationic Iridium Complexes-based Light-emitting Electrochemical Cells

    NASA Astrophysics Data System (ADS)

    Zeng, Qunying; Li, Fushan; Guo, Tailiang; Shan, Guogang; Su, Zhongmin

    2016-06-01

    Solution-processable light-emitting electrochemical cells (LECs) with simple device architecture have become an attractive candidate for application in next generation lighting and flat-panel displays. Herein, single layer LECs employing two cationic Ir(III) complexes showing highly efficient blue-green and yellow electroluminescence with peak current efficiency of 31.6 cd A‑1 and 40.6 cd A‑1, respectively, have been reported. By using both complexes in the device, color-tunable LECs with a single spectral peak in the wavelength range from 499 to 570 nm were obtained by varying their rations. In addition, the fabrication of efficient LECs was demonstrated based on low cost doctor-blade coating technique, which was compatible with the roll to roll fabrication process for the large size production. In this work, for the first time, 4 inch LEC devices by doctor-blade coating were fabricated, which exhibit the efficiencies of 23.4 cd A‑1 and 25.4 cd A‑1 for the blue-green and yellow emission, respectively. The exciting results indicated that highly efficient LECs with controllable color could be realized and find practical application in large size lighting and displays.

  8. Manipulating Mn–Mgk cation complexes to control the charge- and spin-state of Mn in GaN

    PubMed Central

    Devillers, Thibaut; Rovezzi, Mauro; Szwacki, Nevill Gonzalez; Dobkowska, Sylwia; Stefanowicz, Wiktor; Sztenkiel, Dariusz; Grois, Andreas; Suffczyński, Jan; Navarro-Quezada, Andrea; Faina, Bogdan; Li, Tian; Glatzel, Pieter; d'Acapito, Francesco; Jakieła, Rafał; Sawicki, Maciej; Majewski, Jacek A.; Dietl, Tomasz; Bonanni, Alberta

    2012-01-01

    Owing to the variety of possible charge and spin states and to the different ways of coupling to the environment, paramagnetic centres in wide band-gap semiconductors and insulators exhibit a strikingly rich spectrum of properties and functionalities, exploited in commercial light emitters and proposed for applications in quantum information. Here we demonstrate, by combining synchrotron techniques with magnetic, optical and ab initio studies, that the codoping of GaN:Mn with Mg allows to control the Mnn+ charge and spin state in the range 3≤n≤5 and 2≥S≥1. According to our results, this outstanding degree of tunability arises from the formation of hitherto concealed cation complexes Mn-Mgk, where the number of ligands k is pre-defined by fabrication conditions. The properties of these complexes allow to extend towards the infrared the already remarkable optical capabilities of nitrides, open to solotronics functionalities, and generally represent a fresh perspective for magnetic semiconductors. PMID:23056914

  9. Large Size Color-tunable Electroluminescence from Cationic Iridium Complexes-based Light-emitting Electrochemical Cells

    PubMed Central

    Zeng, Qunying; Li, Fushan; Guo, Tailiang; Shan, Guogang; Su, Zhongmin

    2016-01-01

    Solution-processable light-emitting electrochemical cells (LECs) with simple device architecture have become an attractive candidate for application in next generation lighting and flat-panel displays. Herein, single layer LECs employing two cationic Ir(III) complexes showing highly efficient blue-green and yellow electroluminescence with peak current efficiency of 31.6 cd A−1 and 40.6 cd A−1, respectively, have been reported. By using both complexes in the device, color-tunable LECs with a single spectral peak in the wavelength range from 499 to 570 nm were obtained by varying their rations. In addition, the fabrication of efficient LECs was demonstrated based on low cost doctor-blade coating technique, which was compatible with the roll to roll fabrication process for the large size production. In this work, for the first time, 4 inch LEC devices by doctor-blade coating were fabricated, which exhibit the efficiencies of 23.4 cd A−1 and 25.4 cd A−1 for the blue-green and yellow emission, respectively. The exciting results indicated that highly efficient LECs with controllable color could be realized and find practical application in large size lighting and displays. PMID:27278527

  10. The Relation between the Physical Properties of Self-Assembling Cationic Lipid:DNA Complexes and Gene Delivery

    NASA Astrophysics Data System (ADS)

    Ahmad, A.; Slack, N. L.; Evans, Heather M.; Lin, Alison; Martin, A.; Safinya, C. R.

    2000-03-01

    The use of cationic lipids (CL) as carriers of genes (DNA sequences) for delivery in cells is a promising alternative to viral-carriers. Previous work on CL:DNA complexes has focused on binary mixtures of lipids and has shown that the optimal gene delivery vehicle may be mediated by physical properties of the lipid self-assembly(1). Using x-ray diffraction and biological assays, we show that membrane charge density and geometric shape may be universal parameters for successful gene delivery by binary CL mixtures in vitro. Preliminary results from complexes containing novel ternary CL mixtures further elucidate key parameters for gene delivery. Funded by NIH R01-GM59288-01 and R37-AI12520-24, UCBiotechnology Research and Education Program (97-02), NSF-DMR-9972246. 1. J. Raedler et al, Science 275, 810 (1997), Koltover et al Science 281, 78-81 (1998), Koltover et al, Biophysical Journal 77, 95 (1999), A. J. Lin, N. L. Slack, A. Ahmad, I. Koltover, C. X. George, C. E. Samuel, C. R. Safinya, Journal of Drug Targeting (to appear)

  11. Phosphorescence imaging of homocysteine and cysteine in living cells based on a cationic iridium(III) complex.

    PubMed

    Xiong, Liqin; Zhao, Qiang; Chen, Huili; Wu, Yanbo; Dong, Zesheng; Zhou, Zhiguo; Li, Fuyou

    2010-07-19

    Homocysteine (Hcy) and cysteine (Cys) are crucial to the physiological balance in living systems. Specific detection of intracellular Hcy and Cys is of growing importance. Herein, we demonstrated phosphorescence imaging of intracellular Hcy and Cys using a cationic iridium(III) complex Ir(pba)(2)(bpy)(+).PF(6)(-) [pba = 4-(2-pyridyl)benzaldehyde, bpy = bipyridine] containing aldehyde groups as a luminescent probe. Upon addition of Hcy or Cys to a semiaqueous solution of Ir(pba)(2)(bpy)(+), a change in luminescence from yellow to red was visible to the naked eye. The successful chemical reaction of the aldehyde in Ir(pba)(2)(bpy)(+) with Hcy and Cys to form thiazinane and thiazolidine was confirmed by (1)H NMR. Moreover, complexation with Hcy and Cys disturbed the p-pi conjugation between the aldehyde group and the bpy moiety, and led to the excited states switching to [dpi(Ir)-pi(N(wedge)N)*] (3)MLCT and [pi(C(wedge)N)-pi(N(wedge)N)*] (3)LLCT from (pi-pi*)(pba(-)) (3)IL. Furthermore, the MTT assay was used to determine that the probe has low cytotoxicity. Importantly, cell imaging experiments demonstrated that the probe is membrane permeable and can monitor the changes of Hcy/Cys within living cells in a ratiometric mode. PMID:20565069

  12. Dimerization of the octaethylporphyrin {pi} cation radical complex of cobalt(II): Thermodynamic, kinetic, and spectroscopic studies

    SciTech Connect

    Ni, Y.; Lee, S.; Wayland, B.B.

    1999-08-23

    One electron oxidation of cobalt(II) can occur from either the cobalt d or porphyrin {pi} orbitals depending on the choice of porphyrin and reaction media. Oxidation of (octaethylporphyrinato)cobalt(II), (OEP)Co{sup II} (1), in the presence of ligands such as H{sub 2}O and CO produces diamagnetic five and six coordinate complexes of cobalt(III). In the absence of additional ligands to coordinate with Co(III) the first oxidation of [(OEP)Co{sup II}]{sup +} (2). Metalloporphyrin {pi} cation radical complexes and dimers of the OEP derivatives have been extensively investigated. This article reports on the interconversion of the paramagnetic (S = 1) monomer, [(OEP)Co{sup II}]{sup +} (2), with a diamagnetic dimer, [(OEP)-Co{sup II}]{sub 2}{sup 2+} (3), in dichloromethane solvant. {sup 1}H NMR shift and line width studies in CD{sub 2}Cl{sub 2} are applied in evaluating the thermodynamic and activation parameters for homolytic dissociation of the diamagnetic dimer (3).

  13. Complex functions of phosphatidylinositol 4,5-bisphosphate in regulation of TRPC5 cation channels.

    PubMed

    Trebak, Mohamed; Lemonnier, Loic; DeHaven, Wayne I; Wedel, Barbara J; Bird, Gary S; Putney, James W

    2009-02-01

    The canonical transient receptor potential (TRPC) proteins have been recognized as key players in calcium entry pathways activated through phospholipase-C-coupled receptors. While it is clearly demonstrated that members of the TRPC3/6/7 subfamily are activated by diacylglycerol, the mechanism by which phospholipase C activates members of the TRPC1/4/5 subfamily remains a mystery. In this paper, we provide evidence for both negative and positive modulatory roles for membrane polyphosphoinositides in the regulation of TRPC5 channels. Depletion of polyphosphatidylinositol 4-phosphate and phosphatidylinositol 4,5-bisphosphate (PIP2) through inhibition of phosphatidylinositol 4-kinase activates calcium entry and membrane currents in TRPC5-expressing but not in TRPC3- or TRPC7-expressing cells. Inclusion of polyphosphatidylinositol 4-phosphate or PIP2, but not phosphatidylinositol 3,4,5-trisphosphate, in the patch pipette inhibited TRPC5 currents. Paradoxically, depletion of PIP2 with a directed 5-phosphatase strategy inhibited TRPC5. Furthermore, when the activity of single TRPC5 channels was examined in excised patches, the channels were robustly activated by PIP2. These findings indicate complex functions for regulation of TRPC5 by PIP2, and we propose that membrane polyphosphoinositides may have at least two distinct functions in regulating TRPC5 channel activity. PMID:18665391

  14. On the stability of cationic complexes of neon with helium--solving an experimental discrepancy.

    PubMed

    Bartl, Peter; Denifl, Stephan; Scheier, Paul; Echt, Olof

    2013-10-21

    Helium nanodroplets are doped with neon and ionized by electrons. The size-dependence of the ion abundance of HenNex(+), identified in high-resolution mass spectra, is deduced for complexes containing up to seven neon atoms and dozens of helium atoms. Particularly stable ions are inferred from anomalies in the abundance distributions. Two pronounced anomalies at n = 11 and 13 in the HenNe(+) series confirm drift-tube data reported by Kojima et al. [T. M. Kojima et al., Z. Phys. D, 1992, 22, 645]. The discrepancy with previously published spectra of neon-doped helium droplets, which did not reveal any abundance anomalies [T. Ruchti et al., J. Chem. Phys., 1998, 109, 10679-10687; C. A. Brindle et al., J. Chem. Phys., 2005, 123, 064312], is most likely due to limited mass resolution, which precluded unambiguous analysis of contributions from different ions with identical nominal mass. However, calculated dissociation energies of HenNe(+) reported so far do not correlate with the present data, possibly because of challenges in correctly treating the linear, asymmetric [He-Ne-He](+) ionic core in HenNe(+). Anomalies identified in the distributions of HenNex(+) for x > 1, including prominent ones at He12Ne2(+) and He14Ne2(+), may help to better understand solvation of Ne(+) and Nex(+) in helium. PMID:23958826

  15. Cationic conjugated polymer/fluoresceinamine-hyaluronan complex for sensitive fluorescence detection of CD44 and tumor-targeted cell imaging.

    PubMed

    Huang, Yanqin; Yao, Xin; Zhang, Rui; Ouyang, Lang; Jiang, Rongcui; Liu, Xingfen; Song, Caixia; Zhang, Guangwei; Fan, Quli; Wang, Lianhui; Huang, Wei

    2014-01-01

    Simple, rapid, and sensitive detection of CD44 is of paramount importance since it plays pivotal roles in tumor initiation, growth and metastasis. Herein, we describe a novel method for sensitive, visual and facile fluorescence detection of CD44 and CD44-mediated cancer cell imaging, using a probe based on cationic conjugated polymer (CCP)-PFEP and fluoresceinamine-hyaluronan (FA-HA). HA is an anionic natural glycosaminoglycan that can specifically bind to the overexpressed CD44 on various kinds of cancer cells. PFEP and FA-HA formed a complex through electronic interactions, resulting in a highly efficient fluorescence resonance energy transfer (FRET) from PFEP to FA-HA; moreover, the efficiencies of FRET correlated with the concentrations of CD44 because the specific binding of HA-CD44 would separate FA-HA away from PFEP. This method did not require laborious and expensive dual-labeling or protein-labeling needed in previously reported detection methods of CD44. Just mix the sample and test solution containing the PFEP/FA-HA complex, and the results allowed naked-eye detection by observing fluorescent color of solutions with the assistance of a UV lamp. Most importantly, the use of a conjugated polymer with excellent amplification property as well as the specific binding of HA-CD44 endowed this method with high sensitivity and specificity, making it applicable for reliable quantitative detection of CD44. Furthermore, the PFEP/FA-HA complex formed nanoparticles in aqueous solution, and the nanoparticles can be selectively taken up by MCF-7 cells (cancer cell) through the HA-CD44 interaction, thereby giving rise to a dual-color tumor-targeted imaging probe with good photostability. The development of this fluorescent probe showed promising potential to make a reliable and routine method available for early diagnosis of cancer. PMID:25278260

  16. Polymeric heterometallic Pb-Ag iodometallates, iodoplumbates and iodoargentates with lanthanide complex cations as templates.

    PubMed

    Fang, Wang; Tang, Chunying; Chen, Ruihong; Jia, Dingxian; Jiang, Wenqing; Zhang, Yong

    2013-11-14

    Heterometallic Pb-Ag iodometallates [Ln(DMF)8]2Pb3Ag10I22 [Ln = Ce(1), Pr(2)] were prepared by the reactions of PbI2, AgNO3 and KI in dimethylformamide (DMF) templated by [Ln(DMF)8](3+) complexes formed in situ by stirring LnCl3 in DMF. The same reactions in the absence of AgNO3 or PbI2 afforded iodoplumbate [Pr(DMF)9]2[Pr(DMF)8]Pb11I31 (3), and iodoargentates [Ln(DMF)8]Ag6I9 [Ln = Ce(4), Pr(5)], respectively. Compounds 1 and 2 contain a ternary one-dimensional polymeric [Pb3Ag10I22](6-) anion self-assembled from five AgI4, one PbI6 and one PbI4 primary units via edge- and face-sharing. Twelve PbI6 octahedra are interlinked via sharing of common faces to generate a 1D zigzag [Pb11I31(9-)]n chain in 3, which represents a new member of iodoplumbate aggregates. In 4 and 5, three AgI4 tetrahedra connect through common edges to form the [Ag6I12](6-) building block. The [Ag6I12](6-) blocks are further interlinked by sharing common edges, resulting in the 1D [Ag6I9(3-)]n chain. Optical absorption spectra showed that the synthesized Ag-iodoplumbate and iodoplumbate have potential for being used as semiconductors. Our results show that heterometallic halometallate properties can be tuned by combining structural units with different symmetries, enabling the synthesis of specific functional materials. PMID:24005846

  17. Chiral Nanostructures from Helical Copolymer-Metal Complexes: Tunable Cation-π Interactions and Sergeants and Soldiers Effect.

    PubMed

    Arias, Sandra; Bergueiro, Julián; Freire, Félix; Quiñoá, Emilio; Riguera, Ricardo

    2016-01-13

    Poly(phenylacetylene) (PPA) copolymers containing (R)- or (S)-MPA as minor chiral pendant can be forced to selectively adopt the right- o left-handed helix, in the presence of small amounts of Na(+) or Ag(+) ("Sergeants and Soldiers Effect") by addition of a donor cosolvent. The helical sense depends exclusively on the chiral monomer/donor cosolvent ratio, and this allows a perfect on/off tuning of the helicity of the copolymer. When the amount of the donor cosolvent is low, the metal ion complex is stabilized by a cation-π interaction, which is selectively cleaved when the amount of cosolvent is higher. Macroscopically chiral nanospheres and nanotubes composed by helical copolymers with P or M helical sense are also described. Our results demonstrate that it is possible to obtain the two enantiomeric helical structures (P and M helicities) and the corresponding nanospheres and nanotubes from a single helical copolymer, by controlled activation/deactivation of the Sergeant and Soldiers Effect with a donor cosolvent. PMID:26578292

  18. Cholesterol derived cationic lipids as potential non-viral gene delivery vectors and their serum compatibility.

    PubMed

    Ju, Jia; Huan, Meng-Lei; Wan, Ning; Hou, Yi-Lin; Ma, Xi-Xi; Jia, Yi-Yang; Li, Chen; Zhou, Si-Yuan; Zhang, Bang-Le

    2016-05-15

    Cholesterol derivatives M1-M6 as synthetic cationic lipids were designed and the biological evaluation of the cationic liposomes based on them as non-viral gene delivery vectors were described. Plasmid pEGFP-N1, used as model gene, was transferred into 293T cells by cationic liposomes formed with M1-M6 and transfection efficiency and GFP expression were tested. Cationic liposomes prepared with cationic lipids M1-M6 exhibited good transfection activity, and the transfection activity was parallel (M2 and M4) or superior (M1 and M6) to that of DC-Chol derived from the same backbone. Among them, the transfection efficiency of cationic lipid M6 was parallel to that of the commercially available Lipofectamine2000. The optimal formulation of M1 and M6 were found to be at a mol ratio of 1:0.5 for cationic lipid/DOPE, and at a N/P charge mol ratio of 3:1 for liposome/DNA. Under optimized conditions, the efficiency of M1 and M6 is greater than that of all the tested commercial liposomes DC-Chol and Lipofectamine2000, even in the presence of serum. The results indicated that M1 and M6 exhibited low cytotoxicity, good serum compatibility and efficient transfection performance, having the potential of being excellent non-viral vectors for gene delivery. PMID:27072908

  19. Reactions of cationic transition metal acetonitrile complexes [M(CH3CN)n]m+ with GaCp*: novel gallium complexes of iron, cobalt, copper and silver.

    PubMed

    Bollermann, Timo; Puls, Arik; Gemel, Christian; Cadenbach, Thomas; Fischer, Roland A

    2009-02-28

    The reactions of the cationic transition metal acetonitrile complexes [M(CH3CN)n]m+ (m = 2: M = Fe, Co and m = 1: M = Cu, Ag) with GaCp* were investigated. The reaction of [Fe(CH3CN)6][BArF]2 (BAr(F) = [B{C6H3(CF3)2}4) with GaCp* leads to [Cp*Fe(GaCp*)3][BAr(F)] (1) via a redox neutral Cp* transfer and [Ga2Cp*][BAr(F)] as a by-product while the formation of [Cp*Co(GaCp*)3][BAr(F)]2 (2) from [Co(CH3CN)6][BAr(F)]2 is accompanied by oxidation of Co(II) to Co(III) with GaCp* as the oxidant. The reactions of [Cu(CH3CN)4][BAr(F)] and Ag[BPh4] with GaCp* lead to the formation of the homoleptic compounds [Cu(GaCp*)4][BAr(F)] (4) and [Ag(GaCp*)4][BPh4] (5), while treatment of Ag[CF3SO3] with GaCp* leads to the dimeric complex [Ag2(GaCp*)3(micro-GaCp*)2][CF3SO3]2 (6). All compounds were characterized by NMR spectroscopy, single crystal X-ray diffraction and elemental analysis. PMID:19462658

  20. Phosphorus dendrimers and photodynamic therapy. Spectroscopic studies on two dendrimer-photosensitizer complexes: Cationic phosphorus dendrimer with rose bengal and anionic phosphorus dendrimer with methylene blue.

    PubMed

    Dabrzalska, Monika; Zablocka, Maria; Mignani, Serge; Majoral, Jean Pierre; Klajnert-Maculewicz, Barbara

    2015-08-15

    Dendrimers due to their unique architecture may play an important role in drug delivery systems including chemotherapy, gene therapy and recently, photodynamic therapy as well. We investigated two dendrimer-photosensitizer systems in context of potential use of these systems in photodynamic therapy. The mixtures of an anionic phosphorus dendrimer of the second generation and methylene blue were studied by UV-vis spectroscopy while that of a cationic phosphorus dendrimer (third generation) and rose bengal were investigated by spectrofluorimetric methods. Spectroscopic analysis of these two systems revealed the formation of dendrimer-photosensitizer complexes via electrostatic interactions as well as π stacking. The stoichiometry of the rose bengal-cationic dendrimer complex was estimated to be 7:1 and 9:1 for the methylene blue-anionic dendrimer complex. The results suggest that these polyanionic or polycationic phosphorus dendrimers can be promising candidates as carriers in photodynamic therapy. PMID:26117192

  1. X-ray, spectroscopic and semiempirical investigation of the structure of lasalocid 6-bromohexyl ester and its complexes with alkali metal cations

    NASA Astrophysics Data System (ADS)

    Huczyński, Adam; Ratajczak-Sitarz, Małgorzata; Katrusiak, Andrzej; Brzezinski, Bogumil

    2011-07-01

    The ionophoric antibiotic lasalocid acid has been converted to a novel 6-bromohexyl ester (LASBR) and its structure has been determined in the crystal by X-ray diffraction and in solution by NMR and FT-IR methods. In the crystal two symmetry-independent LASBR molecules are present. The structure of LASBR in solution is slightly different because the strongest intramolecular C(1) dbnd O⋯H sbnd (3)O hydrogen bond in the pseudo-aromatic ring becomes partially broken and a new hydrogen bond between O(4)H and carbonyl group C(13) dbnd O is formed. LASBR forms complexes with Li +, Na + and K + cations of exclusively 1:1 stoichiometry. The structures of complexes have been studied and visualized using semi-empirical calculation based on results of spectrometric and spectroscopic investigation. It is demonstrated that in contrast to lasalocid acid the novel ester forms preferential complexes with Li + cation.

  2. Thermo- and solvent-responsive polymer complex created from supramolecular complexation between a helix-forming polysaccharide and a cationic polythiophene.

    PubMed

    Shiraki, Tomohiro; Dawn, Arnab; Tsuchiya, Youichi; Shinkai, Seiji

    2010-10-01

    The helical structure is one of key structural components for both biological systems and artificial chiral systems. So far, we have succeeded in fabricating "tight" insulated molecular wires consisting of a triple-stranded cohelical structure formed through supramolecular wrapping of synthetic polymers by a helix-forming polysaccharide (schizophyllan). Herein, we have designed a new modified polysaccharide (Cur-oeg) to form a "loose" macromolecular complex with a conjugated polymer (CP) that allows structural changes in response to external stimuli. Cur-oeg forms a helical complex with an achiral cationic polythiophene (PT1), and the effective conjugation length is changed by temperature, showing a large absorption peak shift from 403 to 482 nm between 85 and 5 °C. According to the change in the conjugation system, the fluorescence and the induced circular dichroism show the continuous spectral shifts under temperature control. The color changes in the absorption and the fluorescence are detectable with observation by the naked eye and are reversibly controlled under thermal cycles, indicating that this system has the function of a "molecular thermometer". It is shown that the induced thermoresponsiveness is associated with structural rearrangement of the helical conformation of PT1 in the complex. Moreover, another unique responsiveness is discovered for the film state: that is, the film color is varied when it is exposed to the vapor of water or methanol (vaporchromism), resulting from the structural change of PT1 occurring even in the film state. These flexible molecular motions in both the solution state and the film state can be applicable to the design of CP-based smart sensors, polarized materials, switching devices, etc. PMID:20836560

  3. FT-IR, 1H, 13C NMR, ESI-MS and semiempirical investigation of the structures of Monensin phenyl urethane complexes with the sodium cation.

    PubMed

    Huczyński, Adam

    2013-06-01

    In this paper three forms of phenyl urethane of Monensin i.e. its acid form (H-MU) and its 1:1 complex with NaClO4 (H-MU-Na) and its sodium salt (Na-MU) were obtained and their structures were studied by FT-IR, (1)H and (13)C NMR, ESI MS and PM5 methods. The FT-IR data of Na-MU complexes demonstrate that the C=O urethane group is not engaged in the complexation of the sodium cation. However spectroscopic studies of H-MU-Na complex show that the structure in which this C=O urethane groups participate in the complexation is also present, but it is in the minority. The PM5 semiempirical calculations allow visualisation of all structures and determination of the hydrogen bond parameters. PMID:23578536

  4. The electronic structure of vanadium monochloride cation (VCl{sup +}): Tackling the complexities of transition metal species

    SciTech Connect

    DeYonker, Nathan J.; Halfen, DeWayne T.; Ziurys, Lucy M.; Allen, Wesley D.

    2014-11-28

    Six electronic states (X {sup 4}Σ{sup −}, A {sup 4}Π, B {sup 4}Δ, {sup 2}Φ, {sup 2}Δ, {sup 2}Σ{sup +}) of the vanadium monochloride cation (VCl{sup +}) are described using large basis set coupled cluster theory. For the two lowest quartet states (X {sup 4}Σ{sup −} and A {sup 4}Π), a focal point analysis (FPA) approach was used that conjoined a correlation-consistent family of basis sets up to aug-cc-pwCV5Z-DK with high-order coupled cluster theory through pentuple (CCSDTQP) excitations. FPA adiabatic excitation energies (T{sub 0}) and spectroscopic constants (r{sub e}, r{sub 0}, B{sub e}, B{sub 0}, D{sup ¯}{sub e}, H{sub e}, ω{sub e}, v{sub 0}, α{sub e}, ω{sub e}x{sub e}) were extrapolated to the valence complete basis set Douglas-Kroll (DK) aug-cc-pV∞Z-DK CCSDT level of theory, and additional treatments accounted for higher-order valence electron correlation, core correlation, and spin-orbit coupling. Due to the delicate interplay between dynamical and static electronic correlation, single reference coupled cluster theory is able to provide the correct ground electronic state (X {sup 4}Σ{sup −}), while multireference configuration interaction theory cannot. Perturbations from the first- and second-order spin orbit coupling of low-lying states with quartet spin multiplicity reveal an immensely complex rotational spectrum relative to the isovalent species VO, VS, and TiCl. Computational data on the doublet manifold suggest that the lowest-lying doublet state ({sup 2}Γ) has a T{sub e} of ∼11 200 cm{sup −1}. Overall, this study shows that laboratory and theoretical rotational spectroscopists must work more closely in tandem to better understand the bonding and structure of molecules containing transition metals.

  5. Confocal Microscopy Studies of Cationic Lipid/dna Complexes Reveal Distinct Pathways of Gene Delivery in Cells as a Function of Structure

    NASA Astrophysics Data System (ADS)

    Lin, Alison J.; Slack, Nelle L.; Ahmad, Ayesha; Evans, Heather M.; George, Cyril X.; Samuel, Charles E.; Safinya, Cyrus R.

    2000-03-01

    We have identified multiple pathways of gene delivery in mouse L cells using cationic lipids as carriers of DNA. Transfection, the process of delivering foreign DNA into cells, using cationic lipid/DNA (CL-DNA) complexes was monitored by laser confocal microscopy. By following the progress of fluorescently labelled lipid and DNA, we have determined distinct pathways of entry of complexes into cells and the subsequent DNA release from the complexes. We have correlated the microscopy results with the x-ray diffraction data on complex structures and the corresponding transfection efficiencies. X-ray diffraction results elucidated the structures of CL-DNA complexes as a function of the membrane charge density of the system. Luciferase protein assays disclosed novel trends of transfection efficiencies along the structural phase diagram. Similar results were obtained with GFP plasmids. Funded by NIH R01-GM59288-01, R37-AI12520-24, NSF-DMR 9972246, UC-Biotechnology Research and Education Program (97-02).

  6. Many-body exchange-repulsion in polarizable molecular mechanics. I. Orbital-based approximations and applications to hydrated metal cation complexes.

    PubMed

    Chaudret, Robin; Gresh, Nohad; Parisel, Olivier; Piquemal, Jean-Philip

    2011-11-15

    We have quantified the extent of the nonadditivity of the short-range exchange-repulsion energy, E(exch-rep), in several polycoordinated complexes of alkali, alkaline-earth, transition, and metal cations. This was done by performing ab initio energy decomposition analyses of interaction energies in these complexes. The magnitude of E(exch-rep(n-body, n > 2)) was found to be strongly cation-dependent, ranging from close to zero for some alkali metal complexes to about 6 kcal/mol for the hexahydrated Zn(2+) complex. In all cases, the cation-water molecules, E(exch-rep(three-body)), has been found to be the dominant contribution to many-body exchange-repulsion effects, higher order terms being negligible. As the physical basis of this effect is discussed, a three-center exponential term was introduced in the SIBFA (Sum of Interactions Between Fragments Ab initio computed) polarizable molecular mechanics procedure to model such effects. The three-body correction is added to the two-center (two-body) overlap-like formulation of the short-range repulsion contribution, E(rep), which is grounded on simplified integrals obtained from localized molecular orbital theory. The present term is computed on using mostly precomputed two-body terms and, therefore, does not increase significantly the computational cost of the method. It was shown to match closely E(three-body) in a series of test cases bearing on the complexes of Ca(2+), Zn(2+), and Hg(2+). For example, its introduction enabled to restore the correct tetrahedral versus square planar preference found from quantum chemistry calculations on the tetrahydrate of Hg(2+) and [Hg(H(2)O)(4)](2+). PMID:21793002

  7. Cu(II) and Cu(I) coordination complexes involving two tetrathiafulvalene-1,3-benzothiazole hybrid ligands and their radical cation salts.

    PubMed

    Yokota, Sayo; Tsujimoto, Keijiro; Hayashi, Sadayoshi; Pointillart, Fabrice; Ouahab, Lahcène; Fujiwara, Hideki

    2013-06-01

    Preparations, crystal structure analyses, and magnetic property investigations on a new Cu(II)(hfac)2 complex coordinated with two TTF-CH═CH-BTA ligands, where hfac is hexafluoroacetylacetonate, TTF is tetrathiafulvalene, and BTA is 1,3-benzothiazole, are reported together with those of its dicationic AsF6(-) salt, [Cu(hfac)2(TTF-CH═CH-BTA)2](AsF6)2, in which each TTF part is in a radical cation state. In these Cu(II)(hfac)2 complexes, two ligands are bonded to the central Cu atom of the Cu(hfac)2 part through the nitrogen atom of the 1,3-benzothiazole ring and occupy the two apical positions of the Cu(hfac)2 complex with an elongated octahedral geometry. These two ligands are located parallelly in a transverse head-to-tail manner, and the Cu(hfac)2 moiety is closely sandwiched by these two ligands. In the AsF6(-) salt of the Cu(hfac)2 complex, each TTF dimer is separated by the AsF6(-) anions and has no overlap with each other within the one-dimensional arrays, resulting in an insulating behavior. Both Cu(hfac)2 complexes showed the simple Curie-like temperature dependence of paramagnetic susceptibilities (χM), indicating that no interaction exists between the paramagnetic Cu(II) d spins. Furthermore, crystal structure analysis and magnetic/conducting properties of a radical cation ReO4(-) salt of the Cu(I) complex with two TTF-CH═CH-BTA ligands, [Cu(TTF-CH═CH-BTA)2](ReO4)2, are also described. Two nitrogen atoms of the ligands are connected to the central Cu(I) in a linear dicoordination with a Cu-N bond length of 1.879(9) Å. Two TTF parts of the neighboring complexes form a dimerized structure, and such a TTF dimer forms a one-dimensional uniform array along the a direction with a short S-S contact of 3.88 Å. Magnetic property measurement suggested the existence of a strongly antiferromagnetic one-dimensional uniform chain of S = 1/2 spins that originate from the radical cation states of the TTF dimers. Due to the construction of the one

  8. The nitrate dihydrate of an aquadicopper(II) complex cation with guanidinoacetic acid and a novel trianionic disubstituted guanidine as ligands at 120 K.

    PubMed

    Felcman, Judith; Howie, R Alan; Lopes de Miranda, Jussara; Skakle, Janet M S; Wardell, James L

    2003-03-01

    The structure of the title compound, aqua[mu-(N(1)-carboxylatomethylguanidino)oxidoacetato](mu-guanidinoacetic acid)dicopper(II) nitrate dihydrate, [Cu(2)(C(5)H(6)N(3)O(5))(C(3)H(7)N(3)O(2))(H(2)O)]NO(3) x 2H(2)O, contains two enantiomers of the dicopper(II) complex cation that comprise water, neutral zwitterionic guanidinoacetic acid and the trianion of (N(1)-carboxymethylguanidino)hydroxyacetic acid as ligands. Extensive hydrogen bonding creates three-dimensional connectivity but is largely confined to layers that each contain both cation enantiomers. These layers are related to one another by crystallographic symmetry and are therefore identical in composition and connectivity. PMID:12711772

  9. A comparative study of model halogen-bonded, π-hole-bonded and cationic complexes involving NCX AND H2O (X = F, Cl, Br)

    NASA Astrophysics Data System (ADS)

    McDowell, Sean A. C.; Joseph, Jerelle A.

    2015-01-01

    A MP2/6-311+ +G(d,p) study of NCX (X = F, Cl, Br) has shown that it is possible to attach an electrophile (H+, Be2+) to the positive halogen X surface of NCX. The stability and properties of model halogen-bonded and π-hole carbon-bonded NCX/H2O complexes were found to be significantly affected by H+ or Be2+ cationic attachment at the N atom. The halogen-bonded complexes are destabilised by binding at the N, while an attached proton enhances the binding in the π-hole bonded dimers. For the attached Be2+, an unusual complex was obtained with the NCF subunit, whereas the complexes containing Cl and Br were destabilised by the interaction.

  10. Study of complexation process between 4'-nitrobenzo-15-crown-5 and yttrium(III) cation in binary mixed non-aqueous solvents using conductometric method

    NASA Astrophysics Data System (ADS)

    Habibi, N.; Rounaghi, G. H.; Mohajeri, M.

    2012-12-01

    The complexation reaction of macrocyclic ligand (4'-nitrobenzo-15C5) with Y3+ cation was studied in acetonitrile-methanol (AN-MeOH), acetonitrile-ethanol (AN-EtOH), acetonitrile-dimethylformamide (AN-DMF) and ethylacetate-methanol (EtOAc-MeOH) binary mixtures at different temperatures using conductometry method. The conductivity data show that in all solvent systems, the stoichiometry of the complex formed between 4'-nitrobenzo-15C5 and Y3+ cation is 1: 1 (ML). The stability order of (4'-nitrobenzo-15C5). Y3+ complex in pure non-aqueous solvents at 25°C was found to be: EtOAc > EtOH > AN ≈ DMF > MeOH, and in the case of most compositions of the binary mixed solvents at 25°C it was: AN≈MeOH ≈ AN-EtOH > AN-DMF > EtOAc-MeOH. But the results indicate that the sequence of the stability of the complex in the binary mixed solutions changes with temperature. A non-linear behavior was observed for changes of log K f of (4'-nitrobenzo-15C5 · Y3+) complex versus the composition of the binary mixed solvents, which was explained in terms of solvent-solvent interactions and also the hetero-selective solvation of the species involved in the complexation reaction. The values of thermodynamic parameters (Δ H {c/ℴ} and Δ S {c/ℴ}) for formation of the complex were obtained from temperature dependent of the stability constant using the van't Hoff plots. The results represent that in most cases, the complex is both enthalpy and entropy stabilized and the values and also the sign of thermodynamic parameters are influenced by the nature and composition of the mixed solvents.

  11. Ratiometric Molecular Probes Based on Dual Emission of a Blue Fluorescent Coumarin and a Red Phosphorescent Cationic Iridium(III) Complex for Intracellular Oxygen Sensing

    PubMed Central

    Yoshihara, Toshitada; Murayama, Saori; Tobita, Seiji

    2015-01-01

    Ratiometric molecular probes RP1 and RP2 consisting of a blue fluorescent coumarin and a red phosphorescent cationic iridium complex connected by a tetra- or octaproline linker, respectively, were designed and synthesized for sensing oxygen levels in living cells. These probes exhibited dual emission with good spectral separation in acetonitrile. The photorelaxation processes, including intramolecular energy transfer, were revealed by emission quantum yield and lifetime measurements. The ratios (RI=(Ip/If)) between the phosphorescence (Ip) and fluorescence (If) intensities showed excellent oxygen responses; the ratio of RI under degassed and aerated conditions (RI0/RI) was 20.3 and 19.6 for RP1 and RP2. The introduction of the cationic Ir (III) complex improved the cellular uptake efficiency compared to that of a neutral analogue with a tetraproline linker. The emission spectra of the ratiometric probes internalized into living HeLa or MCF-7 cells could be obtained using a conventional microplate reader. The complex RP2 with an octaproline linker provided ratios comparable to the ratiometric measurements obtained using a microplate reader: the ratio of the RI value of RP2 under hypoxia (2.5% O2) to that under normoxia (21% O2) was 1.5 and 1.7 for HeLa and MCF-7 cells, respectively. Thus, the intracellular oxygen levels of MCF-7 cells could be imaged by ratiometric emission measurements using the complex RP2. PMID:26066988

  12. Properties of cationic monosubstituted tetraalkylammonium cyclodextrin derivatives - their stability, complexation ability in solution or when deposited on solid anionic surface.

    PubMed

    Popr, Martin; Filippov, Sergey K; Matushkin, Nikolai; Dian, Juraj; Jindřich, Jindřich

    2015-01-01

    The thermal stability of the monosubstituted cationic cyclodextrin (CD) derivatives PEMEDA-β-CD and PEMPDA-β-CD, which differ in their substituent linker length (ethylene and propylene, respectively), was studied via (1)H NMR experiments. PEMPDA-β-CD exhibited higher resistance towards the Hofmann degradation and was chosen as a more suitable host molecule for further studies. Inclusion properties of PEMPDA-β-CD in solution with a series of simple aromatic guests (salicylic acid, p-methoxyphenol and p-nitroaniline) were determined by isothermal titration calorimetry (ITC) and compared to the native β-CD. Permanently charged cationic CD derivatives were successfully deposited on the anionic solid surface of polymeric Nafion(®) 117 membrane via electrostatic interactions. Deposition kinetics and coverage of the surface were determined by ELSD. Finally, the ability of the CD derivatives bound to the solid surface to encapsulate aromatic compounds from aqueous solution was measured by UV-vis spectroscopy. The obtained results are promising for future industrial applications of the monosubstituted β-CD derivatives, because the preparation of cationic CD derivatives is applicable in large scale, without the need of chromatographic purification. Their ionic deposition on a solid surface is simple, yet robust and a straightforward process as well. PMID:25815069

  13. Impact of Substituents on Excited-State and Photosensitizing Properties in Cationic Iridium(III) Complexes with Ligands of Coumarin 6.

    PubMed

    Takizawa, Shin-Ya; Ikuta, Naoya; Zeng, Fanyang; Komaru, Shohei; Sebata, Shinogu; Murata, Shigeru

    2016-09-01

    A series of bis-cyclometalated cationic iridium (Ir) complexes were synthesized employing two coumarin 6 ligands and a 2,2'-bipyridine (bpy) with various substituents as new sensitizers, realizing both features of strong visible-light absorption and long-lived excited state. Complexes 2-4, with electron-donating methyl and methoxy groups, absorbed visible light strongly (ε: 126 000-132 000 M(-1) cm(-1)) and exhibited room-temperature phosphorescence with remarkably long lifetimes (21-23 μs) in dichloromethane. In contrast, the excited state of prototype complex 1 without any substituents was short-lived, particularly in highly polar acetonitrile. Phosphorescence of complex 5 with the strong electron-withdrawing CF3 groups was too weak to be detected at room temperature even in less polar dichloromethane. The triplet energies of their coumarin ligand-centered ((3)LC) phosphorescent states were almost invariable, demonstrating that selective tuning of the excited-state lifetime is possible through this "simple chemical modification of the bpy ligand" (we name it the "SCMB" method). The spectroscopic and computational investigations in this study suggest that a potential source of the nonradiative deactivation is a triplet ligand-to-ligand charge-transfer state ((3)LLCT state, coumarin 6 → bpy) and lead us to conclude that the energy level of this dark (3)LLCT state, as well as its thermal population, is largely dependent on the substituents and solvent polarity. In addition, the significant difference in excited-state lifetime was reflected in the photosensitizing ability of complexes 1-5 in visible-light-driven hydrogen generation using sodium ascorbate and a cobalt(III) diglyoxime complex as an electron donor and a water-reduction catalyst, respectively. This study suggests that the SCMB method should be generally effective in controlling the excited state of other bis-cyclometalated cationic Ir(III) complexes. PMID:27548036

  14. Intrinsic affinities of alkali cations for 15-crown-5 and 18-crown-6: Bond dissociation energies of gas-phase M{sup +}-crown ether complexes

    SciTech Connect

    More, M.B.; Ray, D.; Armentrout, P.B.

    1999-01-20

    Bond dissociation energies (BDEs) of M{sup +}[c-(C{sub 2}H{sub 4}O){sub 5}] and M{sup +}[c-(C{sub 2}H{sub 4}O){sub 6}] for M = Na, K, Rb, and Cs are reported. The BDEs are determined experimentally by analysis of the thresholds for collision-induced dissociation of the cation-crown ether complexes by xenon measured by using guided ion beam mass spectrometry. In all cases, the primary and lowest energy dissociation channel observed experimentally in endothermic loss of the ligand molecule. The cross section thresholds are interpreted to yield 0 and 298 K BDEs after accounting for the effects of multiple ion-molecule collisions, internal energy of the complexes, and unimolecular decay rates. For both 18-crown-6 and 15-crown-5, the BDEs decrease monotonically with increasing cation size. These results indicate that the intrinsic affinity of c-(C{sub 2}H{sub 4}O){sub 5} and c-(C{sub 2}H{sub 4}O){sub 6} for M{sup +} is determined principally by the charge density of the cation not by the ratio of the ionic radius to the cavity size. The BDEs reported here are in fair agreement with recent ab initio calculations at the MP2 level with 6-31+G* basis sets. The experimental values are systematically smaller than the computed values by 8 {+-} 2 kJ/mol per metal-oxygen interaction. The existence of less strongly bound isomers in the experimental apparatus for Rb{sup +}(15-crown-5) and Cs{sup +}(15-crown-5) appears likely, but their absence for Na{sup +} and K{sup +} complexes indicates interesting metal-dependent dynamics to the formation of such isomers.

  15. Influence of cations on the complexation yield of DOTATATE with yttrium and lutetium: a perspective study for enhancing the 90Y and 177Lu labeling conditions.

    PubMed

    Asti, Mattia; Tegoni, Matteo; Farioli, Daniela; Iori, Michele; Guidotti, Claudio; Cutler, Cathy S; Mayer, Pat; Versari, Annibale; Salvo, Diana

    2012-05-01

    The DOTA macrocyclic ligand can form stable complexes with many cations besides yttrium and lutetium. For this reason, the presence of competing cationic metals in yttrium-90 and lutetium-177 chloride solutions can dramatically influence the radiolabeling yield. The aim of this study was to evaluate the coordination yield of yttrium- and lutetium-DOTATATE complexes when the reaction is performed in the presence of varying amounts of competing cationic impurities. In the first set of experiments, the preparation of the samples was performed by using natural yttrium and lutetium (20.4 nmol). The molar ratio between DOTATATE and these metals was 1 to 1. Metal competitors (Pb(2+), Zn(2+), Cu(2+), Fe(3+), Al(3+), Ni(2+), Co(2+), Cr(3+)) were added separately to obtain samples with varying molar ratio with respect to yttrium or lutetium (0.1, 0.5, 1, 2 and 10). The final solutions were analyzed through ultra high-performance liquid chromatography with an UV detector. In the second set of experiments, an amount of (90)Y or (177)Lu chloride (6 MBq corresponding to 3.3 and 45 pmol, respectively) was added to the samples, and a radio-thin layer chromatography analysis was carried out. The coordination of Y(3+) and Lu(3+) was dramatically influenced by low levels of Zn(2+), Cu(2+) and Co(2+). Pb(2+) and Ni(2+) were also shown to be strong competitors at higher concentrations. Fe(3+) was expected to be a strong competitor, but the effect on the incorporation was only partly dependent on its concentration. Al(3+) and Cr(3+) did not compete with Y(3+) and Lu(3+) in the formation of DOTATATE complexes. PMID:22172388

  16. Synthesis, crystal structure and characterization of a new mixed ligand cationic-anionic nickel(II) complex containing 1,4-diazepane

    NASA Astrophysics Data System (ADS)

    Sain, Saugata; Saha, Rajat; Pilet, Guillaume; Bandyopadhyay, Debasis

    2010-12-01

    A new mixed ligand cationic-anionic nickel(II) complex, [NiL 2][Ni(NCS) 4(H 2O) 2] ( 1), where L = 1,4-diazepane has been synthesized by reacting nickel perchlorate with 1,4-diazepane and ammonium thiocyanate in the 1:1:2 M ratio. The complex has been characterized by elemental analysis, IR spectroscopy, TGA and single crystal X-ray diffraction studies. Structural studies reveal the presence of two independent mononuclear complex ions in 1 viz., a square planar [NiL 2] 2+ and an octahedral [Ni(NCS) 4(H 2O) 2] 2- which are held together by H-bonding to form a 3D supramolecular structure in the solid state.

  17. Toward fluorine-free blue-emitting cationic iridium complexes: to generate emission from the cyclometalating ligands with enhanced triplet energy.

    PubMed

    He, Lei; Wang, Zhen; Duan, Lian; Yang, Chunpeng; Tang, Ruiren; Song, Xiangzhi; Pan, Chunyue

    2016-04-01

    A route toward fluorine-free blue-emitting cationic iridium complexes, to generate emission from the cyclometalating ligands with enhanced triplet energy, has been proposed and demonstrated. Attaching electron-donating groups to the pyridine moieties of the ppy-type cyclometalating ligands (Hppy is 2-phenylpyridine) enhances the triplet ((3)π-π*) energy of the ligand, and the use of electron-rich or non-conjugated ancillary ligands ensures that the emission is generated from the (3)π-π* states of cyclometalating ligands. By this molecular design, [Ir(buoppy)2(pzpy)]PF6 (1) and [Ir(buoppy)2(bim-cb)]PF6 (2) have been developed, with 4-butoxy-2-phenylpyridine (buoppy) as the cyclometalating ligand and electron-rich 2-(1H-pyrazol-1-yl)pyridine (pzpy) or non-conjugated N-heterocyclic dicarbene (bim-cb) as the ancillary ligands. Complexes 1 and 2 give emission with major emission peaks around 465 nm, which is among the bluest reported for fluorine-free cationic iridium complexes. For both complexes, the emission is generated from the (3)π-π* states centered on buoppy. For complex 1, the charge-transfer (Ir/buoppy → pzpy) state is dominated by non-radiative deactivation and it behaves as a non-radiative deactivation channel for the emissive buoppy-centered (3)π-π* states which lies close to the charge-transfer state in energy. Such a non-radiative deactivation channel is largely suppressed in the rigid matrix, and is eliminated in complex 2 with a non-conjugated dicarbene ancillary ligand. PMID:26918443

  18. Gene transfer by cationic surfactants is essentially limited by the trapping of the surfactant/DNA complexes onto the cell membrane: a fluorescence investigation.

    PubMed

    Clamme, J P; Bernacchi, S; Vuilleumier, C; Duportail, G; Mély, Y

    2000-08-25

    The interaction between complexes of plasmid DNA with cetyltrimethylammonium bromide (CTAB) and L929 fibroblasts was first examined using confocal microscopy. The complexes labeled with the DNA intercalator, YOYO-1, were found to be trapped onto the external face of the plasma membrane; a feature that may constitute a major limiting step in transfection. Moreover, since no cytotoxic effect appeared in these conditions, we further inferred that the CTAB molecules remained bound to the DNA. The interaction of the complexes with the membranes was best modeled with neutral vesicles. From anisotropy thermotropic curves of DPHpPC-labeled vesicles and fluorescence resonance energy transfer measurements between these vesicles and YOYO-labeled complexes, we evidenced that the binding of the complexes to the vesicle surface opened the micelle-like domains and unwound DNA. However, DNA was not released but remained stably bound via electrostatic interactions to the CTAB molecules incorporated in the external liposome leaflet. Consequently, the large diameter of the unwound plasmid DNA is likely the major factor that precludes its internalization into the cells by endocytosis. In contrast, anionic vesicles that mimic the cytoplasmic facing monolayer of the plasma membrane rapidly released DNA from the complex. This may explain the previously reported high transfection efficiency of DNA complexed with liposomes composed of neutral lipids and cationic surfactants, since the latter may destabilize the endosomal membrane and induce the release of DNA in the cytoplasm. PMID:11030593

  19. Human 17β-hydroxysteroid dehydrogenase-ligand complexes: crystals of different space groups with various cations and combined seeding and co-crystallization

    NASA Astrophysics Data System (ADS)

    Zhu, D.-W.; Han, Q.; Qiu, W.; Campbell, R. L.; Xie, B.-X.; Azzi, A.; Lin, S.-X.

    1999-01-01

    Human estrogenic 17β-hydroxysteroid dehydrogenase (17β-HSD1) is responsible for the synthesis of active estrogens that stimulate the proliferation of breast cancer cells. The enzyme has been crystallized using a Mg 2+/PEG (3500)/β-octyl glucoside system [Zhu et al., J. Mol. Biol. 234 (1993) 242]. The space group of these crystals is C2. Here we report that cations can affect 17β-HSD1 crystallization significantly. In the presence of Mn 2+ instead of Mg 2+, crystals have been obtained in the same space group with similar unit cell dimensions. In the presence of Li + and Na + instead of Mg 2+, the space group has been changed to P2 12 12 1. A whole data set for a crystal of 17ß-HSD1 complex with progesterone grown in the presence of Li + has been collected to 1.95 Å resolution with a synchrotron source. The cell dimensions are a=41.91 Å, b=108.21 Å, c=117.00 Å. The structure has been preliminarily determined by molecular replacement, yielding important information on crystal packing in the presence of different cations. In order to further understand the structure-function relationship of 17β-HSD1, enzyme complexes with several ligands have been crystallized. As the steroids have very low aqueous solubility, we used a combined method of seeding and co-crystallization to obtain crystals of 17β-HSD1 complexed with various ligands. This method provides ideal conditions for growing complex crystals, with ligands such as 20α-hydroxysteroid progesterone, testosterone and 17β-methyl-estradiol-NADP +. Several complex structures have been determined with reliable electronic density of the bound ligands.

  20. Halometallate complexes of germanium(II) and (IV): probing the role of cation, oxidation state and halide on the structural and electrochemical properties.

    PubMed

    Bartlett, Philip N; Cummings, Charles Y; Levason, William; Pugh, David; Reid, Gillian

    2014-04-22

    The Ge(IV) chlorometallate complexes, [EMIM]2 [GeCl6 ], [EDMIM]2 [GeCl6 ] and [PYRR]2 [GeCl6 ] (EMIM=1-ethyl-3-methylimidazolium; EDMIM=2,3-dimethyl-1-ethylimidazolium; PYRR=N-butyl-N-methylpyrrolidinium) have been synthesised and fully characterised; the first two also by single-crystal X-ray diffraction. The imidazolium chlorometallates exhibited significant CH⋅⋅⋅Cl hydrogen bonds, resulting in extended supramolecular assemblies in the solid state. Solution (1) H NMR data also showed cation-anion association. The synthesis and characterisation of Ge(II) halometallate salts [EMIM][GeX3 ] (X=Cl, Br, I) and [PYRR][GeCl3 ], including single-crystal X-ray analyses for the homologous series of imidazolium salts, are reported. In these complexes, the intermolecular interactions are much weaker in the solid state and they appear not to be significantly associated in solution. Cyclic-voltammetry experiments on the Ge(IV) species in CH2 Cl2 solution showed two distinct, irreversible reduction waves attributed to Ge(IV) -Ge(II) and Ge(II) -Ge(0) , whereas the Ge(II) species exhibited one irreversible reduction wave. The potential for the Ge(II) -Ge(0) reduction was unaffected by changing the cation, although altering the oxidation state of the precursor from Ge(IV) to Ge(II) does have an effect; for a given cation, reduction from the [GeCl3 ](-) salts occurred at a less cathodic potential. The nature of the halide co-ligand also has a marked influence on the reduction potential for the Ge(II) -Ge(0) couple, such that the reduction potentials for the [GeX3 ](-) salts become significantly less cathodic when the halide (X) is changed Cl→Br→I. PMID:24644266

  1. Characterization of complexation of poly (N-isopropylacrylamide-co-2-(dimethylamino) ethyl methacrylate) thermoresponsive cationic nanogels with salmon sperm DNA

    PubMed Central

    Moselhy, Jim; Vira, Tasnim; Liu, Fei-Fei; Wu, Xiao Yu

    2009-01-01

    Thermoresponsive cationic nanogel (TCNG) networks based on N-isopropylacrylamide (NIPAM), 2-(dimethylamino)ethyl methacrylate (DMAEMA), and quaternary alkyl ammonium halide salts of DMAEMA (DMAEMAQ) were synthesized by dispersion polymerization technique. The thermoresponsive properties of TCNGs and TCNG-salmon sperm DNA (sasDNA) polyplexes were characterized in aqueous media of various pH and ionic strength. P[NIPAM] and P[NIPAM/DMAEMA] TCNGs exhibited sharp volume phase transition (VPT) in water at critical temperatures (Tc) of 32 °C and 36 °C, respectively. Quaternized P[NIPAM/DMAEMAQ] TCNGs did not undergo sharp VPT up to 50 °C. The VPT of uncomplexed TCNGs were sensitive to the ionic composition and ionic strength of salts in solution, but were insensitive to pH in the range 5.0 to 7.4. The VPT of P[NIPAM/DMAEMAQ]/sasDNA diminished in magnitude with increasing Wp/Wd suggesting greater compaction of the polyplexes. The distinct phase-transition properties of P[NIPAM/DMAEMA]/sasDNA and P[NIPAM/DMAEMAQ]/sasDNA polyplexes were attributed to the condensing capability of polycations and to differences in the spatial distribution of structural charges in quaternized and nonquaternized networks. The findings demonstrate that stable TCNGs can be prepared with controllable responsive properties determined by the nature of the cationic charge incorporated and may have potential as vehicles for DNA delivery. PMID:19774114

  2. Self-Assembly of Nanostructured, Complex, Multi-cation Films via Spontaneous Phase Separation and Strain-driven Ordering

    SciTech Connect

    Goyal, Amit; Wee, Sung Hun; Stocks, George Malcolm; Zuev, Yuri L; More, Karren Leslie; Meng, Jianyong; Zhong, Jianxin

    2013-01-01

    Spontaneous self-assembly of a multi-cation nanophase in another multi-cation matrix phase is a promising bottom-up approach to fabricate novel, nanocomposite structures for a range of applications. In an effort to understand the mechanisms for such self-assembly, we report on complimentary experimental and theoretical studies to first understand and then control or guide the self-assembly of insulating BaZrO3 (BZO) nanodots within REBa2Cu3O7- (RE=rare earth elements including Y, REBCO) superconducting films. It was determined that the strain field developed around BZO nanodots embedded in REBCO matrix is a key driving force dictating the self-assembly of BZO nanodots along REBCO c-axis. The size selection and spatial ordering of BZO self-assembly were simulated using thermodynamic and kinetic models. The BZO self-assembly was controllable by tuning the interphase strain field. REBCO superconducting films with BZO defects arrays self-assembled to align in both vertical (REBCO c-axis) and horizontal (REBCO ab-planes) directions, resulted in the maximized pinning and Jc performance for all field angles with smaller angular Jc anisotropy. The work has broad implications for fabrication of controlled self-assembled nanostructures for a range of applications via strain-tuning.

  3. Highly Active Electrolytes for Rechargeable Mg Batteries Based on [Mg2(μ-Cl)2]2+ Cation Complex in Dimethoxyethane

    SciTech Connect

    Cheng, Yingwen; Stolley, Ryan M.; Han, Kee Sung; Shao, Yuyan; Arey, Bruce W.; Washton, Nancy M.; Mueller, Karl T.; Helm, Monte L.; Sprenkle, Vincent L.; Liu, Jun; Li, Guosheng

    2015-01-01

    Highly active electrolytes based on a novel [Mg2(μ-Cl)2]2+ cation complex for reversible Mg deposition were developed and analyzed in this work. These electrolytes were formulated in dimethoxyethane through dehalodimerization of non-nucleophilic MgCl2 by reacting with either Mg salts (such as Mg(TFSI)2, TFSI= bis(trifluoromethane)sulfonylimide) or Lewis acid salts (such as AlEtCl2 or AlCl3). The cation complex was identified for the first time as [Mg2(μ-Cl)2(DME)4]2+ (DME=dimethoxyethane) and its molecular structure was characterized by single crystal X-ray diffraction, Raman spectroscopy and NMR. The electrolyte synthesis process was studied and rational approaches for formulating highly active electrolytes were proposed. Through control of the anions, electrolytes with efficiency close to 100%, wide electrochemical window (up to 3.5V) and high ionic conductivity (> 6 mS/cm) were obtained. The electrolyte synthesis and understandings developed in this work could bring significant opportunities for rational formulation of electrolytes with the general formula [Mg2(μ-Cl)2(DME)4][anion]x for practical Mg batteries.

  4. Conductometric study of complexation process between dibenzo-18-crown-6 and K+, Na+, and La3+ cations in some binary mixed non-aqueous solvents

    NASA Astrophysics Data System (ADS)

    Khoshnood, Razieh Sanavi; Teymoori, Mostafa; Hatami, Elaheh; Balanezhad, Azadeh Zafar

    2015-09-01

    The complexation reactions between K+, Na+, and La3+ cations and the macrocyclic ligand dibenzo-18-crown-6 (DB18C6) were studied in acetionitrile (AN)-dimethylformamide (DMF) binary mixtures. Also, the complexation of K+ and Na+ in 50% ethanol (EtOH)-50% DMF and 50% EtOH-50% AN binary mixtures was studied. The conductivity data show that the stochiometry of all the complexes is 1: 1. A non-linear behavior was observed for the log K f variation vs. composition of binary solvent, which was discussed in terms of heteroselective solvation and solvent-solvent interactions in binary solutions. It was found that the stability order of the complexes changes with composition of the mixed solvents. The stability sequence for AN-DMF (25 and 50 mol % DMF) solutions and pure AN at 25°C is [K(DB18C6)]+ > [Na(DB18C6)]+ > [La(DB18C6)]3+. However, at 75 mol % DMF it changes to [Na(DB18C6)]+ > [K(DB18C6)]+ > [La(DB18C6)]3+. The thermodynamical values (Δ H {/c po}, Δ S {/c po}) for these complexation reactions were determined from the temperature dependence of the stability constants. The thermodynamics of the complexation reactions is affected by the nature and composition of the mixed solvents.

  5. Unexpected anion effect in the alkoxylation of alkynes catalyzed by N-heterocyclic carbene (NHC) cationic gold complexes.

    PubMed

    Biasiolo, Luca; Trinchillo, Marina; Belanzoni, Paola; Belpassi, Leonardo; Busico, Vincenzo; Ciancaleoni, Gianluca; D'Amora, Angela; Macchioni, Alceo; Tarantelli, Francesco; Zuccaccia, Daniele

    2014-11-01

    The intermolecular alkoxylation of alkynes is the oldest application of cationic gold(I) catalysts; however, no systematic experimental data about the role of the anion are available. In this contribution, the role of the anion in this catalytic reaction as promoted by a N-heterocyclic carbene-based gold catalyst, [(NHC)AuX] (X=BARF(-) , BF4 (-) , OTf(-) , OTs(-) , TFA(-) , or OAc(-) ) is analyzed, through a combined experimental (NMR spectroscopy) and theoretical (DFT calculation) approach. The most important factor seems to be the ability to abstract the proton from the methanol during the nucleophilic attack, and such ability is related to the anion basicity. On the other hand, too high coordination power or basicity of the anion worsens the catalytic performance by preventing alkyne coordination or by forming too much free methoxide in solution, which poisons the catalyst. The intermediate coordinating power and basicity of the OTs(-) anion provides the best compromise to achieve efficient catalysis. PMID:25263571

  6. Density functional theory studies on decomposition of ethyl-palladium complexes: an important role of cationic species

    NASA Astrophysics Data System (ADS)

    Raharintsalama, Rado; Munakata, Hiroaki; Koyama, Michihisa; Kubo, Momoji; Miyamoto, Akira

    2005-05-01

    Density functional theory calculations were applied to investigate the β-hydrogen-elimination of the ethyl-palladium complexes, cis-(Me 3P) 2(Et)PdHX, where X = Cl, Br or I, to form ethene and hydrido-palladium complexes. Effects of substitution of halogen ligands and coordination of solvent molecules on geometric parameters and energies were investigated. Studies on solvated reaction intermediates revealed the agostic ethyl-palladium complexes to be important in the decomposition processes of the ethyl-palladium complexes.

  7. Influences of the propyl group on the van der Waals structures of 4-propylaniline complexes with one and two argon atoms studied by electronic and cationic spectroscopy

    SciTech Connect

    Yang, Zhijun; Gu, Quanli; Trindle, Carl O.; Knee, J. L.

    2015-07-21

    4-propylaniline complexes with one and two argon atoms formed in the molecular beam were studied in the first excited electronic state, S{sub 1}, using resonance enhanced two-photon ionization spectroscopy and in the cation ground state, D{sub 0}, using mass analyzed threshold ionization spectroscopy. The combination of electronic and cationic spectra of the clusters allows two conformations to be identified in both aniline-Ar{sub 1} and aniline-Ar{sub 2}, which are assigned to either the gauche configuration or anti-configuration of 4-propylaniline. The gauche isomer exhibits complex bands shifted 29 cm{sup −1} and 89 cm{sup −1} from the S{sub 1} origin bands and 83 cm{sup −1} and 148 cm{sup −1} from the ionization potential assigned to the Ar{sub 1} and Ar{sub 2} complexes, respectively. For the anti-rotamer, the corresponding shifts actually become nearly additive, 53 cm{sup −1} and 109 cm{sup −1} for the S{sub 1} origin bands, and 61 cm{sup −1} and 125 cm{sup −1} for the ionization potentials. Ab initio calculations provide insights into the influences of the propyl and amino groups on the positions of the argon atoms within the clusters. In addition, the binding energy of one argon with the gauche isomer of 4-propylaniline has been measured to be 550 ± 5 cm{sup −1} in the D{sub 0} state, 496 ± 5 cm{sup −1} in the S{sub 1} state, and 467 ± 5 cm{sup −1} in the neutral ground state, S{sub 0}.

  8. Quantitative investigations of cation complexation of photochromic 8-benzothiazole-substituted benzopyran: towards metal-ion sensors.

    PubMed

    Zakharova, Marianna I; Coudret, Christophe; Pimienta, Véronique; Micheau, Jean Claude; Delbaere, Stéphanie; Vermeersch, Gaston; Metelitsa, Anatoly V; Voloshin, Nikolai; Minkin, Vladimir I

    2010-02-01

    The photochromic, thermochromic and metallochromic behaviour of a series of three spiro[indoline-8-(benzothiazol-2-yl)-benzopyrans] has been investigated. The thermodynamic and kinetic parameters of their thermal equilibrium between the ring-closed (spiro) and ring-opened (merocyanine) isomeric forms have been determined using UV-Vis absorption and (1)H NMR spectroscopies. By adding Co(ii) and Ni(ii) ions in acetonitrile solution, 1 : 1 and 1 : 2 metal : merocyanine complexes are formed simultaneously. Using appropriate numerical methods, the kinetic analysis of the complexation allowed us to determine accurately key thermodynamic and spectroscopic parameters of the metal complexes. Results showed that the complexation strength is very sensitive to the size of the indoline nitrogen substituent. Complexation can be reversed by shining white light on the coloured complexes which regenerates the inactive spiropyran form, and releases the metallic ion; hence, these systems display fully reversible negative photochromism. The Zn(ii) complexes exhibit intense fluorescence in the 600-800 nm wavelength range. All these behaviours make these spiropyrans bearing benzothiazole heterocycles promising building blocks for the future construction of photodynamic chemosensors for transition metal ions. PMID:20126795

  9. Crystal structure, spectroscopy, DFT studies and thermal characterization of Cobalt(II) complex with 2-protonated aminopyridinium cation as ligand

    NASA Astrophysics Data System (ADS)

    Mhadhbi, Noureddine; Saïd, Salem; Elleuch, Slim; Naïli, Houcine

    2016-03-01

    Single crystals of a new organic-inorganic hybrid compound (2-HAMP)2[CoBr4], (2-HAMP = 2-protonated aminopyridinium cation) was synthesized and characterized by X-Ray diffraction at room temperature, DTA-TG measurement, FT-IR and FT-Raman spectroscopies and optical absorption. Its crystal structure is a packing of alternated organic and inorganic layers parallel to (a, b) plane. The different components are connected by a network of N/C-H⋯Br hydrogen bonds and halogen⋯halogen interactions. These hydrogen bonds give notable vibrational effects. Theoretical calculations were performed using density functional theory (DFT) for studying the molecular structure, vibrational spectra and optical properties of the investigated molecule in the ground state. The optimized geometrical parameters obtained by DFT calculations are in good agreement with single crystal XRD data. The energy and oscillator strength calculated by Time-Dependent Density Functional Theory (TD-DFT) results complements with the experimental findings. The simulated spectra satisfactorily coincide with the experimental UV-Visible spectrum. The results show good consistent with the experiment and confirm the contribution of metal orbital to the HOMO-LUMO boundary. Thermal analysis studies indicate the presence of three phase transitions at 68, 125 and 172 °C, which are confirmed by X-ray powder diffraction as a function of temperature.

  10. Cationic conjugated polyelectrolyte/molecular beacon complex for sensitive, sequence-specific, real-time DNA detection.

    PubMed

    Feng, Xuli; Duan, Xinrui; Liu, Libin; An, Lingling; Feng, Fude; Wang, Shu

    2008-11-01

    A new fluorescence method has been developed for DNA detection at room temperature in a sensitive, selective, economical, and real-time manner that interfaces the superiority of a molecular beacon in mismatch discrimination with the light-harvesting property of water-soluble conjugated polyelectrolytes. The probe solution contains a cationic conjugated polyelectrolyte (PFP-NMe3+), a molecular beacon with a five base pairs double-stranded stem labeled at the 5'-terminus with fluorescein (DNA P-Fl), and ethidium bromide (EB, a specific intercalator of dsDNA). The electrostatic interactions between DNA P-Fl and PFP-NMe3+ keep them in close proximity, facilitating the fluorescence resonance energy transfer (FRET) from PFP-NMe3+ to fluorescein. Upon adding a complementary strand to the probe solution, the conformation of DNA P-Fl transits into dsDNA followed by the intercalation of EB into the grooves. Two-step FRET, from PFP-NMe3+ to DNA P-Fl (FRET-1), followed by FRET from DNA P-Fl to EB (FRET-2) takes place. In view of the observed fluorescein or EB emission changes, DNA can be detected in aqueous solution. Because the base mismatch in target DNA inhibits the transition of DNA P-Fl from the stem-loop to duplex structure, single nucleotide mismatch can be clearly detected. PMID:18834161

  11. Cationic-perylene-G-quadruplex complex based fluorescent biosensor for label-free detection of Pb(2+).

    PubMed

    Zhao, Xu-Hua; Gong, Liang; Wu, Yuan; Zhang, Xiao-Bing; Xie, Jun

    2016-03-01

    In this work we use a water-soluble cationic perylene derivative (compound 1) as the G-quadruplex (G4) structure fluorescence indicator to construct a fluorescent biosensor for simple, rapid and label-free detection of Pb(2+). In the absence of Pb(2+), strong electrostatic interactions between compound 1 and the G-rich DNA probe (PW17) induced the aggregation of compound 1 and resulted in the fluorescence quenching. In the presence of Pb(2+), the PW17 formed Pb(2+)-stabilized G4 structure, which reduced the aggregation of compound 1 and gave rise to high fluorescence. This allowed us to use convenient "mix-and-detect" protocol for quantitative analysis of Pb(2+). Since Pb(2+) can specially induce PW17 to form compact DNA fold, our proposed biosensor displayed high selectivity for Pb(2+). It also exhibited a high sensitivity to Pb(2+), with a limit of detection of 5.0nM observed. Furthermore, the biosensor was applied for the detection of Pb(2+) in urine and paint samples, and both showed satisfactory results. PMID:26717819

  12. Molecular complexation of curcumin with pH sensitive cationic copolymer enhances the aqueous solubility, stability and bioavailability of curcumin.

    PubMed

    Kumar, Sunny; Kesharwani, Siddharth S; Mathur, Himanshi; Tyagi, Mohit; Bhat, G Jayarama; Tummala, Hemachand

    2016-01-20

    Curcumin is a natural dietary compound with demonstrated potential in preventing/treating several chronic diseases in animal models. However, this success is yet to be translated to humans mainly because of its poor oral bioavailability caused by extremely low water solubility. This manuscript demonstrates that water insoluble curcumin (~1μg/ml) forms highly aqueous soluble complexes (>2mg/ml) with a safe pH sensitive polymer, poly(butyl-methacrylate-co-(2-dimethylaminoethyl) methacrylate-co-methyl-methacrylate) when precipitated together in water. The complexation process was optimized to enhance curcumin loading by varying several formulation factors. Acetone as a solvent and polyvinyl alcohol as a stabilizer with 1:2 ratio of drug to polymer yielded complexes with relatively high loading (~280μg/ml) and enhanced solubility (>2mg/ml). The complexes were amorphous in solid and were soluble only in buffers with pHs less than 5.0. Hydrogen bond formation and hydrophobic interactions between curcumin and the polymer were recorded by infrared spectroscopy and nuclear magnetic resonance spectroscopy, respectively. Molecular complexes of curcumin were more stable at various pHs compared to unformulated curcumin. In mice, these complexes increased peak plasma concentration of curcumin by 6 times and oral bioavailability by ~20 times. This is a simple, economic and safer strategy of enhancing the oral bioavailability of curcumin. PMID:26588875

  13. Changes of conductance and compressibility of bilayer lipid membranes induced by oligonucleotide-cationic polyene antibiotic complexes.

    PubMed

    Hianik, Tibor; Ostatnik, Lukas; Polohova, Vladimira; Bolard, Jacques

    2008-11-01

    The positively charged polyene molecule amphotericin B 3-dimethylaminopropylamide (AMA) is an efficient agent for the delivery of antisense oligodeoxyribonucleotides (ODN) into target cells. In the present study, bilayer lipid membrane (BLM) conductance, elasticity modulus perpendicular to the membrane plane, surface potential and electrical capacitance were measured by conductance and electrostriction methods in the presence of AMA, pure or complexed to 20-mer single stranded ODN at different ratios. Pure AMA did not induce changes in conductance of cholesterol-containing BLM, but did induce an increase in elasticity modulus and surface potential. ODN/AMA complexes changed BLM properties depending on the charge ratio. The most pronounced effect on membrane conductance was observed for positively charged ODN/AMA complexes (charge ratio rho-/+=0.1), while for negatively charged complexes these changes were less marked/apparent, correlating to substantially lower binding constants. The effect of ODN/AMA complexes on elasticity modulus and charge potential was biphasic. After an increase in both values, a decrease was observed for higher incubation times and ODN/AMA concentrations. These results are interpreted as indicating that the membrane property changes result from the large AMA aggregates induced by the presence of the negatively charged ODN, which condensate on these aggregates. It is suggested that the decrease of elasticity modulus and surface potential in the presence of increasing incubation time and AMA concentration result from desorption of the complexes in the complex-free compartment of the BLM cell, or appearance of a non-linear conductance of the lipid bilayer. The first alternative would explain the AMA-induced transmembrane transfer of ODN. PMID:17904427

  14. Halometallate Complexes of Germanium(II) and (IV): Probing the Role of Cation, Oxidation State and Halide on the Structural and Electrochemical Properties

    PubMed Central

    Bartlett, Philip N; Cummings, Charles Y; Levason, William; Pugh, David; Reid, Gillian

    2014-01-01

    The GeIV chlorometallate complexes, [EMIM]2[GeCl6], [EDMIM]2[GeCl6] and [PYRR]2[GeCl6] (EMIM=1-ethyl-3-methylimidazolium; EDMIM=2,3-dimethyl-1-ethylimidazolium; PYRR=N-butyl-N-methylpyrrolidinium) have been synthesised and fully characterised; the first two also by single-crystal X-ray diffraction. The imidazolium chlorometallates exhibited significant C–H⋅⋅⋅Cl hydrogen bonds, resulting in extended supramolecular assemblies in the solid state. Solution 1H NMR data also showed cation–anion association. The synthesis and characterisation of GeII halometallate salts [EMIM][GeX3] (X=Cl, Br, I) and [PYRR][GeCl3], including single-crystal X-ray analyses for the homologous series of imidazolium salts, are reported. In these complexes, the intermolecular interactions are much weaker in the solid state and they appear not to be significantly associated in solution. Cyclic-voltammetry experiments on the GeIV species in CH2Cl2 solution showed two distinct, irreversible reduction waves attributed to GeIV–GeII and GeII–Ge0, whereas the GeII species exhibited one irreversible reduction wave. The potential for the GeII–Ge0 reduction was unaffected by changing the cation, although altering the oxidation state of the precursor from GeIV to GeII does have an effect; for a given cation, reduction from the [GeCl3]− salts occurred at a less cathodic potential. The nature of the halide co-ligand also has a marked influence on the reduction potential for the GeII–Ge0 couple, such that the reduction potentials for the [GeX3]− salts become significantly less cathodic when the halide (X) is changed Cl→Br→I. PMID:24644266

  15. Zn(2+) and Cd(2+) cationized serine complexes: infrared multiple photon dissociation spectroscopy and density functional theory investigations.

    PubMed

    Coates, Rebecca A; Boles, Georgia C; McNary, Christopher P; Berden, Giel; Oomens, Jos; Armentrout, P B

    2016-08-10

    The gas-phase structures of zinc and cadmium dications bound to serine (Ser) are investigated by infrared multiple photon dissociation (IRMPD) action spectroscopy using the free electron laser FELIX, in combination with ab initio calculations. To identify the structures of the experimentally observed species, [Zn(Ser-H)CH3CN](+) and CdCl(+)(Ser), the measured action spectra are compared to linear absorption spectra calculated at the B3LYP/6-311+G(d,p) level for Zn(2+) containing complexes and B3LYP/def2-TZVP levels for Cd(2+) containing complexes. Good agreement between the observed IRMPD spectra and the predicted spectra allows identification of the isomers present. The intact amino acid interacting with cadmium chloride adopts a tridentate chelation involving the amino acid backbone amine and carbonyl groups as well as the hydroxyl group of the side-chain, [N,CO,OH]. The presence of two low-energy conformers is observed for the deprotonated serine-zinc complex, with the same tridentate coordination as for the cadmium complex but proton loss occurs at both the hydroxyl side-chain, [N,CO,O(-)], and the carboxylic acid of the amino acid backbone, [N,CO(-),OH]. These results are profitably compared with the analogous results previously obtained for comparable complexes with cysteine. PMID:27465924

  16. Dynamic chiral-at-metal stability of tetrakis(d/l-hfc)Ln(III) complexes capped with an alkali metal cation in solution.

    PubMed

    Lin, Yiji; Zou, Fang; Wan, Shigang; Ouyang, Jie; Lin, Lirong; Zhang, Hui

    2012-06-14

    Chiral tetrakis(β-diketonate) Ln(III) complexes Δ-[NaLa(d-hfc)(4)(CH(3)CN)] (1) and Λ-[NaLa(l-hfc)(4) (CH(3)CN)] (2) (d/l-hfc(-) = 3-heptafluo-robutylryl-(+)/(-)-camphorate) are a pair of enantiomers and crystallize in the same Sohncke space group (P2(1)2(1)2(1)) with dodecahedral (DD) geometry. Typically positive and negative exciton splitting patterns around 320 nm were observed in the solid-state circular dichroism (CD) spectra of complexes 1 and 2, which indicate that their shell configurational chiralities are Δ and Λ, respectively. The apparent bisignate couplets in the solid-state CD spectra of [CsLn(d-hfc)(4)(H(2)O)] [Ln = La (3), Yb (5)] and [CsLn(l-hfc)(4)(H(2)O)] [Ln = La (4), Yb (6)] show that they are a pair of enantiomers and their absolute configurations are denoted Δ and Λ, respectively. The crystallographic data of 5 reveals that its coordination polyhedron is the square antiprism (SAP) geometry and it undergoes a phase transition from triclinic (α phase, P1) to monoclinic (β phase, C2) upon cooling. The difference between the two phases is brought about by the temperature dependent behaviour of the coordination water molecules, but this did not affect the configurational chirality of the Δ-SAP-[Yb(d-hfc)(4)](-) moiety. Furthermore, time-dependent CD, UV-vis and (19)F NMR were applied to study the solution behavior of these complexes. It was found that the chiral-at-metal stability of the three pairs of complexes is different and affected by both the Ln(3+) and M(+) ion size. The results show that the Cs(+) cation can retain the metal center chirality and stablize the structures of [Ln(d/l-hfc)(4)](-) or the dissociated tris(d/l-hfc)Ln(III) species in solution for a longer time than that of the Na(+) cation, and it is important that the Cs(+) ion successfully lock the configurational chirality around the Yb(3+) center of the complex species in solution. This is reasoned by the short Cs(+)···FC, Cs(+)···O-Yb and Cs(+)···Yb(3

  17. SO2-Binding Properties of Cationic η6,η1-NCN-Pincer Arene Ruthenium Platinum Complexes: Spectroscopic and Theoretical Studies

    SciTech Connect

    Bonnet, Sylvestre A.; Van Lenthe, Joop H.; van Dam, Hubertus JJ; van Koten, Gerard; Klein Gebbink, Robertus J M

    2011-03-01

    The SO2-binding properties of a series of η6,η1-NCN-pincer ruthenium platinum complexes have been studied by both UV-visible spectroscopy, and theoretical calculations. When an electronwithdrawing [Ru(C5R5)]+ fragment (R = H or Me) is η6-coordinated to the phenyl ring of the NCNpincer platinum fragment (cf. [2]+ and [3]+, see scheme 1), the characteristic orange coloration (pointing to η1- SO2 binding to Pt) of a solution of the parent NCN-pincer platinum complex 1 in dichloromethane upon SO2-bubbling is not observed. However, when the ruthenium center is η6- coordinated to a phenyl substituent linked in para-position to the carbon-to-platinum bond, i.e. complex [4]+, the SO2-binding property of the NCN-platinum center seems to be retained, as bubbling SO2 into a solution of the latter complex produces the characteristic orange color. We performed theoretical calculations at the MP2 level of approximation and TD-DFT studies, which enabled us to interpret the absence of color change in the case of [2]+ as an absence of coordination of SO2 to platinum. We analyze this absence or weaker SO2-coordination in dichloromethane to be a consequence of the relative electron-poorness of the platinum center in the respective η6- ruthenium coordinated NCN-pincer platinum complexes, that leads to a lower binding energy and an elongated calculated Pt-S bond distance. We also discuss the effects of electrostatic interactions in these cationic systems, which also seems to play a destabilizing role for complex [2(SO2)]+.

  18. Regioisomerism in cationic sulfonyl-substituted [Ir(C^N)2(N^N)](+) complexes: its influence on photophysical properties and LEC performance.

    PubMed

    Ertl, Cathrin D; Gil-Escrig, Lidón; Cerdá, Jesús; Pertegás, Antonio; Bolink, Henk J; Junquera-Hernández, José M; Prescimone, Alessandro; Neuburger, Markus; Constable, Edwin C; Ortí, Enrique; Housecroft, Catherine E

    2016-08-01

    A series of regioisomeric cationic iridium complexes of the type [Ir(C^N)2(bpy)][PF6] (bpy = 2,2'-bipyridine) is reported. The complexes contain 2-phenylpyridine-based cyclometallating ligands with a methylsulfonyl group in either the 3-, 4- or 5-position of the phenyl ring. All the complexes have been fully characterized, including their crystal structures. In acetonitrile solution, all the compounds are green emitters with emission maxima between 493 and 517 nm. Whereas substitution meta to the Ir-C bond leads to vibrationally structured emission profiles and photoluminescence quantum yields of 74 and 77%, placing a sulfone substituent in a para position results in a broad, featureless emission band, an enhanced quantum yield of 92% and a shorter excited-state lifetime. These results suggest a larger ligand-centred ((3)LC) character of the emissive triplet state in the case of meta substitution and a more pronounced charge transfer (CT) character in the case of para substitution. Going from solution to the solid state (powder samples and thin films), the emission maxima are red-shifted for all the complexes, resulting in green-yellow emission. Data obtained from electrochemical measurements and density functional theory calculations parallel the photophysical trends. Light-emitting electrochemical cells (LECs) based on the complexes were fabricated and evaluated. A maximum efficiency of 4.5 lm W(-1) at a maximum luminance of 940 cd m(-2) was observed for the LEC with the complex incorporating the sulfone substituent in the 4-position when operated under pulsed current driving conditions. PMID:27171612

  19. Cationic heteroleptic cyclometalated iridium(III) complexes containing phenyl-triazole and triazole-pyridine clicked ligands.

    PubMed

    Felici, Marco; Contreras-Carballada, Pablo; Smits, Jan M M; Nolte, Roeland J M; Williams, René M; De Cola, Luisa; Feiters, Martin C

    2010-03-01

    Novel heteroleptic iridium complexes containing the 1-substituted-4-phenyl-1H-1,2,3-triazole (phtl) cyclometalating ligand have been synthesized. The 3+2 Huisgen dipolar cycloaddition method ('click' chemistry) was utilized to prepare a class of bidentate ligands (phtl) bearing different substituents on the triazole moiety. By using various ligands (phtl-R1 and pytl-R2) (R1 = adamantane, methyl and R2 = adamantane, methyl, beta-cyclodextrin, ursodeoxycholic acid), we prepared a small library of new luminescent ionic iridium complexes [Ir(phtr-R1)2(pytl-R2)]Cl and report on their photophysical properties. The flexibility of the clicking approach allows a straightforward control on the chemical-physical properties of the complexes by varying the nature of the substituent on the ligand. PMID:20336031

  20. Calculation of structural parameters of a Van Der Waals complex of the CO molecule with a Li+ cation

    NASA Astrophysics Data System (ADS)

    Bulanin, K. M.; Bulychev, V. P.; Buturlimova, M. V.

    2015-12-01

    The equilibrium nuclear configuration and the potential energy and dipole moment component surfaces of an isolated Li+-CO complex are calculated quantum-mechanically in the MP4(SDQ)/6-311++G(3df) approximation. The geometrical parameters and the binding energy of the complex are determined. The frequencies and intensities for the fundamental transitions are calculated in the harmonic approximation. The one-, two-, and three-dimensional anharmonic vibrational Schrödinger equations are solved using the variational method. The energies of states of a three-dimensional vibrational system, anharmonic constants, and the frequencies and intensities of fundamental transitions are determined with the anharmonic interactions taken into account. The changes in the frequency and intensity of the C-O stretching vibration upon the formation of the complex are predicted.

  1. Synthesis and cation-binding studies of gold(I) complexes bearing oligoether isocyanide ligands with ester and amide as linkers.

    PubMed

    Hau, Franky Ka-Wah; Yam, Vivian Wing-Wah

    2016-01-01

    A series of dinuclear gold(I) isocyanide complexes of bis(alkynyl)calix[4]arene was designed and synthesized, and their photophysical and cation recognition properties were studied. Complex 1, [{calix[4]arene-(OCH2CONH-C6H4C≡C)2}{Au(CN-C6H4O(CH2CH2O)2CH3)}2], was found to show a high selectivity towards Al(3+) in CH2Cl2-MeCN (1 : 1 v/v). Upon addition of Al(3+), drastic changes in the electronic absorption, emission and (1)H NMR spectra were observed. These changes have been attributed to the formation of Au(I)Au(i) interactions induced by the high binding affinity of the amide site for the Al(3+) ion, instead of the high binding affinity expected of the oligoether site for alkali and alkaline earth metal ions. Further studies with the control complex, [{calix[4]arene-(OOC-C6H4C≡C)2}{Au(CN-C6H4O(CH2CH2O)2CH3)}2] (4), indicated that the amide carbonyl oxygen in the flexible pendants is crucial for the binding of Al(3+). PMID:26606327

  2. Preparation of highly efficient MRI contrast agents through complexation of cationic Gd(III)-containing metallosurfactant with biocompatible polyelectrolytes.

    PubMed

    Chen, Yingying; Zhu, Qin; Cui, Xinghui; Tang, Weijun; Yang, Heng; Yuan, Yuan; Hu, Aiguo

    2014-09-22

    Novel contrast agents were developed through assembling of Gd(III) -containing metallosurfactant (MS) with biocompatible polyelectrolytes sodium hyaluronate (HA), heparinsodium (HS) and dextran sulfate sodium (DSS). The formed polyelectrolyte-surfactant complexes showed different structural patterns as the charge ratio increased, including spherical aggregates, rod-like aggregates and network patterns in monovalent HA system, while spherical structures emerged in multivalent HS and DSS systems. Energy dispersive spectroscopy analysis and scanning electron microscopy mapping showed the presence of Gd(III) in these complexes. Inductively coupled plasma atomic emission spectrometry was further used to quantify the contents of Gd(III) in the assemblies. T1 magnetic resonance imaging showed that these Gd(III) -loaded complexes exhibited relaxivity of up to 63.81 mM(-1)  s(-1) , much higher than that of Ominiscan (4.64 mM(-1)  s(-1) ). The cytotoxicity test in vitro demonstrated the excellent biocompatibility of these complexes, which is essential for clinical application. PMID:25116812

  3. Inner-sphere complexation of cations at the rutile-water interface: A concise surface structural interpretation with the CD and MUSIC model

    NASA Astrophysics Data System (ADS)

    Ridley, Moira K.; Hiemstra, Tjisse; van Riemsdijk, Willem H.; Machesky, Michael L.

    2009-04-01

    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

  4. inner-sphere complexation of cations at the rutile-water interface: A concise surface structural interpretation with the CD and MUSIC model

    SciTech Connect

    Ridley, Mora K.; Hiemstra, T; Van Riemsdijk, Willem H.; Machesky, Michael L.

    2009-01-01

    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

  5. The rectal complex and Malpighian tubules of the cabbage looper (Trichoplusia ni): regional variations in Na+ and K+ transport and cation reabsorption by secondary cells.

    PubMed

    O'Donnell, Michael J; Ruiz-Sanchez, Esau

    2015-10-01

    In larvae of most Lepidoptera the distal ends of the Malpighian tubules are closely applied to the rectal epithelia and are ensheathed within the perinephric membrane, thus forming the rectal complex. The cryptonephric Malpighian tubules within the rectal complex are bathed in fluid within a functional compartment, the perinephric space, which is separate from the haemolymph. In this study, the scanning ion-selective electrode technique (SIET) was used to measure transport of Na(+) and K(+) across the rectal complex and across multiple regions of the Malpighian tubules of larvae of the cabbage looper Trichoplusia ni. Measurements were made in an intact preparation in which connections of the tubules upstream to the rectal complex and downstream to the urinary bladder and gut remained intact. SIET measurements revealed reabsorption of Na(+) and K(+) across the intact rectal complex and into the bath (haemolymph), with K(+) fluxes approximately twice as large as those of Na(+). Analyses of fluxes in larvae with empty guts, found in recently moulted larvae, versus those with full guts highlighted differences in the rates of K(+) or Na(+) transport within tubule regions that appeared morphologically homogeneous, such as the rectal lead. The distal rectal lead of larvae with empty guts reabsorbed K(+), whereas the same region secreted K(+) in tubules of larvae with full guts. SIET measurements of the ileac plexus also indicated a novel role for secondary (type II) cells in cation reabsorption. Secondary cells reabsorb K(+), whereas the adjacent principal (type I) cells secrete K(+). Na(+) is reabsorbed by both principal and secondary cells, but the rate of reabsorption by the secondary cells is approximately twice the rate in the adjacent principal cells. PMID:26491192

  6. The phosphate clamp: sequence selective nucleic acid binding profiles and conformational induction of endonuclease inhibition by cationic Triplatin complexes

    PubMed Central

    Prisecaru, Andreea; Molphy, Zara; Kipping, Ralph G.; Peterson, Erica J.; Qu, Yun; Kellett, Andrew; Farrell, Nicholas P.

    2014-01-01

    The substitution-inert polynuclear platinum(II) complex (PPC) series, [{trans-Pt(NH3)2(NH2(CH2)nNH3)}2-μ-(trans-Pt(NH3)2(NH2(CH2)nNH2)2}](NO3)8, where n = 5 (AH78P), 6 (AH78 TriplatinNC) and 7 (AH78H), are potent non-covalent DNA binding agents where nucleic acid recognition is achieved through use of the ‘phosphate clamp' where the square-planar tetra-am(m)ine Pt(II) coordination units all form bidentate N–O–N complexes through hydrogen bonding with phosphate oxygens. The modular nature of PPC–DNA interactions results in high affinity for calf thymus DNA (Kapp ∼5 × 107 M−1). The phosphate clamp–DNA interactions result in condensation of superhelical and B-DNA, displacement of intercalated ethidium bromide and facilitate cooperative binding of Hoechst 33258 at the minor groove. The effect of linker chain length on DNA conformational changes was examined and the pentane-bridged complex, AH78P, was optimal for condensing DNA with results in the nanomolar region. Analysis of binding affinity and conformational changes for sequence-specific oligonucleotides by ITC, dialysis, ICP-MS, CD and 2D-1H NMR experiments indicate that two limiting modes of phosphate clamp binding can be distinguished through their conformational changes and strongly suggest that DNA condensation is driven by minor-groove spanning. Triplatin-DNA binding prevents endonuclease activity by type II restriction enzymes BamHI, EcoRI and SalI, and inhibition was confirmed through the development of an on-chip microfluidic protocol. PMID:25414347

  7. Vitamin C interaction with cobalt-ammine cations. Synthesis, spectroscopic and structural characterization of cobalt-pentammine and cobalt-tetrammine sugar complexes containing L-ascorbate anion.

    PubMed

    Tajmir-Riahi, H A

    1986-11-01

    Interaction between [Co(NH3)5Cl]Cl2, [Co(NH3)4Cl2]Cl and L-ascorbic acid has been investigated in aqueous solution and solid complexes of the type [Co(NH3)5 ascorbate]Cl2 X H2O and [Co(NH3)4 ascorbate]Cl2 X H2O have been isolated and characterized by 13C-NMR, FT-IR and electron absorption spectroscopy. Spectroscopic and other evidence suggested that the sugar anion binds monodentately in the [Co(NH3)5 ascorbate]2+ cation via the ionized O3 oxygen atom and bidentately in [Co(NH3)4 ascorbate]2+ through the O1 and O4 oxygen atoms, resulting in a six-coordinate geometry around the Co(III) ion. The intermolecular sugar hydrogen-bonding network is perturbed upon sugar metalation and the sugar moiety shows a similar conformation to that of the sodium ascorbate compound in these series of cobalt-ammine complexes. PMID:3814746

  8. 1H, 13C NMR, FT-IR, ESI MS and PM5 studies of a new 3,6,9-trioxadecylamide of monensin A and its complexes with Li +, Na + and K + cations

    NASA Astrophysics Data System (ADS)

    Łowicki, Daniel; Huczyński, Adam; Brzezinski, Bogumil; Bartl, Franz

    2011-03-01

    A new 3,6,9-trioxadecylamide of monensin A (M-AM4) has been synthesised and its ability to form complexes with Li +, Na + and K + cations has been studied by ESI mass spectrometry, 1H and 13C NMR, FT-IR spectroscopy and PM5 semiempirical method. The ESI MS data indicate that M-AM4 forms complexes with Li +, Na + and K + of exclusively 1:1 stoichiometry which are stable up to cv = 70 V. The formation of the M-AM4-Na + is strongly favoured. Above cv = 70 the fragmentation process is observed. The spectroscopic studies show that the structures of the M-AM4 and its complexes with the cations of 1:1 stoichiometry are stabilized by intramolecular hydrogen bonds in which the OH groups are always involved. The C dbnd O amide group is engaged in the complexation process of each cation. The M-AM4-K + complex can also assume a structure in which the C dbnd O amide group does not participate in the complexation but the complexes of such structure do not dominate.

  9. A combined experimental and quantum mechanical investigation on some selected metal complexes of L-serine with first row transition metal cations

    NASA Astrophysics Data System (ADS)

    Mandal, Shilpi; Das, Gunajyoti; Askari, Hassan

    2015-02-01

    In the current study a joint solvent-free synthetic and computational approach has been adopted to explore the coordination properties of L-serine with the doubly charged cations of nickel, copper and zinc. The reaction products were characterized by elemental analyses, molar conductance, EDAX-SEM, TEM, TG/DTA, infrared, electronic absorption and fluorescence spectroscopy. Quantum chemical calculations, carried out in gas and aqueous phase using the BHandHLYP and MP2 methods in conjunction with 6-311++G(d,p) basis set, provide valuable insights concerning the interaction enthalpies and free energies; vibrational and absorption spectra along with various other molecular and electronic properties of the metal complexes. This study reveals that L-serine binds to the metal ions in a bi-dentate manner through its amino and carboxylate groups exhibiting highest binding affinity towards Cu(II) among the three metal ions considered here. As compared to the MP2 method, the spin-delocalized situations of the open-shell Cu(II) complex of L-serine have been better described at the BHandHLYP level. The physical origin of the molecular interactions of L-serine with the metal ions has also been examined by performing energy decomposition analysis (EDA). Effects of the aqueous environment are evident on the structure and stability of the metal complexes. The vibrational spectroscopic data furnished at MP2/6-311++G(d,p) level, which provide a good account of the structural changes inflicted in the molecular geometry of L-serine as a result of metal coordination, are in better agreement with our experimental observations as compared to those produced at the BHandHLYP/6-311++G(d,p) level.

  10. Biological in vitro and in vivo studies of a series of new asymmetrical cationic [99mTc(N)(DTC-Ln)(PNP)]+ complex (DTC-Ln = alicyclic dithiocarbamate and PNP = diphosphinoamine).

    PubMed

    Bolzati, Cristina; Cavazza-Ceccato, Mario; Agostini, Stefania; Refosco, Fiorenzo; Yamamichi, Yoshihiro; Tokunaga, Shinji; Carta, Davide; Salvarese, Nicola; Bernardini, Daniele; Bandoli, Giuliano

    2010-05-19

    (99m)Tc(N)-DBODC5 is a cationic mixed compound under clinical investigation as potential myocardial imaging agent. In spite of this, analogously to the other cationic (99m)Tc-agents, presents a relatively low first-pass extraction. Thus, modification of (99m)Tc(N)-DBODC(5) direct to increase its first-pass extraction keeping unaltered the favorable imaging properties would be desirable. This work describes the synthesis and biological evaluation of a series of novel cationic (99m)Tc-nitrido complexes, of general formula [(99m)TcN(DTC-Ln)(PNP)](+) (DTC-Ln= alicyclic dithiocarbamates; PNP = diphosphinoamine), as potential radiotracers for myocardial perfusion imaging. The synthesis of cationic (99m)Tc-(N)-complexes were accomplished in two steps. Biodistribution studies were performed in rats and compared with the distribution profiles of (99m)Tc(N)-DBODC5 and (99m)Tc-Sestamibi. The metabolisms of the most promising compounds were evaluated by HPLC methods. Biological studies revealed that most of the complexes have a high initial and persistent heart uptake with rapid clearance from nontarget tissues. Among tested compounds, 2 and 12 showed improved heart uptake with respect to the gold standard (99m)Tc-complexes with favorable heart-to-liver and slightly lower heart-to-lung ratios. Chromatographic profiles of (99m)Tc(N)-radioactivity extracted from tissues and fluids were coincident with the native compound evidencing remarkable in vivo stability of these agents. This study shows that the incorporation of alicyclic dithiocarbamate in the [(99m)Tc(N)(PNP)](+) building block yields to a significant increase of the heart uptake at early injection point suggesting that the first-pass extraction fraction of these novel complexes may be increased with respect to the other cationic (99m)Tc-agents keeping almost unaltered the favorable target/nontarget ratios. PMID:20402465

  11. Luminescence dynamics and {sup 13}C NMR characteristics of dinuclear complexes exhibiting coupled lanthanide(III) cation pairs

    SciTech Connect

    Matthews, K.D.; Bailey-Folkes, S.A.; Kahwa, I.A.

    1992-08-20

    Luminescence and cross-polarization magic angle spinning (CP-MAS) {sup 13}C NMR properties of lanthanide dinuclear macrocyclic complexes of a compartmental Schiff base chelate (1) derived from the condensation of 2,6-diformyl-p-cresol and 3,6-dioxa-1,8-octanediamine are reported. The Schiff base chromophore in 1 is a strong light absorber and an efficient sensitizer for intense Tb{sup 3+}({sup 5}D{sub 4}) and Eu{sup 3+}({sup 5}D{sub 0})(T < 110 K ) emission which does not exhibit self-quenching effects. Emission from Tb{sup 3+} is sensitized by the ligand singlet state; in striking contrast, Eu{sup 3+} emission is sensitized by the triplet state and reveals an unusual nonradiative quenching process at T > 110 K with a thermal barrier of {approx} 2300 cm{sup {minus}1}. Weak emission is observed from Dy{sup 3+}({sup 4}F{sub 9/2}), Sm{sup 3+}({sup 4}G{sub 5/2}), and Pr{sup 3+}({sup 1}D{sub 2}) diluted in Gd{sup 3+} (i.e., from Gd{sup 3+}-Ln{sup 3+} heteropairs, Ln = Pr, Sm, Dy). Intramolecular metal-metal (Ln-Ln = 4 {Angstrom}) interactions account for the greatly quenched emission from Sm{sup 3+}-Sm{sup 3+} and Dy{sup 3+}-Dy{sup 3+} homopairs compared to Gd{sup 3+}-Ln heteropairs (Ln = Sm, Dy). Gd{sup 3+}-Ln{sup 3+} emission lifetimes at 77 K are 1610 (Tb{sup 3+}), 890 (Eu{sup 3+}), 14 (Dy{sup 3+}) and {approx} 13 {mu}s (Sm{sup 3+}). Nonradiative relaxation processes at 77 K in dilute Ln{sup 3+}:Gd{sub 2}1(NO{sub 3}){sub 4}{center_dot}H{sub 2}O, being temperature independent for Sm{sup 3+} and Eu{sup 3+} but temperature dependent for Tb{sup 3+}, follow the energy gap law with {alpha} {approx} - 10{sup {minus}3} cm and B {approx} 2 x 10{sup 8} s{sup {minus}1}. CP-MAS data show paramagnetic broadening of {sup 13}C resonances which increases with the magnetic moment of Ln{sup 3+}. Surprisingly, no significant shifts in resonance positions corresponding to the changing nature of paramagnetic Ln{sup 3+} ions are observed. 43 refs., 8 figs., 2 tabs.

  12. Reaction of cationic transition metal complexes with furan, thiophene, and pyrrole. Model studies relevant to hydrodeoxygenation, hydrodesulfurization, and hydrodenitrogenation

    SciTech Connect

    Bakhtiar, R.; Jacobson, D.B.

    1995-12-01

    Hydrodesulfurization, denitrogenation, and deoxygenation reactions are important reactions in many research areas such as the removal of nitrogen and sulfur from coal. In this report, reactions of Fe{sup +} and FeL{sup +} (L = O, C{sub 4}H{sub 6}, c-C{sub 5}H{sub 6}, c-C{sub 5}H{sub 6}, C{sub 6}H{sub 6}, C{sub 5}H{sub 4}(=CH{sub 2})) with thiophene, furan, and pyrrole in the gas phase by using Fourier transform mass spectrometry (FTMS) are described. Fe{sup +}, Fe(C{sub 5}H{sub 5}){sup +}, and FeC{sub 6}H{sub 6}{sup +} yield exclusive, rapid adduct formation with thiophene, furan, and pyrrole. The iron-diene complex FeC{sub 4}H{sub 6}{sup +}, Fe(c-C{sub 5}H{sub 6}){sup +}), as well as FeC{sub 5}H{sub 4}(=CH{sub 2}){sup +} and FeO{sup +} are quite reactive. An intriguing reaction is the predominant, direct extrusion of CO from furan by FeC{sub 4}H{sub 6}{sup +}, Fe(c-C{sub 5}H{sub 6}){sup +}, Fe(C{sub 5}H{sub 4}(=CH{sub 2}){sup +}. In addition, FeC{sub 4}H{sub 6}{sup +} and Fe(c-C{sub 5}H{sub 6}){sup +} yield minor amounts of HCN extrusion from pyrrole. The absence of CS extrusion from thiophene may be due to the higher energy requirements than that for CO extrusion from furan or HCN extrusion from pyrrole. The dominant reaction channel for reaction of Fe(c-C{sub 5}H{sub 6}){sup +} with pyrrole and thiophene is hydrogen atom displacement which implies D{sup 0}(Fe(C{sub 5}H{sub 5}){sup +}-C{sub 4}H{sub 4}X) > D{sup 0}(Fe(C{sub 5}H{sub 5}){sup +}-H) = 46 {+-} 5 kcal/mol. D{sup 0}(Fe{sup +}-C{sub 4}H{sub 4}S) and D{sup 0}(Fe{sup +}C{sub 4}H{sub 5}N) = D{sup 0}(Fe{sup +}-C{sub 4}H{sub 6}) = 48 {+-} 5 kcal/mol. Finally, D{sup 0}(Fe{sup +}-C{sub 4}H{sub 4}O) > D{sup 0}(Fe{sup +}-C{sub 2}H{sub 4}) = 39.9 {+-} 1.4 kcal/mol and D{sup 0}(Fe{sup +}-C{sub 4}H{sub 4}O) < D{sup 0}(Fe{sup +}-C{sub 6}H{sub 6}) = 55 {+-} 5 kcal/mol. FeO{sup +} reacts rapidly with thiophene, furan, and pyrrole to yield initial loss of CO followed by additional neutral losses.

  13. Cyclometalated Iminophosphorane Gold(III) and Platinum(II) Complexes. A Highly Permeable Cationic Platinum(II) Compound with Promising Anticancer Properties.

    PubMed

    Frik, Malgorzata; Fernández-Gallardo, Jacob; Gonzalo, Oscar; Mangas-Sanjuan, Víctor; González-Alvarez, Marta; Serrano del Valle, Alfonso; Hu, Chunhua; González-Alvarez, Isabel; Bermejo, Marival; Marzo, Isabel; Contel, María

    2015-08-13

    New organometallic gold(III) and platinum(II) complexes containing iminophosphorane ligands are described. Most of them are more cytotoxic to a number of human cancer cell lines than cisplatin. Cationic Pt(II) derivatives 4 and 5, which differ only in the anion, Hg2Cl6(2-) or PF6(-) respectively, display almost identical IC50 values in the sub-micromolar range (25-335-fold more active than cisplatin on these cell lines). The gold compounds induced mainly caspase-independent cell death, as previously reported for related cycloaurated compounds containing IM ligands. Cycloplatinated compounds 3, 4, and 5 can also activate alternative caspase-independent mechanisms of death. However, at short incubation times cell death seems to be mainly caspase dependent, suggesting that the main mechanism of cell death for these compounds is apoptosis. Mercury-free compound 5 does not interact with plasmid (pBR322) DNA or with calf thymus DNA. Permeability studies of 5 by two different assays, in vitro Caco-2 monolayers and a rat perfusion model, have revealed a high permeability profile for this compound (comparable to that of metoprolol or caffeine) and an estimated oral fraction absorbed of 100%, which potentially makes it a good candidate for oral administration. PMID:26147404

  14. Formation of Polyion Complex (PIC) Micelles and Vesicles with Anionic pH-Responsive Unimer Micelles and Cationic Diblock Copolymers in Water.

    PubMed

    Ohno, Sayaka; Ishihara, Kazuhiko; Yusa, Shin-Ichi

    2016-04-26

    A random copolymer (p(A/MaU)) of sodium 2-(acrylamido)-2-methylpropanesulfonate (AMPS) and sodium 11-methacrylamidoundecanate (MaU) was prepared via conventional radical polymerization, which formed a unimer micelle under acidic conditions due to intramolecular hydrophobic interactions between the pendant undecanoic acid groups. Under basic conditions, unimer micelles were opened up to an expanded chain conformation by electrostatic repulsion between the pendant sulfonate and undecanoate anions. A cationic diblock copolymer (P163M99) consisting of poly(3-(methacrylamido)propyl)trimethylammonium chloride (PMAPTAC) and hydrophilic polybetaine, 2-(methacryloyloxy)ethylphosphorylcholine (MPC), blocks was prepared via controlled radical polymerization. Mixing of p(A/MaU) and P163M99 in 0.1 M aqueous NaCl under acidic conditions resulted in the formation of spherical polyion complex (PIC) micelles and vesicles, depending on polymer concentration before mixing. Shapes of the PIC micelles and vesicles changed under basic conditions due to collapse of the charge balance between p(A/MaU) and P163M99. The PIC vesicles can incorporate nonionic hydrophilic guest molecules, and the PIC micelles and vesicles can accept hydrophobic guest molecules in the hydrophobic core formed from p(A/MaU). PMID:27048989

  15. Cyclometalated Iminophosphorane Gold(III) and Platinum(II) Complexes. A Highly Permeable Cationic Platinum(II) Compound with Promising Anticancer Properties

    PubMed Central

    2015-01-01

    New organometallic gold(III) and platinum(II) complexes containing iminophosphorane ligands are described. Most of them are more cytotoxic to a number of human cancer cell lines than cisplatin. Cationic Pt(II) derivatives 4 and 5, which differ only in the anion, Hg2Cl62– or PF6– respectively, display almost identical IC50 values in the sub-micromolar range (25–335-fold more active than cisplatin on these cell lines). The gold compounds induced mainly caspase-independent cell death, as previously reported for related cycloaurated compounds containing IM ligands. Cycloplatinated compounds 3, 4, and 5 can also activate alternative caspase-independent mechanisms of death. However, at short incubation times cell death seems to be mainly caspase dependent, suggesting that the main mechanism of cell death for these compounds is apoptosis. Mercury-free compound 5 does not interact with plasmid (pBR322) DNA or with calf thymus DNA. Permeability studies of 5 by two different assays, in vitro Caco-2 monolayers and a rat perfusion model, have revealed a high permeability profile for this compound (comparable to that of metoprolol or caffeine) and an estimated oral fraction absorbed of 100%, which potentially makes it a good candidate for oral administration. PMID:26147404

  16. Scope and Mechanistic Analysis for Chemoselective Hydrogenolysis of Carbonyl Compounds Catalyzed by a Cationic Ruthenium Hydride Complex with a Tunable Phenol Ligand.

    PubMed

    Kalutharage, Nishantha; Yi, Chae S

    2015-09-01

    A cationic ruthenium hydride complex, [(C6H6)(PCy3)(CO)RuH](+)BF4(-) (1), with a phenol ligand was found to exhibit high catalytic activity for the hydrogenolysis of carbonyl compounds to yield the corresponding aliphatic products. The catalytic method showed exceptionally high chemoselectivity toward the carbonyl reduction over alkene hydrogenation. Kinetic and spectroscopic studies revealed a strong electronic influence of the phenol ligand on the catalyst activity. The Hammett plot of the hydrogenolysis of 4-methoxyacetophenone displayed two opposite linear slopes for the catalytic system 1/p-X-C6H4OH (ρ = -3.3 for X = OMe, t-Bu, Et, and Me; ρ = +1.5 for X = F, Cl, and CF3). A normal deuterium isotope effect was observed for the hydrogenolysis reaction catalyzed by 1/p-X-C6H4OH with an electron-releasing group (kH/kD = 1.7-2.5; X = OMe, Et), whereas an inverse isotope effect was measured for 1/p-X-C6H4OH with an electron-withdrawing group (kH/kD = 0.6-0.7; X = Cl, CF3). The empirical rate law was determined from the hydrogenolysis of 4-methoxyacetophenone: rate = kobsd[Ru][ketone][H2](-1) for the reaction catalyzed by 1/p-OMe-C6H4OH, and rate = kobsd[Ru][ketone][H2](0) for the reaction catalyzed by 1/p-CF3-C6H4OH. Catalytically relevant dinuclear ruthenium hydride and hydroxo complexes were synthesized, and their structures were established by X-ray crystallography. Two distinct mechanistic pathways are presented for the hydrogenolysis reaction on the basis of these kinetic and spectroscopic data. PMID:26235841

  17. Photoinduced electron transfer between the cationic complexes Ru(NH3)5pz2+ and trans-RuCl([15]aneN4)NO2+ mediated by phosphate ion: visible light generation of nitric oxide for biological targets.

    PubMed

    da Silva, Roberto S; Marchesi, Mario S P; Khin, Chosu; Lunardi, Claure N; Bendhack, Lusiane M; Ford, Peter C

    2007-06-21

    The photochemical behavior of the tetraazamacrocyclic complex trans-RuCl([15]ane)(NO)2+ (RuNO2+) in a 10 mM phosphate buffer solution, pH 7.4, and in the presence of Ru(NH3)5pz2+ (Rupz2+) is reported. Irradiation (436 nm) of an aqueous solution containing both cationic complexes as PF6- salts labilizes NO from RuNO2+ with a quantum yield (phiNO) dependent on the concentration of Rupz2+ with a maximum value of phiNO (1.03(11)x10(-3) einstein mol-1) found for a solution with equimolar concentrations (5x10(-5) M) of the two complexes in phosphate buffer solution. The quantitative behavior of this system suggests that the two cations undergo preassociation such that photoexcitation of the visible absorbing Rupz2+ is followed by electron or energy transfer to RuNO2+, which does not absorb appreciably at the excitation wavelength, and this leads to NO release from the reduced nitrosyl complex. Notably, the NO release was not seen in the absence of phosphate buffer; thus, it appears that phosphate ions mediate NO generation, perhaps by facilitating formation of a supramolecular complex between the two ruthenium cations. Reexamination of the cyclic voltammetry of Rupz2+ showed that the electrochemical behavior of this species is also affected by the presence of the phosphate buffer. PMID:17439277

  18. Design and Synthesis of Amphiphilic and Luminescent Tris-Cyclometalated Iridium(III) Complexes Containing Cationic Peptides as Inducers and Detectors of Cell Death via a Calcium-Dependent Pathway.

    PubMed

    Hisamatsu, Yosuke; Shibuya, Ai; Suzuki, Nozomi; Suzuki, Toshihiro; Abe, Ryo; Aoki, Shin

    2015-05-20

    Cationic amphiphilic peptides have the potential to function as agents for the treatment of microbial infections and cancer therapy. The cationic and hydrophobic parts of these molecules allow them to associate strongly with negatively charged bacterial or cancer cell membranes, thus exerting antimicrobial and anticancer activities through membrane disruption. Meanwhile, cyclometalated iridium(III) complexes such as fac-Ir(ppy)3 (ppy = 2-phenylpyridine) and fac-Ir(tpy)3 (tpy = 2-(4'-tolyl)pyridine) possess C3-symmetric structures and excellent photophysical properties as phosphorescence materials, which make them important candidates for use in biological applications such as chemosensors, biolabeling, living cell staining, in vivo tumor imaging, and anticancer agents. We recently reported on some regioselective substitution reactions of Ir(tpy)3 and Ir(ppy)3 at the 5'-position (p-position with respect to the C-Ir bond) on the 2-phenylpyridine ligands and their subsequent conversions to a variety of functional groups. We report here on the design and synthesis of amphiphilic and luminescent tris-cyclometalated Ir complexes in which cationic peptides are attached through alkyl chain linkers that work as inducers and detectors of cell death. Ir complexes containing cationic peptides such as a KKGG sequence and alkyl chain linkers of adequate length (C6 and C8) exhibit considerable cytotoxicity against cancer cells such as Jurkat, Molt-4, HeLa-S3, and A549 cells, and that dead cells are well stained with these Ir complexes. Furthermore, an Ir complex in which the KKGG peptide is attached through a C6 linker displayed lower cytotoxicity against normal mouse lymphocytes. Mechanistic studies suggest that Ir complexes containing the KKGG peptide interact with anionic molecules on the cell surface and/or membrane receptors to trigger the Ca(2+) dependent pathway and intracellular Ca(2+) response, resulting in necrosis accompanied by membrane disruption. PMID:25875312

  19. Addition, cycloaddition, and metathesis reactions of the cationic carbyne complexes [Cp(CO)[sub 2]Mn[triple bond]CCH[sub 2]R][sup +] and neutral vinylidene complexes Cp(CO)[sub 2]M=C=C(H)R (M = Mn, Re)

    SciTech Connect

    Terry, M.R.; Mercando, L.A.; Kelley, C.; Geoffroy, G.L. ); Nombel, P.; Lugan, N.; Mathieu, R. ); Ostrander, R.L.; Owens-Waltermire, B.E.; Rheingold, A.L. )

    1994-03-01

    The cationic alkylidyne complexes [Cp(CO)[sub 2]M=VCCH[sub 2]R][sup +] (M = Re, R = H; M = Mn, R = H, Me, Ph) undergo facile deprotonation to give the corresponding neutral vinylidene complexes Cp(CO)[sub 2]M=C=C(H)R. For [Cp(CO)[sub 2]Re=VCCH[sub 3

  20. Exploring the influence of crystal environment on the geometry of bis(pyridine-2,6-dicarboxylato) chromium (III) anionic complexes containing various cationic moieties: Synthesis, structures and Hirshfeld surface analysis

    NASA Astrophysics Data System (ADS)

    Yousefi, Zakieh; Eshtiagh-Hosseini, Hossein; Salimi, Alireza; Janiak, Agnieszka

    2015-03-01

    Two chromium (III) complexes with pyridine-2,6-dicarboxylate ligand have been synthesized with various cations yielding new compounds: (2a4mpy)2[Cr(pydc)2]2 · 9H2O (I) and (bphda)[Cr(pydc)2]2 · DMF · 4H2O (II) where pydc = pyridine-2,6-dicarbocylate anion, 2a4mpy = 2-amino-4-methylpyrimidinium cation and bphda = 1,1‧-bisphenyl-4,4‧-diaminium cation. These compounds have been characterized by IR spectroscopy, CHN microanalysis and X-ray structural studies along with a detailed analysis of Hirshfeld surface and 2D fingerprint plot as an assisting tool for decoding of the intermolecular interactions. In both complex fragments, Cr(III) atoms are surrounded by four oxygen atoms and two nitrogen atoms from two pydc ligands, forming a distorted octahedral environment. Crystal packing in both compounds is mostly governed by strong Osbnd H⋯O and Nsbnd H⋯O classical hydrogen bond interactions and assisted by the interactions involving π-electrons, namely π⋯π off-face stacking, carbonyl⋯π or lone pair⋯π. All these interactions lead to rather complex three-dimensional structures. In this regard, the fingerprint plots enabled to explore the role of intermolecular interactions types on the distorted geometry of titled complexes and analogous structures retrieved from Cambridge Structural Database (CSD).

  1. Three ion-pair complexes containing bis(maleonitriledithiolate)copper(II) anion and substituted 2-aminopyridinium cations: Syntheses, crystal structures, and magnetic properties

    NASA Astrophysics Data System (ADS)

    Liu, Yin; Ou, Shu-Hua; Li, Jin-Ni; Liao, Xiao-Lan; Zheng, Xiao-Xu; Luo, Cui-Ping; Yang, Le-Min; Zhou, Jia-Rong; Ni, Chun-Lin

    2016-04-01

    Three new ion-pair complexes, [2-ClBz-2‧-NH2Py]2[Cu(mnt)2](1), [2-Cl-4-ClBz-2-NH2Py]2[Cu(mnt)2](2) and [2-Cl-4-BrBz-2‧-NH2Py]2[Cu(mnt)2]·C2H5OH(3) ([2-Cl-4-RBz-2‧-NH2Py]+ = 1-(2‧-chloro-4‧-Rbenzyl)-2-aminopyridinium, R = H, Cl, Br; mnt2- = maleonitriledithiolate), were synthesized and characterized by elemental analyses, IR, UV-visible, single crystal X-ray diffraction and magnetic measurements. Both 1 and 2 crystallize in the monoclinic space group P2(1)/c, and the [Cu(mnt)2]2- anions and the cations form a 1D network structure through the N-HṡṡṡN hydrogen bonds. While the anions in 3 form a ladder-like chain through the C-HṡṡṡN interactions between the [Cu(mnt)2]2- anions and CH3CH2OH molecules. Some weak interactions such as πṡṡṡπ, CuṡṡṡN, ClṡṡṡC, and C-HṡṡṡCl, O-HṡṡṡCl, C-HṡṡṡS, N-HṡṡṡO, N-HṡṡṡN and C-HṡṡṡN hydrogen bonds in three molecular solids generate further a 3D network structure. The magnetic measurement reveals that 1 shows a very weak ferromagnetic interaction, and 2 exhibits a transition from ferromagnetic to antiferromagnetic coupling about 15 K, while 3 shows an antiferromagnetic coupling feature with θ = -12.51 K when the temperature is lowered.

  2. Dehydrogenation of ammonia-borane by cationic Pd(II) and Ni(II) complexes in a nitromethane medium: hydrogen release and spent fuel characterization.

    PubMed

    Kim, Sung-Kwan; Hong, Sung-Ahn; Son, Ho-Jin; Han, Won-Sik; Michalak, Artur; Hwang, Son-Jong; Kang, Sang Ook

    2015-04-28

    A highly electrophilic cationic Pd(II) complex, [Pd(MeCN)4][BF4]2 (1), brings about the preferential activation of the B-H bond in ammonia-borane (NH3·BH3, AB). At room temperature, the reaction between 1 in CH3NO2 and AB in tetraglyme leads to Pd nanoparticles and formation of spent fuels of the general formula MeNHxBOy as reaction byproducts, while 2 equiv. of H2 is efficiently released per AB equiv. at room temperature within 60 seconds. For a mechanistic understanding of dehydrogenation by 1, the chemical structures of spent fuels were intensely characterized by a series of analyses such as elemental analysis (EA), X-ray photoelectron spectroscopy (XPS), solid state magic-angle-spinning (MAS) NMR spectra ((2)H, (13)C, (15)N, and (11)B), and cross polarization (CP) MAS methods. During AB dehydrogenation, the involvement of MeNO2 in the spent fuels showed that the mechanism of dehydrogenation catalyzed by 1 is different from that found in the previously reported results. This AB dehydrogenation derived from MeNO2 is supported by a subsequent digestion experiment of the AB spent fuel: B(OMe)3 and N-methylhydroxylamine ([Me(OH)N]2CH2), which are formed by the methanolysis of the AB spent fuel (MeNHxBOy), were identified by means of (11)B NMR and single crystal structural analysis, respectively. A similar catalytic behavior was also observed in the AB dehydrogenation catalyzed by a nickel catalyst, [Ni(MeCN)6][BF4]2 (2). PMID:25799252

  3. Effect of buffer cations and of H3O+ on the charge states of native proteins. Significance to determinations of stability constants of protein complexes.

    PubMed

    Verkerk, Udo H; Peschke, Michael; Kebarle, Paul

    2003-06-01

    The progressive reduction of charge in charge states of non-denatured proteins (lysozyme, ubiquitin, and cytochrome c), observed with nanospray in the positive ion mode, when the buffer salt ammonium acetate is replaced by ethylammonium acetates (EtNH(3)Ac, Et(2)NH(2)Ac and Et(3)NHAc) is rationalized on the basis of the charge residue model (CRM). The charge states of the multiply protonated protein are shown to be controlled by the increasing gas-phase basicities, GB(B), of the bases(B) NH(3), EtNH(2), Et(2)NH and Et(3)N. Charge states derived from evaluated apparent gas-phase basicities GB(app) of the basic side-chains of the protein and the known GB(B) of the above bases are found to be in agreement with the experimentally observed charge states. This is a requirement of the CRM, because in this model the small positive ions (the buffer cations in the present case) at the surface of the electrospray droplets are the excess ions that provide the charge of the final small droplet that contains the protein molecule and on evaporation of the solvent transfer the charge to the protein. The observed charge states in the absence of buffer salts, i.e. pure water, are attributed to excess H(3)O(+) ions produced by the electrolysis process that attends electrospray. A proposed extended mechanism provides predictions of factors that determine the sensitivity for detection of the multiply protonated proteins. Consideration of restraints imposed by the CRM lead to some simple predictions for conditions that should be present to obtain accurate determinations by electrospray and nanospray of stability constants for the protein-complex equilibrium in aqueous solution. PMID:12827631

  4. Cationic Conjugated Polymer/Hyaluronan-Doxorubicin Complex for Sensitive Fluorescence Detection of Hyaluronidase and Tumor-Targeting Drug Delivery and Imaging.

    PubMed

    Huang, Yanqin; Song, Caixia; Li, Huichang; Zhang, Rui; Jiang, Rongcui; Liu, Xingfen; Zhang, Guangwei; Fan, Quli; Wang, Lianhui; Huang, Wei

    2015-09-30

    Hyaluronidase (HAase) is becoming a new type of tumor marker since it has been demonstrated to be overexpressed in various kinds of cancer cells. In this study, we described a novel fluorescence method for sensitive, rapid, and convenient HAase detection and tumor-targeting drug delivery and imaging, using a probe prepared by electrostatic assembly of a cationic conjugated polymer (CCP) and anionic hyaluronan (HA) conjugated with the anticancer drug doxorubicin (Dox). The CCP we used was poly{[9,9-bis(6'-(N,N,N-diethylmethylammonium)hexyl)-2,7-fluorenylene ethynylene]-alt-co-[2,5-bis(3'-(N,N,N-diethylmethylammonium)-1'-oxapropyl)-1,4-phenylene]} tetraiodide (PFEP). HA is a natural mucopolysaccharide that can be hydrolyzed by HAase into fragments with low molecular weights. In the PFEP/HA-Dox complex, the fluorescence of PFEP was efficiently quenched due to electron transfer from PFEP to Dox. After the PFEP/HA-Dox complex was exposed to HAase or was taken up by cancer cells through the specific binding between HA and CD44 receptor, HA was degraded by HAase to release the Dox, leading to the recovery of PFEP fluorescence to the "turn-on" state. Moreover, the degree of fluorescence recovery was quantitatively correlated with the concentrations of HAase. Compared with many previously reported methods, our work did not require laborious multiple modifications of HA that may affect the activity of HAase. This point, combined with the excellent optoelectronic property of conjugated polymer, endowed this method with high sensitivity (detection limit: 0.075 U/mL), high specificity, and rapid response, making it applicable for reliable and routine detection of HAase. This fluorescent probe was successfully utilized to detect HAase levels in human urine samples; furthermore, it can also be employed as a multifunctional system by realizing tumor-targeting drug delivery and cell imaging simultaneously. The development of this fluorescence method showed promising potential for

  5. Cationic lipid-mediated nucleic acid delivery: beyond being cationic.

    PubMed

    Rao, N Madhusudhana

    2010-03-01

    Realization of the potential of nucleic acids as drugs is intricately linked to their in vivo delivery. Cationic lipids demonstrated tremendous potential as safe, efficient and scalable in vitro carriers of nucleic acids. For in vivo delivery of nucleic acids, the extant two component liposomal preparations consisting of cationic lipids and nucleic acids have been largely found to be insufficient. Being a soft matter, liposomes readily respond to many physiological variables leading to complex component and morphological changes, thus confounding the efforts in a priori identification of a "competent" formulation. In the recent past many chemical moieties that provide advantage in facing the challenges of barriers in vivo, were incorporated into cationic lipids to improve the transfection efficiency. The cationic lipids, essential for DNA condensation and protection, definitely require additional components to be efficient in vivo. In addition, formulations of cationic lipid carriers with non-lipidic components, mainly peptides, have demonstrated success in in vivo transfection. The present review describes some recent successes of in vivo nucleic acid delivery by cationic lipids. PMID:20060819

  6. The cation-π interaction.

    PubMed

    Dougherty, Dennis A

    2013-04-16

    The chemistry community now recognizes the cation-π interaction as a major force for molecular recognition, joining the hydrophobic effect, the hydrogen bond, and the ion pair in determining macromolecular structure and drug-receptor interactions. This Account provides the author's perspective on the intellectual origins and fundamental nature of the cation-π interaction. Early studies on cyclophanes established that water-soluble, cationic molecules would forego aqueous solvation to enter a hydrophobic cavity if that cavity was lined with π systems. Important gas phase studies established the fundamental nature of the cation-π interaction. The strength of the cation-π interaction (Li(+) binds to benzene with 38 kcal/mol of binding energy; NH4(+) with 19 kcal/mol) distinguishes it from the weaker polar-π interactions observed in the benzene dimer or water-benzene complexes. In addition to the substantial intrinsic strength of the cation-π interaction in gas phase studies, the cation-π interaction remains energetically significant in aqueous media and under biological conditions. Many studies have shown that cation-π interactions can enhance binding energies by 2-5 kcal/mol, making them competitive with hydrogen bonds and ion pairs in drug-receptor and protein-protein interactions. As with other noncovalent interactions involving aromatic systems, the cation-π interaction includes a substantial electrostatic component. The six (four) C(δ-)-H(δ+) bond dipoles of a molecule like benzene (ethylene) combine to produce a region of negative electrostatic potential on the face of the π system. Simple electrostatics facilitate a natural attraction of cations to the surface. The trend for (gas phase) binding energies is Li(+) > Na(+) > K(+) > Rb(+): as the ion gets larger the charge is dispersed over a larger sphere and binding interactions weaken, a classical electrostatic effect. On other hand, polarizability does not define these interactions. Cyclohexane is

  7. The Cation-π Interaction

    PubMed Central

    DOUGHERTY, DENNIS A.

    2014-01-01

    CONSPECTUS The chemistry community now recognizes the cation-π interaction as a major force for molecular recognition, joining the hydrophobic effect, the hydrogen bond, and the ion pair in determining macromolecular structure and drug-receptor interactions. This Account provides the author’s perspective on the intellectual origins and fundamental nature of the cation-π interaction. Early studies on cyclophanes established that water-soluble, cationic molecules would forgo aqueous solvation to enter a hydrophobic cavity if that cavity was lined with π systems. Important gas phase studies established the fundamental nature of the cation-π interaction. The strength of the cation-π interaction – Li+ binds to benzene with 38 kcal/mol of binding energy; NH4+ with 19 kcal/mol– distinguishes it from the weaker polar-π interactions observed in the benzene dimer or water-benzene complexes. In addition to the substantial intrinsic strength of the cation-π interaction in gas phase studies, the cation-π interaction remains energetically significant in aqueous media and under biological conditions. Many studies have shown that cation-π interactions can enhance binding energies by 2 – 5 kcal/mol, making them competitive with hydrogen bonds and ion pairs in drug-receptor and protein-protein interactions. As with other noncovalent interactions involving aromatic systems, the cation-π interaction includes a substantial electrostatic component. The six (four) Cδ−–Hδ+ bond dipoles of a molecule like benzene (ethylene) combine to produce a region of negative electrostatic potential on the face of the π system. Simple electrostatics facilitate a natural attraction of cations to the surface. The trend for (gas phase) binding energies is Li+>Na+>K+>Rb+: as the ion gets larger the charge is dispersed over a larger sphere and binding interactions weaken, a classical electrostatic effect. On other hand, polarizability does not define these interactions. Cyclohexane

  8. The structure and binding energies of the van der Waals complexes of Ar and N2 with phenol and its cation, studied by high level ab initio and density functional theory calculations

    NASA Astrophysics Data System (ADS)

    Vincent, Mark A.; Hillier, Ian H.; Morgado, Claudio A.; Burton, Neil A.; Shan, Xiao

    2008-01-01

    We have investigated, using both ab initio and density functional theory methods, the minimum energy structures and corresponding binding energies of the van der Waals complexes between phenol and argon or the nitrogen molecule, and the corresponding complexes involving the phenol cation. Structures were obtained at the MP2 level using a large basis, and the corresponding energies were corrected for basis set superposition error (BSSE), higher order electron correlation effects, and for basis set size. The structures of the global minima were further refined for the effects of BSSE and the corresponding binding energies were evaluated. For each neutral species, we find only a single true minimum, π bonded for argon and OH bonded for nitrogen. For both cationic species, we find that the OH-bonded complex is preferred over other minima which we have identified as having Ar or N2 between exogeneous atoms. The ab initio calculations are generally in excellent agreement with experimental binding energies and rotational constants. We find that the B3LYP functional is particularly poor at describing these complexes, while a density functional theory (DFT) method with an empirical correction for dispersive interactions (DFT-D) is very successful, as are some of the new functionals proposed by Zhao and Truhlar [J. Phys. Chem. A 109, 5656 (2005); J. Chem. Theory Comput. 2, 1009 (2006); Phys. Chem. Chem. Phys. 7, 2701 (2005); J. Phys. Chem. A 108, 6908 (2004)]. Both the ab initio and DFT-D methods accurately predict the intermolecular vibrational modes.

  9. A theoretical investigation of the energetics and spectroscopic properties of the gas-phase linear proton-bound cation-molecule complexes, XCH(+)-N2 (X = O, S).

    PubMed

    Begum, Samiyara; Subramanian, Ranga

    2016-01-01

    The structural features, spectroscopic properties, and interaction energies of the linear proton-bound complexes of OCH(+) and its sulfur analog SCH(+) with N2 were investigated using the high-level ab initio methods MP2 and CCSD(T) as well as density functional theory with the aug-cc-pVXZ (X = D, T) basis sets. The rotational constants along with the vibrational frequencies of the cation-molecule complexes are reported here. A comparison of the interaction energies of the OCH(+)-N2 and SCH(+)-N2 complexes with those of the OCH(+)-CO and OCH(+)-OC complexes was also performed. The energies of all the complexes were determined at the complete basis set (CBS) limit. CS shows higher proton affinity at the C site than CO does, so the complex OCH(+)-N2 is relatively strongly bound and has a higher interaction energy than the SCH(+)-N2 complex. Symmetry-adapted perturbation theory (SAPT) was used to decompose the total interaction energies of the complexes into the attractive electrostatic interaction energy (E elst), induction energy (E ind), dispersion energy (E disp), and repulsive exchange energy (E exch). We found that the ratio of E ind to E disp is large for these linear proton-bound complexes, meaning that inductive effects are favored in these complexes. The bonding characteristics of the linear complexes were elucidated using natural bond orbital (NBO) theory. NBO analysis showed that the attractive interaction is caused by NBO charge transfer from the lone pair on N to the σ*(C-H) antibonding orbital in XCH(+)-N2 (X = O, S). The quantum theory of atoms in molecules (QTAIM) was used to analyze the strengths of the various bonds within and between the cation and molecule in each of these proton-bound complexes in terms of the electron density at bond critical points (BCP). Graphical Abstract Linear proton-bound complexes of OCH(+)-N2 and SCH(+)-N2. In these complexes, inductive effect is favored over dispersive effect. The attractive interaction is the NBO

  10. Properties of cationic monosubstituted tetraalkylammonium cyclodextrin derivatives – their stability, complexation ability in solution or when deposited on solid anionic surface

    PubMed Central

    Popr, Martin; Filippov, Sergey K; Matushkin, Nikolai; Dian, Juraj

    2015-01-01

    Summary The thermal stability of the monosubstituted cationic cyclodextrin (CD) derivatives PEMEDA-β-CD and PEMPDA-β-CD, which differ in their substituent linker length (ethylene and propylene, respectively), was studied via 1H NMR experiments. PEMPDA-β-CD exhibited higher resistance towards the Hofmann degradation and was chosen as a more suitable host molecule for further studies. Inclusion properties of PEMPDA-β-CD in solution with a series of simple aromatic guests (salicylic acid, p-methoxyphenol and p-nitroaniline) were determined by isothermal titration calorimetry (ITC) and compared to the native β-CD. Permanently charged cationic CD derivatives were successfully deposited on the anionic solid surface of polymeric Nafion® 117 membrane via electrostatic interactions. Deposition kinetics and coverage of the surface were determined by ELSD. Finally, the ability of the CD derivatives bound to the solid surface to encapsulate aromatic compounds from aqueous solution was measured by UV–vis spectroscopy. The obtained results are promising for future industrial applications of the monosubstituted β-CD derivatives, because the preparation of cationic CD derivatives is applicable in large scale, without the need of chromatographic purification. Their ionic deposition on a solid surface is simple, yet robust and a straightforward process as well. PMID:25815069

  11. Methane activation by cobalt cluster cations, Con+ (n=2-16): Reaction mechanisms and thermochemistry of cluster-CHx (x=0-3) complexes

    NASA Astrophysics Data System (ADS)

    Citir, Murat; Liu, Fuyi; Armentrout, P. B.

    2009-02-01

    The kinetic energy dependences of the reactions of Con+ (n =2-16) with CD4 are studied in a guided ion beam tandem mass spectrometer over the energy range of 0-10 eV. The main products are hydride formation, ConD+, dehydrogenation to form ConCD2+, and double dehydrogenation yielding ConC+. These primary products decompose to form secondary and higher order products, ConCD+, Con-1D+, Con-1C+, Con-1CD+, and Con-1CD2+ at higher energies. Adduct formation of ConCD4+ is also observed for the largest cluster cations, n ≥10. In general, the efficiencies of the single and double dehydrogenation processes increase with cluster size, although the hexamer cation shows a reduced reactivity compared to its neighbors. All reactions exhibit thresholds, and cross sections for the various primary and secondary reactions are analyzed to yield reaction thresholds from which bond energies for cobalt cluster cations to D, C, CD, CD2, and CD3 are determined. The relative magnitudes of these bond energies are consistent with simple bond order considerations. Bond energies for larger clusters rapidly reach relatively constant values, which are used to estimate the chemisorption energies of the C, CD, CD2, and CD3 molecular fragments to cobalt surfaces.

  12. Hybrid organic-inorganic chlorozincate and a molecular zinc complex involving the in situ formed imidazo[1,5-a]pyridinium cation: serendipitous oxidative cyclization, structures and photophysical properties.

    PubMed

    Buvaylo, Elena A; Kokozay, Vladimir N; Linnik, Rostyslav P; Vassilyeva, Olga Yu; Skelton, Brian W

    2015-08-14

    Two novel compounds, the organic-inorganic hybrid [L](2)[ZnCl(4)] (1) and the coordination complex LZnCl(3) (2), where L is the 2-methyl-3-(pyridin-2-yl)imidazo[1,5-a]pyridinium cation, were prepared using the oxidative condensation-cyclization of 2-pyridinecarbaldehyde and CH(3)NH(2)·HCl in methanol in the presence of Zn(2+) cations. The metal-free interaction of the organic components afforded the salt [L][Cl]·1.5H(2)O (3). The use of methylamine hydrochloride instead of its aqueous solution is believed to be responsible for the cyclocondensation with the formation of L instead of the expected Schiff base ligand. Compounds 1-3 have been obtained as single crystals and characterized by elemental analysis, IR, NMR spectroscopy, and single-crystal X-ray diffraction techniques. The structure of 1 is described as layers of cations and anions stacked along the c-axis, with the minimum ZnZn distance being 8.435 Å inside a layer. In the crystal lattice of 3, the cations are arranged in stacks propagating along the a-axis; the 1D H-bonding polymer built of chloride ions and water molecules runs parallel to a column of stacked cations. The organic cations in salts 1 and 3 show various patterns of π-π stacking. The discrete molecular structure of 2 shows coordination of a Zn atom to the N(pyridyl) atom, which enables one of the chloride atoms attached to the metal centre to interact with a π-system of the positively charged imidazolium ring. Numerous C-HCl contacts in a 1-3 are seen as space-filling van der Waals interactions of minor importance in determining crystal packing. The (1)H NMR studies suggest that the Zn-N coordination found in the solid-state structure of 2 is not retained in dmso, and 1, 2 and 3 are completely dissociated in solution. The emission spectra of 1 and 2 (λ(max) = 455 and 445 nm, respectively) exhibit red-shifts of fluorescence wavelength when compared to 3 and differ in the shapes and maxima of the emission as well as in relative

  13. A complete map of the ion chemistry of the naphthalene radical cation? DFT and RRKM modeling of a complex potential energy surface

    NASA Astrophysics Data System (ADS)

    Solano, Eduardo A.; Mayer, Paul M.

    2015-09-01

    The fragmentation mechanisms of the naphthalene molecular ion to [M-C4H2]+•, [M-C2H2]+•, [M-H2]+•, and [M-H•]+ were obtained at the UB3LYP/6-311+G(3df,2p)//UB3LYP/6-31G(d) level of theory and were subsequently used to calculate the microcanonical rate constants, k(E)'s, for all the steps by the Rice-Ramsperger-Kassel-Marcus formalism. The pre-equilibrium and steady state approximations were applied on different regions of the potential energy profiles to obtain the fragmentation k(E)'s and calculate the relative abundances of the ions as a function of energy. These results reproduce acceptably well the imaging photoelectron-photoion coincidence spectra of naphthalene, in the photon-energy range 14.0-18.8 eV that was previously reported by our group. Prior to dissociation, the molecular ion rapidly equilibrates with a set of isomers that includes the Z- and E-phenylvinylacetylene (PVA) radical cations. The naphthalene ion is the predominant isomer below 10 eV internal energy, with the other isomers remaining at steady state concentrations. Later on, new steady-state intermediates are formed, such as the azulene and 1-phenyl-butatriene radical cations. The naphthalene ion does not eject an H atom directly but eliminates an H2 molecule in a two-step fragmentation. H• loss occurs instead from the 1-phenyl-butatriene ion. The PVA ions initiate the ejection of diacetylene (C4H2) to yield the benzene radical cation. Acetylene elimination yields the pentalene cation at low energies (where it can account for 45.9%-100.0% of the rate constant of this channel), in a three-step mechanism starting from the azulene ion. However, above 7.6 eV, the major [M-C2H2]+• structure is the phenylacetylene cation.

  14. A complete map of the ion chemistry of the naphthalene radical cation? DFT and RRKM modeling of a complex potential energy surface.

    PubMed

    Solano, Eduardo A; Mayer, Paul M

    2015-09-14

    The fragmentation mechanisms of the naphthalene molecular ion to [M-C4H2](+•), [M-C2H2](+•), [M-H2](+•), and [M-H(•)](+) were obtained at the UB3LYP/6-311+G(3df,2p)//UB3LYP/6-31G(d) level of theory and were subsequently used to calculate the microcanonical rate constants, k(E)'s, for all the steps by the Rice-Ramsperger-Kassel-Marcus formalism. The pre-equilibrium and steady state approximations were applied on different regions of the potential energy profiles to obtain the fragmentation k(E)'s and calculate the relative abundances of the ions as a function of energy. These results reproduce acceptably well the imaging photoelectron-photoion coincidence spectra of naphthalene, in the photon-energy range 14.0-18.8 eV that was previously reported by our group. Prior to dissociation, the molecular ion rapidly equilibrates with a set of isomers that includes the Z- and E-phenylvinylacetylene (PVA) radical cations. The naphthalene ion is the predominant isomer below 10 eV internal energy, with the other isomers remaining at steady state concentrations. Later on, new steady-state intermediates are formed, such as the azulene and 1-phenyl-butatriene radical cations. The naphthalene ion does not eject an H atom directly but eliminates an H2 molecule in a two-step fragmentation. H(•) loss occurs instead from the 1-phenyl-butatriene ion. The PVA ions initiate the ejection of diacetylene (C4H2) to yield the benzene radical cation. Acetylene elimination yields the pentalene cation at low energies (where it can account for 45.9%-100.0% of the rate constant of this channel), in a three-step mechanism starting from the azulene ion. However, above 7.6 eV, the major [M-C2H2](+•) structure is the phenylacetylene cation. PMID:26374033

  15. A complete map of the ion chemistry of the naphthalene radical cation? DFT and RRKM modeling of a complex potential energy surface

    SciTech Connect

    Solano, Eduardo A.; Mayer, Paul M.

    2015-09-14

    The fragmentation mechanisms of the naphthalene molecular ion to [M–C{sub 4}H{sub 2}]{sup +•}, [M–C{sub 2}H{sub 2}]{sup +•}, [M–H{sub 2}]{sup +•}, and [M–H{sup •}]{sup +} were obtained at the UB3LYP/6-311+G(3df,2p)//UB3LYP/6-31G(d) level of theory and were subsequently used to calculate the microcanonical rate constants, k(E)’s, for all the steps by the Rice-Ramsperger-Kassel-Marcus formalism. The pre-equilibrium and steady state approximations were applied on different regions of the potential energy profiles to obtain the fragmentation k(E)’s and calculate the relative abundances of the ions as a function of energy. These results reproduce acceptably well the imaging photoelectron-photoion coincidence spectra of naphthalene, in the photon-energy range 14.0–18.8 eV that was previously reported by our group. Prior to dissociation, the molecular ion rapidly equilibrates with a set of isomers that includes the Z- and E-phenylvinylacetylene (PVA) radical cations. The naphthalene ion is the predominant isomer below 10 eV internal energy, with the other isomers remaining at steady state concentrations. Later on, new steady-state intermediates are formed, such as the azulene and 1-phenyl-butatriene radical cations. The naphthalene ion does not eject an H atom directly but eliminates an H{sub 2} molecule in a two-step fragmentation. H{sup •} loss occurs instead from the 1-phenyl-butatriene ion. The PVA ions initiate the ejection of diacetylene (C{sub 4}H{sub 2}) to yield the benzene radical cation. Acetylene elimination yields the pentalene cation at low energies (where it can account for 45.9%–100.0% of the rate constant of this channel), in a three-step mechanism starting from the azulene ion. However, above 7.6 eV, the major [M–C{sub 2}H{sub 2}]{sup +•} structure is the phenylacetylene cation.

  16. The impacts of cation stoichiometry and substrate surface quality on nucleation, structure, defect formation, and intermixing in complex oxide heteroepitaxy LaCrO3 on SrTiO3(001)

    SciTech Connect

    Qiao, Liang; Zhang, K. H. L; Bowden, Mark E; Varga, Tamas; Shutthanandan, Vaithiyalingam; Colby, Robert; Du, Yingge; Kabius, Bernd; Sushko, Peter V; Biegalski, Michael D; Chambers, S. A.

    2013-01-01

    Our ability to design and fabricate electronic devices with reproducible properties using complex oxides is critically dependent on our ability to controllably synthesize these materials in thin-film form. Structure-property relationships are intimately tied to film and interface composition Here we report on the effect of cation stoichiometry on structural quality and defect formation in LaCrO3 heteroepitaxial films prepared using molecular beam epitaxy. We calculate from first principles the regions of stability of various candidate defects as a function of Cr and O chemical potential, along with the predicted effects of these defects on structural parameters. We show that epitaxial LaCrO3 films readily nucleate and remain coherently strained on SrTiO3(001) over a wide range of La-to-Cr atom ratios, but that La-rich films are of considerably lower structural quality than stoichiometric and Cr-rich films. Cation imbalances are accompanied by anti-site defect formation, as deduced by comparing experimental trends in the c lattice parameter with those from first-principles calculations. Cation mixing occurs at the interface for all La-to-Cr ratios investigated, and is not quenched by deposition on SrTiO3(001) at ambient temperature. Indiffused La atoms occupy Sr sites, most likely facilitated by Sr vacancy formation in STO resulting from high-temperature oxygen annealing required to prepare the substrate. Intermixing is effectively quenched by using molecular beam epitaxy to deposit LaCrO3 at ambient temperature on defect free Si(001). However, analogous pulsed laser deposition on Si is accompanied by cation mixing.

  17. Ion recognition: application of symmetric and asymmetric schiff bases and their complexes for the fabrication of cationic and anionic membrane sensors to determine ions in real samples.

    PubMed

    Faridbod, Farnoush; Ganjali, Mohammad Reza; Dinarvand, Rassoul; Norouzi, Parviz

    2007-08-01

    Schiff base compounds refer to the branch of supra-molecules and can be used as sensing material in the construction of potentiometric ion selective electrodes (ISEs). This relatively modern field has been subject to extensive research in the period of 1999-2007 when more than 100 ISEs employing Schiff bases were constructed. The quantitative high-throughput detection of 29 cations and 7 anions has been demonstrated in various scientific branches, such as biomedicine, pharmacy, biochemistry, pharmacology, environmental chemistry, food technology, and agriculture. This review discusses Schiff base compounds and their applications in the design and development of ion selective sensors and microsensors. PMID:17979636

  18. Effect of the preparation procedure on the structural properties of oligonucleotide/cationic liposome complexes (lipoplexes) studied by electron spin resonance and Zeta potential.

    PubMed

    Ciani, Laura; Ristori, Sandra; Bonechi, Claudia; Rossi, Claudio; Martini, Giacomo

    2007-12-01

    Lipoplexes with different surface charge were prepared from a short oligonucleotide (20 mer, dsAT) inserted into liposomes of 1,2-dioleoyl-3-trimethylammonium-propane (DOTAP) and 1,2-dioleoyl-sn-glycero-3-phospho-ethanolamine (DOPE). The starting liposomes were prepared by two different procedures, i.e. progressive dsAT addition starting from plain liposomes (titration) and direct mixing of dsAT with pure liposomes (point to point preparation). Lipoplexes were characterized from a molecular point of view by Electron Spin Resonance (ESR) of a cationic spin probe and by Nuclear Magnetic Resonance. Structural and surface features were analysed by Zeta potential (zeta) measurements and Cryo-TEM micrographs. The complete set of results allowed to demonstrate that: i) the interactions between dsAT and cationic lipids were strong and occurred at the liposome surface; ii) the overall shape and physicochemical properties of liposomes did not change when short nucleic acid fragments were added before surface charge neutralization; iii) the bilayer structure of the lipids in lipoplexes was substantially preserved at all charge ratios; iv) the physical status of lipoplexes with electrical charge far from neutrality did not depend on the preparation method. PMID:17950520

  19. Cation-cation interactions and cation exchange in a series of isostructural framework uranyl tungstates

    NASA Astrophysics Data System (ADS)

    Balboni, Enrica; Burns, Peter C.

    2014-05-01

    The isotypical compounds (UO2)3(WO6)(H2O)5 (1), Ag(UO2)3(WO6)(OH)(H2O)3 (2), K(UO2)3(WO6)OH(H2O)4 (3), Rb(UO2)3(WO6)(OH)(H2O)3.5 (4), and Cs(UO2)3(WO6)OH(H2O)3 (5) were synthesized, characterized, and their structures determined. Each crystallizes in space group Cc. (1): a=12.979 (3), b=10.238 (2), c=11.302 (2), β=102.044 (2); (2): a=13.148 (2), b=9.520 (1), c=11.083 (2), β=101.568 (2); (3): a=13.111 (8), b=9.930 (6), c=11.242 (7), β=101.024 (7); (4): a=12.940 (2), b=10.231 (2), c=11.259(2), β=102.205 (2); (5): a=12.983 (3), b=10.191 (3), c=11.263 (4), β=101.661 (4). Compounds 1-5 are a framework of uranyl and tungsten polyhedra containing cation-cation interactions. The framework has three symmetrically distinct U(VI) cations, one tungsten, sixteen to eighteen oxygen atoms, and in 2-5, one monovalent cation. Each atom occupies a general position. Each U(VI) cation is present as a typical (UO2)2+ uranyl ion in an overall pentagonal bipyramidal coordination environment. Each pentagonal bipyramid shares two equatorial edges with two other pentagonal bipyramids, forming a trimer. Trimers are connected into chains by edge-sharing with WO6 octahedra. Chains are linked through cation-cation interactions between two symmetrically independent uranyl ions. This yields a remarkably complex system of intersecting channels that extend along [0 0 1] and [-1 1 0]. The cation exchange properties of 2 and 3 were characterized at room temperature and at 140 °C.

  20. The cubyl cation rearrangements.

    PubMed

    Jalife, Said; Mondal, Sukanta; Cabellos, Jose Luis; Martinez-Guajardo, Gerardo; Fernandez-Herrera, Maria A; Merino, Gabriel

    2016-02-25

    Born-Oppenheimer molecular dynamics simulations and high-level ab initio computations predict that the cage-opening rearrangement of the cubyl cation to the 7H(+)-pentalenyl cation is feasible in the gas phase. The rate-determining step is the formation of the cuneyl cation with an activation barrier of 25.3 kcal mol(-1) at the CCSD(T)/def2-TZVP//MP2/def2-TZVP level. Thus, the cubyl cation is kinetically stable enough to be formed and trapped at moderate temperatures, but it may be rearranged at higher temperatures. PMID:26880646

  1. Charge transfer complexes of fullerenes containing C60˙(-) and C70˙(-) radical anions with paramagnetic Co(II)(dppe)2Cl(+) cations (dppe: 1,2-bis(diphenylphosphino)ethane).

    PubMed

    Konarev, Dmitri V; Troyanov, Sergey I; Otsuka, Akihiro; Yamochi, Hideki; Saito, Gunzi; Lyubovskaya, Rimma N

    2016-04-12

    The reduction of Co(II)(dppe)Cl2 with sodium fluorenone ketyl produces a red solution containing the Co(I) species. The dissolution of C60 in the obtained solution followed by the precipitation of crystals with hexane yields a salt {Co(I)(dppe)2(+)}(C60˙(-))·2C6H4Cl2 and a novel complex {Co(dppe)2Cl}(C60) (). With C70, only the crystals of {Co(dppe)2Cl}(C70)·0.5C6H4Cl2 () are formed. Complex contains zig-zag fullerene chains whereas closely packed double chains are formed from fullerenes in . According to the optical spectra and magnetic data charge transfer occurs in both and with the formation of the Co(II)(dppe)2Cl(+) cations and the C60˙(-) or C70˙(-) radical anions. In spite of the close packing in crystals, C60˙(-) or C70˙(-) retain their monomeric form at least down to 100 K. The effective magnetic moments of and of 1.98 and 2.27μB at 300 K, respectively, do not attain the value of 2.45μB expected for the system with two non-interacting S = 1/2 spins at full charge transfer to fullerenes. Most probably diamagnetic {Co(I)(dppe)2Cl}(0) and neutral fullerenes are partially preserved in the samples which can explain the weak magnetic coupling of spins and the absence of fullerene dimerization in both complexes. The EPR spectra of and show asymmetric signals approximated by several lines with g-factors ranging from 2.0009 to 2.3325. These signals originate from the exchange interaction between the paramagnetic Co(II)(dppe)2Cl(+) cations and the fullerene˙(-) radical anions. PMID:26956368

  2. Mechanism of oligonucleotide release from cationic liposomes.

    PubMed Central

    Zelphati, O; Szoka, F C

    1996-01-01

    We propose a mechanism for oligonucleotide (ODN) release from cationic lipid complexes in cells that accounts for various observations on cationic lipid-nucleic acid-cell interactions. Fluorescent confocal microscopy of cells treated with rhodamine-labeled cationic liposome/ fluorescein-labeled ODN (F-ODN) complexes show the F-ODN separates from the lipid after internalization and enters the nucleus leaving the fluorescent lipid in cytoplasmic structures. ODN displacement from the complex was studied by fluorescent resonance energy transfer. Anionic liposome compositions (e.g., phosphatidylserine) that mimic the cytoplasmic facing monolayer of the cell membrane released ODN from the complex at about a 1:1 (-/+) charge ratio. Release was independent of ionic strength and pH. Physical separation of the F-ODN from monovalent and multivalent cationic lipids was confirmed by gel electrophoresis. Fluid but not solid phase anionic liposomes are required, whereas the physical state of the cationic lipids does not effect the release. Water soluble molecules with a high negative linear charge density, dextran sulfate, or heparin also release ODN. However, ATP, spermidine, spermine, tRNA, DNA, polyglutamic acid, polylysine, bovine serum albumin, or histone did not release ODN, even at 100-fold charge excess (-/+). Based upon these results, we propose that the complex, after internalization by endocytosis, induces flip-flop of anionic lipids from the cytoplasmic facing monolayer. Anionic lipids laterally diffuse into the complex and form a charged neutralized ion-pair with the cationic lipids. This leads to displacement of the ODN from the cationic lipid and its release into the cytoplasm. Images Fig. 1 Fig. 3 PMID:8876163

  3. Cation-cation interactions, magnetic communication and reactivity of the pentavalent uraniumion [U(NR)2]+

    SciTech Connect

    Spencer, Liam P; Schelter, Eric J; Boncella, James M; Yang, Ping; Gsula, Robyn L; Scott, Brian L; Thompson, Joe D; Kiplinger, Jacqueline L; Batista, Enrique R

    2009-01-01

    The dimeric bis(imido) uranium complex [{l_brace}U(NtBu)2(I)(tBu2bpy){r_brace}2] (see picture; U green, N blue, I red) has cation-cation interactions between [U(NR)2]+ ions. This f1-f1 system also displays f orbital communication between uranium(V) centers at low temperatures, and can be oxidized to generate uranium(VI) bis(imido) complexes.

  4. Temperature-controlled formation of olygomeric and polymeric compounds based on [Re4Te4(CN)12]4- cluster anions and Tm3+/1,10-phen complex cations

    NASA Astrophysics Data System (ADS)

    Litvinova, Yulia M.; Gayfulin, Yakov M.; Samsonenko, Denis G.; Piryazev, Dmitry A.; Mironov, Yuri V.

    2016-03-01

    Self-assembly reaction of [Re4Te4(CN)12]4- tetrahedral rhenium chalcocyanide cluster anions, Tm3+ cations and 1,10-phenanthroline in an H2O/EtOH medium was investigated at different temperatures. Slow mixing of reagent solutions at the room temperature lead to formation of cluster compound (1) containing unique trimeric anionic fragment [{Tm(phen) (H2O)4}{Tm(phen)2(H2O)3}{Tm(phen)2(H2O)2}{Re4Te4(CN)12}3]3- (A1, phen = 1,10-phenanthroline). Oligomeric anion A1 shows an unusual U-shaped structure build from three cluster anions and three {Tm(phen)n(H2O)m}3+ (n = 1, 2; m = 2-4) complex cations linked to each other by sbnd Ctbnd Nsbnd Tmsbnd Ntbnd Csbnd covalent bonds and two couples of short OH…N hydrogen bonds. At the elevated (80-100 °C) temperatures the initial reaction products were dissolved, however, further increase of temperature up to 150 °C resulted in formation of layered (2D) coordination polymer K[{Tm(phen) (H2O)3}{Re4Te4(CN)12}]·0.5H2O (2). In addition to the experimental and X-Ray structural analysis data, thermal decomposition of compounds is also discussed.

  5. The Impacts of Cation Stoichiometry and Substrate Surface Quality on Nucleation, Structure, Defect Formation, and Intermixing in Complex Oxide Heteroepitaxy–LaCrO3 on SrTiO3(001)

    SciTech Connect

    Qiao, Liang; Zhang, Hongliang; Bowden, Mark E.; Varga, Tamas; Shutthanandan, V.; Colby, Robert J.; Du, Yingge; Kabius, Bernd C.; Sushko, P. V.; Biegalski, Michael D.; Chambers, Scott A.

    2013-06-20

    Our ability to design and fabricate electronic devices with reproducible properties using complex oxides is critically dependent on our ability to controllably synthesize these materials in thin-film form. Structure-property relationships are intimately tied to film and interface composition. Here we report on the effects of cation stoichiometry in LaCrO3 heteroepitaxial films prepared using molecular beam epitaxy. We show that LaCrO3 films grow pseudomorphically on SrTiO3(001) over an wide range of La-to-Cr atom ratios. However, the growth mode and structural quality are sensitive to the La-to-Cr ratio, with La-rich films being of considerably lower structural quality than Cr-rich films. Cation mixing occurs at the interface for all La-to-Cr ratios investigated, and is not quenched by deposition at ambient temperature. Indiffused La atoms occupy Sr sites in the substrate. The presence of defects in the SrTiO3 substrate is implicated in promoting La indiffusion by comparing the properties of LaCrO3/SrTiO3 with those of LaCrO3/Si, both prepared at ambient temperature. Additionally, pulsed laser deposition is shown to result in more extensive interfacial mixing than molecular beam epitaxy for deposition at ambient temperature on Si.

  6. Incorporation of transition metals into Mg Al layered double hydroxides: Coprecipitation of cations vs. their pre-complexation with an anionic chelator

    NASA Astrophysics Data System (ADS)

    Tsyganok, Andrey; Sayari, Abdelhamid

    2006-06-01

    A comparative study on two different methods for preparing Mg-Al layered double hydroxides (LDH) containing various divalent transition metals M ( M=Co, Ni, Cu) has been carried out. The first (conventional) method involved coprecipitation of divalent metals M(II) with Mg(II) and Al(III) cations using carbonate under basic conditions. The second approach was based on the ability of transition metals to form stable anionic chelates with edta 4- (edta 4-=ethylenediaminetetraacetate) that were synthesized and further introduced into LDH by coprecipitation with Mg and Al. The synthesized LDHs were characterized by X-ray diffraction (XRD) and X-ray fluorescence (XRF) methods, thermogravimetry with mass-selective detection of decomposition products (TG-MSD), Fourier transform infrared (FTIR) and Raman spectroscopy techniques. The results obtained were discussed in terms of efficiency of transition metal incorporation into the LDH structure, thermal stability of materials and the ability of metal chelates to intercalate the interlayer space of Mg-Al LDH. Vibrational spectroscopy studies confirmed that the integrity of the metal chelates was preserved upon incorporation into the LDH.

  7. Efficient cross-coupling of aryl Grignard reagents with alkyl halides by recyclable ionic iron(III) complexes bearing a bis(phenol)-functionalized benzimidazolium cation.

    PubMed

    Xia, Chong-Liang; Xie, Cun-Fei; Wu, Yu-Feng; Sun, Hong-Mei; Shen, Qi; Zhang, Yong

    2013-12-14

    A novel bis(phenol)-functionalized benzimidazolium salt, 1,3-bis(3,5-di-tert-butyl-2-hydroxybenzyl)benzimidazolium chloride (H3LCl, 1), was designed and used to prepare ionic iron(III) complexes of the type [H3L][FeX4] (X = Cl, 2; X = Br, 3). Both 2 and 3 were characterized by elemental analysis, Raman spectroscopy, electrospray ionization mass spectrometry and X-ray crystallography. The catalytic performances of 2 and 3 in cross-coupling reactions using aryl Grignard reagents with primary and secondary alkyl halides bearing β-hydrogens were studied. This analysis shows that complex 2 has good potential for alkyl chloride-mediated coupling. In comparison, complex 3 showed slightly lower catalytic activity. After decanting the product contained in the ethereal layer, complex 2 could be recycled at least eight times without significant loss of catalytic activity. PMID:24145602

  8. Square-antiprismatic eight-coordinate complexes of divalent first-row transition metal cations: a density functional theory exploration of the electronic-structural landscape.

    PubMed

    Conradie, Jeanet; Patra, Ashis K; Harrop, Todd C; Ghosh, Abhik

    2015-02-16

    Density functional theory (in the form of the PW91, BP86, OLYP, and B3LYP exchange-correlation functionals) has been used to map out the low-energy states of a series of eight-coordinate square-antiprismatic (D2d) first-row transition metal complexes, involving Mn(II), Fe(II), Co(II), Ni(II), and Cu(II), along with a pair of tetradentate N4 ligands. Of the five complexes, the Mn(II) and Fe(II) complexes have been synthesized and characterized structurally and spectroscopically, whereas the other three are as yet unknown. Each N4 ligand consists of a pair of terminal imidazole units linked by an o-phenylenediimine unit. The imidazole units are the strongest ligands in these complexes and dictate the spatial disposition of the metal three-dimensional orbitals. Thus, the dx(2)-y(2) orbital, whose lobes point directly at the coordinating imidazole nitrogens, has the highest orbital energy among the five d orbitals, whereas the dxy orbital has the lowest orbital energy. In general, the following orbital ordering (in order of increasing orbital energy) was found to be operative: dxy < dxz = dyz ≤ dz(2) < dx(2)-y(2). The square-antiprism geometry does not lead to large energy gaps between the d orbitals, which leads to an S = 2 ground state for the Fe(II) complex. Nevertheless, the dxy orbital has significantly lower energy relative to that of the dxz and dyz orbitals. Accordingly, the ground state of the Fe(II) complex corresponds unambiguously to a dxy(2)dxz(1)dyz(1)dz(2)(1)dx(2)-y(2)(1) electronic configuration. Unsurprisingly, the Mn(II) complex has an S = 5/2 ground state and no low-energy d-d excited states within 1.0 eV of the ground state. The Co(II) complex, on the other hand, has both a low-lying S = 1/2 state and multiple low-energy S = 3/2 states. Very long metal-nitrogen bonds are predicted for the Ni(II) and Cu(II) complexes; these bonds may be too fragile to survive in solution or in the solid state, and the complexes may therefore not be isolable

  9. 1H, 13C, 15N NMR coordination shifts in Fe(II), Ru(II) and Os(II) cationic complexes with 2,2':6',2″-terpyridine.

    PubMed

    Pazderski, Leszek; Pawlak, Tomasz; Sitkowski, Jerzy; Kozerski, Lech; Szlyk, Edward

    2011-05-01

    (1)H, (13)C and (15)N NMR studies of iron(II), ruthenium(II) and osmium(II) bis-chelated cationic complexes with 2,2':6',2″-terpyridine ([M(terpy)(2) ](2+) ; M = Fe, Ru, Os) were performed. Significant shielding of nitrogen-adjacent H(6) and deshielding of H(3'), H(4') protons were observed, both effects being mostly expressed for Fe(II) compounds. The metal-bonded nitrogens were shielded, this effect being much larger for the outer N(1), N(1″) than the inner N(1') atoms, and enhanced in the Fe(II) → Ru(II) → Os(II) series. PMID:21491480

  10. (1)H NMR assignment corrections and (1)H, (13)C, (15)N NMR coordination shifts structural correlations in Fe(II), Ru(II) and Os(II) cationic complexes with 2,2'-bipyridine and 1,10-phenanthroline.

    PubMed

    Pazderski, Leszek; Pawlak, Tomasz; Sitkowski, Jerzy; Kozerski, Lech; Szłyk, Edward

    2010-06-01

    (1)H, (13)C and (15)N NMR studies of iron(II), ruthenium(II) and osmium(II) tris-chelated cationic complexes with 2,2'-bipyridine and 1,10-phenanthroline of the general formula [M(LL)(3)](2+) (M = Fe, Ru, Os; LL = bpy, phen) were performed. Inconsistent literature (1)H signal assignments were corrected. Significant shielding of nitrogen-adjacent protons [H(6) in bpy, H(2) in phen] and metal-bonded nitrogens was observed, being enhanced in the series Ru(II) --> Os(II) --> Fe(II) for (1)H, Fe(II) --> Ru(II) --> Os(II) for (15)N and bpy --> phen for both nuclei. The carbons are deshielded, the effect increasing in the order Ru(II) --> Os(II) --> Fe(II). PMID:20474023

  11. [Sensitive Determination of Chondroitin Sulfate by Fluorescence Recovery of an Anionic Aluminum Phthalocyanine-Cationic Surfactant Ion-Association Complex Used as a Fluorescent Probe Emitting at Red Region].

    PubMed

    Chen, Lin; Huang, Ping; Yang, Hui-qing; Deng, Ya-bin; Guo, Meng-lin; Li, Dong-hui

    2015-08-01

    Determination of chondroitin sulfate in the biomedical field has an important value. The conventional methods for the assay of chondroitin sulfate are still unsatisfactory in sensitivity, selectivity or simplicity. This work aimed at developing a novel method for sensitive and selective determination of chondroitin sulfate by fluorimetry. We found that some kinds of cationic surfactants have the ability to quench the fluorescence of tetrasulfonated aluminum phthalocyanine (AlS4Pc), a strongly fluorescent compound which emits at red region, with high efficiency. But, the fluorescence of the above-mentioned fluorescence quenching system recovered significantly when chondroitin sulfate (CS) exits. Tetradecyl dimethyl benzyl ammonium chloride(TDBAC) which was screened from all of the candidates of cationic surfactants was chosen as the quencher because it shows the most efficient quenching effect. It was found that the fluorescence of AlS4Pc was extremely quenched by TDBAC because of the formation of association complex between AlS4Pc and TDBAC. Fluorescence of the association complex recovered dramatically after the addition of chondroitin sulfate (CS) due to the ability of chondroitin sulfate to shift the association equilibrium of the association, leading to the release of AlS4Pc, thus resulting in an increase in the fluorescence of the reaction system. Based on this phenomenon, a novel method with simplicity, accuracy and sensitivity was developed for quantitative determination of CS. Factors including the reaction time, influencing factors and the effect of coexisting substances were investigated and discussed. Under optimum conditions the linear range of the calibration curve was 0.20~10.0 μg · mL(-1). The detection limit for CS was 0.070 μg · mL(-1). The method has been applied to the analysis of practical samples with satisfied results. This work expands the applications of AlS4Pc in biomedical area. PMID:26672294

  12. Experimental and theoretical studies on the DNA-binding of cationic yttrium(III) complex containing 2,2‧-bipyridine

    NASA Astrophysics Data System (ADS)

    Khorasani-Motlagh, Mozhgan; Noroozifar, Meissam; Akbari, Alireza; Mirkazehi-Rigi, Sohaila

    2015-03-01

    The interaction of DNA with [Y(bpy)(OH2)6]+3, where bpy is 2,2‧-bipyridine has been studied at physiological pH in Tris-HCl buffer. Fluorescence and absorption spectroscopy, agarose gel electrophoresis as well as EB quenching experiments are used to study DNA binding of the complex. The results reveal that DNA have the strong ability to bind with Y(III) complex. The binding constant, Kb and the Stern-Volmer quenching constant, KSV are determined. For characterization of the binding mode between the Y(III) complex and DNA various procedures such as: iodide quenching assay, salt effect and thermodynamical investigation are used. The results suggest that minor groove binding should be the interaction mode of complex to DNA. A gel electrophoresis assay demonstrates the ability of the complex to cleave the DNA via oxidative pathway. Electronic structure of [Y(bpy)(OH2)6]+3 was also carried out applying the density functional theory (DFT) method and applied to explain some obtained experimental observations.

  13. Generating Active "L-Pd(0)" via Neutral or Cationic π-Allylpalladium Complexes Featuring Biaryl/Bipyrazolylphosphines: Synthetic, Mechanistic, and Structure-Activity Studies in Challenging Cross-Coupling Reactions.

    PubMed

    DeAngelis, A J; Gildner, Peter G; Chow, Ruishan; Colacot, Thomas J

    2015-07-01

    Two new classes of highly active yet air- and moisture-stable π-R-allylpalladium complexes containing bulky biaryl- and bipyrazolylphosphines with extremely broad ligand scope have been developed. Neutral π-allylpalladium complexes incorporated a range of biaryl/bipyrazolylphosphine ligands, while extremely bulky ligands were accommodated by a cationic scaffold. These complexes are easily activated under mild conditions and are efficient for a wide array of challenging C-C and C-X (X = heteroatom) cross-coupling reactions. Their high activity is correlated to their facile activation to a 12-electron-based "L-Pd(0)" catalyst under commonly employed conditions for cross-coupling reactions, noninhibitory byproduct release upon activation, and suppression of the off-cycle pathway to form dinuclear (μ-allyl)(μ-Cl)Pd2(L)2 species, supported by structural (single crystal X-ray) and kinetic studies. A broad scope of C-C and C-X coupling reactions with low catalyst loadings and short reaction times highlight the versatility and practicality of these catalysts in organic synthesis. PMID:26035637

  14. Polymer light-emitting diodes based on cationic iridium(III) complexes with a 1,10-phenanthroline derivative containing a bipolar carbazole-oxadiazole unit as the auxiliary ligand

    NASA Astrophysics Data System (ADS)

    Tang, Huaijun; Wei, Liying; Meng, Guoyun; Li, Yanhu; Wang, Guanze; Yang, Furui; Wu, Hongbin; Yang, Wei; Cao, Yong

    2014-11-01

    A 1,10-phenanthroline derivative (co-phen) containing a bipolar carbazole-oxadiazole unit was synthesized and used as the auxiliary ligand in cationic iridium(III) complexes [(ppy)2Ir(co-phen)]PF6 (ppy: 2-phenylpyridine) and [(npy)2Ir(co-phen)]PF6 (npy: 2-(naphthalen-1-yl)pyridine). Two complexes have high thermal stability with the glass-transition temperatures (Tg) of 207 °C and 241 °C, and the same 5% weight-reduction temperatures (ΔT5%) of 402 °C. Both of them were used as phosphorescent dopants in solution-processed polymer light-emitting diodes (PLEDs): ITO/PEDOT: PSS/PVK: PBD: complex (mass ratios 100: 40: x, x = 1.0, 2.0, and 4.0)/CsF/Al. The maximum luminances of the PLEDs using [(ppy)2Ir(co-phen)]PF6 and [(npy)2Ir(co-phen)]PF6 were 12567 cd m-2 and 11032 cd m-2, the maximum luminance efficiencies were 17.3 cd A-1 and 20.4 cd A-1, the maximum power efficiencies were 9.8 lm W-1 and 10.3 lm W-1, and the maximum external quantum efficiencies were 9.3% and 11.4% respectively. The CIE color coordinates were around (0.37, 0.57) and (0.44, 0.54) respectively, corresponding to the yellow green region.

  15. Quantitative analysis of free and bonded forms of volatile sulfur compouds in wine. Basic methodologies and evidences showing the existence of reversible cation-complexed forms.

    PubMed

    Franco-Luesma, Ernesto; Ferreira, Vicente

    2014-09-12

    This paper examines first some basic aspects critical to the analysis of Volatile Sulfur Compounds (VSCs), such as the analytical characteristics of the GC-pFPD system and the stability of the different standard solutions required for a proper calibration. Following, a direct static headspace analytical method for the determination of exclusively free forms of VSCs has been developed. Method repeatability is better than 4%, detection limits for main analytes are below 0.5μgL(-1), and the method dynamic linear range (r(2)>0.99) is expanded by controlling the split ratio in the chromatographic inlet to cover the natural range of occurrence of these compounds in wines. The method gives reliable estimates of headspace concentrations but, as expected, suffers from strong matrix effects with recoveries ranging from 0 to 100% or from 60 to 100 in the cases of H2S and the other mercaptans, respectively. This demonstrates the existence of strong interactions of these compounds with different matrix components. The complexing ability of Cu(2+) and to a lower extent Fe(2+) and Zn(2+) has been experimentally checked. A previously developed method in which the wine is strongly diluted with brine and the volatiles are preconcentrated by HS-SPME, was found to give a reliable estimation of the total amount (free+complexed) of mercaptans, demonstrating that metal-mercaptan complexes are reversible. The comparative analysis of different wines by the two procedures reveals that in normal wines H2S and methanethiol can be complexed at levels above 99%, with averages around 97% for H2S and 75% for methanethiol, while thioethers such as dimethyl sulfide (DMS) are not complexed. Overall, the proposed strategy may be generalized to understand problems caused by VSCs in different matrices. PMID:25064535

  16. Halogenated silanes, radicals, and cations

    NASA Astrophysics Data System (ADS)

    Wang, Liming; He, Yi-Liang

    2008-09-01

    Quantum chemistry study has been carried out on the structure and energetics of halogenated silanes, radicals, and cations (SiHxXy0,+1, X = F, Cl, Br; x + y = 1-4). The geometries are optimized at B3LYP/6-31+G(2df,p) level. The adiabatic ionization energiess (IEas), relative energetics of cations, proton affinities (PAs) of silanes, and the enthalpies of formation are predicted using G3(CC) model chemistry. Non-classical ion complex structures are found for hydrogenated cations and transition states connecting classical and non-classical structures are also located. The most stable cations for silylene and silyl radicals have their classical divalent and trivalent structures, and those for silanes have non-classical structures except for SiH3Br+ and SiH2Br2+. The non-classical structures for halosilane cations imply difficulty in experimentally measurement of the adiabatic ionization energies using photoionization or photoelectron studies. For SiH3X, SiH2X2, and SiHX3, the G3(CC) adiabatic IEas to classical ionic structures closest to their neutrals agree better with the photoelectron spectroscopic measurements. The transition states between classical and non-classical structures also hamper the photoionization determination of the appearance energies for silylene cations from silanes. The G3(CC) results for SiHx0,+1 agree excellently with the photoionization mass spectrometric study, and the results for fluorinated and chlorinated species also agree with the previous theoretical predictions at correlation levels from BAC-MP4 to CCSD(T)/CBS. The predicted enthalpy differences between SiH2Cl+, SiHCl2+, and SiCl3+ are also in accordance with previous kinetics study. The G3(CC) results show large discrepancies to the collision-induced charge transfer and/or dissociation reactions involving SiFx+ and SiClx+ ions, for which the G3(CC) enthalpies of formation are also significantly differed from the previous theoretical predictions, especially on SiFx+ (x = 2-4). The G3

  17. Cationic half-sandwich Ru(II) complexes containing (N,N)-bound Schiff-base ligands: Synthesis, crystal structure analysis and spectroscopic studies

    NASA Astrophysics Data System (ADS)

    Tao, Li; Miao, Qian; Tehrani, Alireza Azhdari; Hajiashrafi, Taraneh; Hu, Mao-Lin; Morsali, Ali

    2016-08-01

    Three Ru(II) half-sandwich complexes containing (N,N)-bound Schiff-base ligands, [(η6-C6H6) RuCl(L1)]PF6 (1) L1 = (E)-1-(6-methylpyridin-2-yl)-N-(p-tolyl)methanimine, [(η6-p-cymene)RuCl(L1)]PF6 (2) and [(η6-p-cymene)RuCl(L2)]PF6(3) L2 = (E)-1-(6-bromopyridin-2-yl)-N-(p-tolyl)methanimine, were synthesized, characterized and their supramolecular structures were analyzed. The crystal packing of these compounds was studied using geometrical analysis and Hirshfeld surface analysis. The fluorescence behavior of these compounds was also studied. TD-DFT calculations were carried out to better understand the fluorescence properties of complexes 1-3. These compounds could be promising for the design of organometallic dye systems.

  18. Baeyer-Villiger oxidation of cyclic ketones with hydrogen peroxide catalyzed by cationic complexes of platinum(II): Selectivity properties and mechanistic studies

    SciTech Connect

    Del Todesco Frisone, M.; Pinna, F.; Strukul, G. )

    1993-01-01

    The catalytic oxidation of simple cyclic ketones with hydrogen peroxide to give the corresponding lactones is reported. The reaction is catalyzed by complexes of Pt(II) of the type [(P-P)Pt(CF[sub 3])(solv)][sup +] (P-P = diphosphine) that may be deactivated by the hydroxy acids formed by hydrolysis of the lactones. The selectivity of the catalyst is studied in the oxidation of substrates like camphor, 2-cyclohexene-1-one, menthone, carvone, and indanones. Cyclobutanone is used to determine the mechanism of the reaction from initial rates studies. The reaction scheme proposed, which accounts for the observed effects of the various reactants, involves the coordination of the ketone on the vacant coordination site of the complex followed by nucleophilic attack of free hydrogen peroxide on the carbonyl carbon. The involvement of a quasi-peroxymetallacyclic intermediate is suggested which rearranges to give the lactone and the starting complex. A comparison with the mechanistic behavior of organic peroxy acids is given. 24 refs., 10 figs., 3 tabs.

  19. Solvent effect on cation-π interactions with Al3+.

    PubMed

    Larrucea, Julen

    2012-09-01

    Cation-π interactions are known to be one of the strongest noncovalent forces in the gas phase, but they rarely occur in a fully solvated environment. The present work used two different ab initio molecular dynamics-based approaches to describe the correlation between the strength of the cation-π interactions and the number of water molecules surrounding the cation. Five different complexes between an aluminum cation and different molecules containing aromatic rings were studied, and the degree of hydration of each complex was varied. Results indicated that cation-π interactions vanish when the aluminum cation is surrounded by more than three water molecules. The results also highlighted the influence of -OH ligands on the interaction strength. PMID:22581060

  20. Detachable strong cation exchange monolith, integrated with capillary zone electrophoresis and coupled with pH gradient elution, produces improved sensitivity and numbers of peptide identifications during bottom-up analysis of complex proteomes.

    PubMed

    Zhang, Zhenbin; Yan, Xiaojing; Sun, Liangliang; Zhu, Guijie; Dovichi, Norman J

    2015-04-21

    A detachable sulfonate-silica hybrid strong cation-exchange monolith was synthesized in a fused silica capillary, and used for solid phase extraction with online pH gradient elution during capillary zone electrophoresis-tandem mass spectrometry (CZE-MS/MS) proteomic analysis. Tryptic digests were prepared in 50 mM formic acid and loaded onto the strong cation-exchange monolith. Fractions were eluted using a series of buffers with lower concentration but higher pH values than the 50 mM formic acid background electrolyte. This combination of elution and background electrolytes results in both sample stacking and formation of a dynamic pH junction and allows use of relatively large elution buffer volumes while maintaining reasonable peak efficiency and resolution. A series of five pH bumps were applied to elute E. coli tryptic peptides from the monolith, followed by analysis using CZE coupled to an LTQ-Orbitrap Velos mass spectrometer; 799 protein groups and 3381 peptides were identified from 50 ng of the digest in a 2.5 h analysis, which approaches the identification rate for this organism that was obtained with an Orbitrap Fusion. We attribute the improved numbers of peptide and protein identifications to the efficient fractionation by the online pH gradient elution, which decreased the complexity of the sample in each elution step and improved the signal intensity of low abundance peptides. We also performed a comparative analysis using a nanoACQUITY UltraPerformance LCH system. Similar numbers of protein and peptide identifications were produced by the two methods. Protein identifications showed significant overlap between the two methods, whereas peptide identifications were complementary. PMID:25822566

  1. Cation locations and dislocations in zeolites

    NASA Astrophysics Data System (ADS)

    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

  2. Cationic spin probe reporting on thermal denaturation and complexation-decomplexation of BSA with SDS. Potential applications in protein purification processes.

    PubMed

    Matei, Iulia; Ariciu, Ana Maria; Neacsu, Maria Victoria; Collauto, Alberto; Salifoglou, Athanasios; Ionita, Gabriela

    2014-09-25

    In this work, we present evidence on the suitability of spin probes to report on the thermal treatment of bovine serum albumin (BSA), in the temperature range 293-343 K, and indirectly monitor the release of sodium dodecyl sulfate (SDS) from its complex with BSA using a covalent gel with β-cyclodextrin (β-CD) in the network. The spin probes used, 5- and 7-doxyl-stearic acids (5-DSA, 7-DSA) or 4-(N,N'-dimethyl-N-hexadecyl)ammonium-2,2',6,6'-tetramethylpiperidine-1-oxyl iodide (CAT16), present similar, fatty acid-like structural features. Their continuous wave electron paramagnetic resonance (CW-EPR) spectra, however, reflect different dynamics when complexed with BSA: a restricted motion for 5-DSA, almost nonsensitive to the heating/cooling cycle, and a faster temperature-dependent dynamic motion for CAT16. Molecular docking allows us to rationalize these results by revealing the different binding modes of 5-DSA and CAT16. The EPR data on the temperature effect on BSA are supported by circular dichroism results projecting recovery, upon cooling, of the initial binding ability of BSA for samples heated to 323 K. The interactions occurring in BSA/SDS/β-CD systems are investigated by CW-EPR and FT-ESEEM spectroscopies. It is found that the covalent gel containing β-CD can efficiently remove SDS from the BSA/SDS complex. The gel is not permeable to BSA but it can encapsulate SDS, thus yielding the free protein in solution and allowing recovery of the native protein conformation. Collectively, the accrued knowledge supports potential applications in protein purification biotechnological processes. PMID:25185116

  3. Electric field effects on nuclear magnetic shielding of the 1:1 and 2:1 (homo and heterochiral) complexes of XOOX' (X, X' = H, CH3) with lithium cation and their chiral discrimination

    NASA Astrophysics Data System (ADS)

    Alkorta, Ibon; Elguero, José; Provasi, Patricio F.; Pagola, Gabriel I.; Ferraro, Marta B.

    2011-09-01

    The set of 1:1 and 2:1 complexes of XOOX' (X, X' = H, CH3) with lithium cation has been studied to determine if they are suitable candidates for chiral discrimination in an isotropic medium via nuclear magnetic resonance spectroscopy. Conventional nuclear magnetic resonance is unable to distinguish between enantiomers in the absence of a chiral solvent. The criterion for experimental detection is valuated by the isotropic part of nuclear shielding polarisability tensors, related to a pseudoscalar of opposite sign for two enantiomers. The study includes calculations at coupled Hartree-Fock and density functional theory schemes for 17O nucleus in each compound. Additional calculations for 1H are also included for some compounds. A huge static homogeneous electric field, perpendicular to the magnetic field of the spectromer, as big as ≈1.7 × 108 V m-1 should be applied to observe a shift of ≈1 ppm for 17O magnetic shielding in the proposed set of complexes.

  4. Electric field effects on nuclear magnetic shielding of the 1:1 and 2:1 (homo and heterochiral) complexes of XOOX' (X, X' = H, CH3) with lithium cation and their chiral discrimination.

    PubMed

    Alkorta, Ibon; Elguero, José; Provasi, Patricio F; Pagola, Gabriel I; Ferraro, Marta B

    2011-09-14

    The set of 1:1 and 2:1 complexes of XOOX' (X, X' = H, CH(3)) with lithium cation has been studied to determine if they are suitable candidates for chiral discrimination in an isotropic medium via nuclear magnetic resonance spectroscopy. Conventional nuclear magnetic resonance is unable to distinguish between enantiomers in the absence of a chiral solvent. The criterion for experimental detection is valuated by the isotropic part of nuclear shielding polarisability tensors, related to a pseudoscalar of opposite sign for two enantiomers. The study includes calculations at coupled Hartree-Fock and density functional theory schemes for (17)O nucleus in each compound. Additional calculations for (1)H are also included for some compounds. A huge static homogeneous electric field, perpendicular to the magnetic field of the spectromer, as big as ≈1.7 × 10(8) V m(-1) should be applied to observe a shift of ≈1 ppm for (17)O magnetic shielding in the proposed set of complexes. PMID:21932885

  5. Predictive complexation models of the impact of natural organic matter and cations on scaling in cooling water pipes: A case study of power generation plants in South Africa

    NASA Astrophysics Data System (ADS)

    Bosire, G. O.; Ngila, J. C.; Mbugua, J. M.

    This work discusses simulative models of Ca and Mg complexation with natural organic matter (NOM), in order to control the incidence of scaling in pipes carrying cooling water at the Eskom power generating stations in South Africa. In particular, the paper reports how parameters such as pH and trace element levels influence the distribution of scaling species and their interactions, over and above mineral phase saturation indices. In order to generate modelling inputs, two experimental scenarios were created in the model solutions: Firstly, the trace metals Cu, Pb and Zn were used as markers for Ca and Mg complexation to humic acid and secondly the effect of natural organic matter in cooling water was determined by spiking model solutions. Labile metal ions and total elements in model solutions and water samples were analysed by square wave anodic stripping voltammetry and inductively coupled plasma optical emission spectrometry (ICP-OES), respectively. ICP-OES results revealed high levels of K, Na, S, Mg and Ca and low levels of trace elements (Cd, Se, Pb, Cu, Mn, Mo, Ni, Al and Zn) in the cooling water samples. Using the Tipping and Hurley's database WHAM in PHREEQC format (T_H.DAT), the total elemental concentrations were run as inputs on a PHREEQC code, at pH 6.8 and defined charge as alkalinity (as HCO3-) For model solutions, PHREEQC inputs were based on (i) free metal differences attributed to competitive effect of Ca and the effect of Ca + Mg, respectively; (ii) total Ca and Mg used in the model solutions and (iii) alkalinity described as hydrogen carbonate. Anodic stripping peak heights were used to calculate the concentration of the free/uncomplexed/labile metal ions (used as tracers) in the model solutions. The objective of modelling was to describe scaling in terms of saturation indices of mineral phases. Accordingly, the minerals most likely to generate scale were further simulated (over a range of pH (3-10) to yield results that mimicked changing p

  6. Innate cation sensitivity in a semiconducting polymer.

    PubMed

    Althagafi, Talal M; Algarni, Saud A; Grell, Martin

    2016-09-01

    Water-gated organic thin film transistors (OTFTs) using the hole transporting semiconducting polymer, poly(2,5-bis(3-hexadecylthiophen-2-yl)thieno[3,2-b]thiophene) (PBTTT), show an innate response of their threshold voltage to the addition of divalent metal cations to the gating water, without deliberately introducing an ion-sensitive component. A similar threshold response is shown for several divalent cations, but is absent for monovalent cations. Response is absent for transistors using the inorganic semiconductor ZnO, or the similar organic semiconductor poly(3-hexylthiophene) (rrP3HT), instead of PBTTT. We assign innate cation sensitivity to residues of the organometallic Pd(0) complex used as catalyst in PBTTT synthesis which bears strong resemblance to typical metal chelating agents. Organometallic Pd(0) residues are absent from ZnO, and also from rrP3HT which is polymerised with a different type of catalyst. However, when Pd(0) complex is deliberately added to rrP3HT casting solutions, resulting OTFTs also display threshold response to a divalent cation. PMID:27343580

  7. Reducible cationic lipids for gene transfer.

    PubMed Central

    Wetzer, B; Byk, G; Frederic, M; Airiau, M; Blanche, F; Pitard, B; Scherman, D

    2001-01-01

    One of the main challenges of gene therapy remains the increase of gene delivery into eukaryotic cells. We tested whether intracellular DNA release, an essential step for gene transfer, could be facilitated by using reducible cationic DNA-delivery vectors. For this purpose, plasmid DNA was complexed with cationic lipids bearing a disulphide bond. This reduction-sensitive linker is expected to be reduced and cleaved in the reducing milieu of the cytoplasm, thus potentially improving DNA release and consequently transfection. The DNA--disulphide-lipid complexation was monitored by ethidium bromide exclusion, and the size of complexes was determined by dynamic light scattering. It was found that the reduction kinetics of disulphide groups in DNA--lipid complexes depended on the position of the disulphide linker within the lipid molecule. Furthermore, the internal structure of DNA--lipid particles was examined by small-angle X-ray scattering before and after lipid reduction. DNA release from lipid complexes was observed after the reduction of disulphide bonds of several lipids. Cell-transfection experiments suggested that complexes formed with selected reducible lipids resulted in up to 1000-fold higher reporter-gene activity, when compared with their analogues without disulphide bonds. In conclusion, reduction-sensitive groups introduced into cationic lipid backbones potentially allow enhanced DNA release from DNA--lipid complexes after intracellular reduction and represent a tool for improved vectorization. PMID:11389682

  8. Novel biscapped and monocapped tris(dioxime) Mn(II) complexes: x-ray crystal structure of the first cationic tris(dioxime) Mn(II) complex [Mn(CDOH)3BPh]OH (CDOH2= 1,2-cyclohexanedione dioxime).

    PubMed

    Hsieh, Wen-Yuan; Liu, Shuang

    2006-06-26

    This report describes the synthesis and characterization of a series of novel biscapped and monocapped tris(dioxime) Mn(II) complexes [Mn(dioxime)3(BR)2] and [Mn(dioxime)3BR]+ (dioxime = cyclohexanedione dioxime (CDOH2) and 1,2-dimethylglyoxyl dioxime (DMGH(2)); R = Me, n-Bu, and Ph). All tris(dioxime) Mn(II) complexes have been characterized by elemental analysis, IR, UV/vis, cyclic voltammetry, ESI-MS, and, in the cases of [Mn(CDOH)3BPh]OH.CHCl3 and [Mn(CDO)(CDOH)2(BBu(OC2H5))2], X-ray crystallography. It was found that biscapped Mn(II) complexes [Mn(dioxime)3(BR)2] are not stable in the presence of water and readily hydrolyze to form monocapped cationic complexes [M(dioxime)3BR]+. This instability is most likely caused by mismatch between the size of Mn(II) and the coordination cavity of the biscapped tris(dioxime) ligands. In contrast, monocapped cationic complexes [M(dioxime)3BR]+ are very stable in aqueous solution even in the presence of PDTA (1,2-diaminopropane-N,N,N',N'-tetraacetic acid) because of the kinetic inertness imposed by the monocapped tris(dioxime) chelators that are able to completely "wrap" Mn(II) into their N6 coordination cavity. [Mn(CDO)3BPh]OH has a distorted trigonal prismatic coordination geometry, with the Mn(II) being bonded by six imine-N donors. The hydroxyl groups from three dioxime chelating arms form very strong intramolecular hydrogen bonds with the hydroxide counterion so that the structure of [Mn(CDOH)3BPh]OH can be considered as being the clathrochelate with the hydroxide counterion as a "cap". PMID:16780325

  9. Cation-Poor Complex Metallic Alloys in Ba(Eu)-Au-Al(Ga) Systems: Identifying the Keys that Control Structural Arrangements and Atom Distributions at the Atomic Level.

    PubMed

    Smetana, Volodymyr; Steinberg, Simon; Mudryk, Yaroslav; Pecharsky, Vitalij; Miller, Gordon J; Mudring, Anja-Verena

    2015-11-01

    Four complex intermetallic compounds BaAu(6±x)Ga(6±y) (x = 1, y = 0.9) (I), BaAu(6±x)Al(6±y) (x = 0.9, y = 0.6) (II), EuAu6.2Ga5.8 (III), and EuAu6.1Al5.9 (IV) have been synthesized, and their structures and homogeneity ranges have been determined by single crystal and powder X-ray diffraction. Whereas I and II originate from the NaZn13-type structure (cF104-112, Fm3̅c), III (tP52, P4/nbm) is derived from the tetragonal Ce2Ni17Si9-type, and IV (oP104, Pbcm) crystallizes in a new orthorhombic structure type. Both I and II feature formally anionic networks with completely mixed site occupation by Au and triel (Tr = Al, Ga) atoms, while a successive decrease of local symmetry from the parental structures of I and II to III and, ultimately, to IV correlates with increasing separation of Au and Tr on individual crystallographic sites. Density functional theory-based calculations were employed to determine the crystallographic site preferences of Au and the respective triel element to elucidate reasons for the atom distribution ("coloring scheme"). Chemical bonding analyses for two different "EuAu6Tr6" models reveal maximization of the number of heteroatomic Au-Tr bonds as the driving force for atom organization. The Fermi levels fall in broad pseudogaps for both models allowing some electronic flexibility. Spin-polarized band structure calculations on the "EuAu6Tr6" models hint to singlet ground states for europium and long-range magnetic coupling for both EuAu6.2Ga5.8 (III) and EuAu6.1Al5.9 (IV). This is substantiated by experimental evidence because both compounds show nearly identical magnetic behavior with ferromagnetic transitions at TC = 6 K and net magnetic moments of 7.35 μB/f.u. at 2 K. The effective moments of 8.3 μB/f.u., determined from Curie-Weiss fits, point to divalent oxidation states for europium in both III and IV. PMID:26479308

  10. Neutral and Cationic Molybdenum Imido Alkylidene N-Heterocyclic Carbene Complexes: Reactivity in Selected Olefin Metathesis Reactions and Immobilization on Silica.

    PubMed

    Sen, Suman; Schowner, Roman; Imbrich, Dominik A; Frey, Wolfgang; Hunger, Michael; Buchmeiser, Michael R

    2015-09-21

    The synthesis and single-crystal X-ray structures of the novel molybdenum imido alkylidene N-heterocyclic carbene complexes [Mo(N-2,6-Me2C6H3)(IMesH2)(CHCMe2Ph)(OTf)2] (3), [Mo(N-2,6-Me2C6H3)(IMes)(CHCMe2Ph)(OTf)2] (4), [Mo(N-2,6-Me2C6H3)(IMesH2)(CHCMe2Ph)(OTf){OCH(CF3)2}] (5), [Mo(N-2,6-Me2C6H3)(CH3CN)(IMesH2)(CHCMe2Ph)(OTf)](+)BArF(-) (6), [Mo(N-2,6-Cl2C6H3)(IMesH2)(CHCMe3)(OTf)2] (7) and [Mo(N-2,6-Cl2C6H3)(IMes)(CHCMe3)(OTf)2] (8) are reported (IMesH2=1,3-dimesitylimidazolidin-2-ylidene, IMes=1,3-dimesitylimidazolin-2-ylidene, BArF(-)=tetrakis-[3,5-bis(trifluoromethyl)phenyl] borate, OTf=CF3SO3(-)). Also, silica-immobilized versions I1 and I2 were prepared. Catalysts 3-8, I1 and I2 were used in homo-, cross-, and ring-closing metathesis (RCM) reactions and in the cyclopolymerization of α,ω-diynes. In the RCM of α,ω-dienes, in the homometathesis of 1-alkenes, and in the ethenolysis of cyclooctene, turnover numbers (TONs) up to 100,000, 210,000 and 30,000, respectively, were achieved. With I1 and I2, virtually Mo-free products were obtained (<3 ppm Mo). With 1,6-hepta- and 1,7-octadiynes, catalysts 3, 4, and 5 allowed for the regioselective cyclopolymerization of 4,4-bis(ethoxycarbonyl)-1,6-heptadiyne, 4,4-bis(hydroxymethyl)-1,6-heptadiyne, 4,4-bis[(3,5-diethoxybenzoyloxy)methyl]-1,6-heptadiyne, 4,4,5,5-tetrakis(ethoxycarbonyl)-1,7-octadiyne, and 1,6-heptadiyne-4-carboxylic acid, underlining the high functional-group tolerance of these novel Group 6 metal alkylidenes. PMID:26249141

  11. Nitrosyl complexes of rhenium. 2. Neutral and cationic monohydride complexes of rhenium(I) resulting from the reaction of ReH/sub 2/(NO)(PPh/sub 3/)/sub 3/ with perchloric acid

    SciTech Connect

    Grundy, K.R.; Robertson, K.N.

    1985-11-06

    The rhenium dihydride complex ReH/sub 2/(NO)(PPh/sub 3/)/sub 3/ reacts with HClO/sub 4/ in the presence of CO with the cleavage of only one hydride ligand. Control of the degree of acidity and the solvent system leads to isolation of compounds such as ReH(OR)(CO)(NO)(PPh/sub 3/)/sub 2/ (R = Me, Et) and (ReH(CO)(NO)(PPh/sub 3/)/sub 3/)ClO/sub 4/. The alkoxide complexes are protonated by HClO/sub 4/ to yield alcohol complexes ReH(ROH.OClO/sub 3/)(CO)(NO)(PPh/sub 3/)/sub 2/. Heating ReH(MeOH.OClO/sub 3/)(CO)(NO)(PPh/sub 3/)/sub 2/ in methanol results in the formal 1,2-elimination of dihydrogen with formation of Re(OMe)(OClO/sub 3/)(CO)(NO)(PPh/sub 3/)/sub 2/. A similar elimination reaction occurs when the alcohol complexes are reacted with halide ions to give ReX(OR)(CO)(NO(PPh/sub 3/)/sub 2/ (X = Cl, Br, I). Reacting the alcohol complexes with base or NaBH/sub 4/ however, regenerates ReH(OR)(CO)(NO)(PPh/sub 3/)/sub 2/. The perchlorate complex, Re(OMe)(OClO/sub 3/)(CO)(NO)(PPh/sub 3/)/sub 2/ reacts with NaBH/sub 4/ to give ReH/sub 2/(CO)(NO)(PPh/sub 3/)/sub 2/ via a borohydride complex. The chloro-alkoxy complexes ReCl(OR)(CO)(NO)(PPh/sub 3/)/sub 2/ also react with HClO/sub 4/ to give alcohol complexes. All structural assignments have been made on the basis of elemental analysis, infrared spectroscopy, /sup 1/H NMR spectroscopy, and deuteration studies. 14 references, 2 figures, 2 tables.

  12. Cationic Bolaamphiphiles for Gene Delivery

    NASA Astrophysics Data System (ADS)

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

    2014-05-01

    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. A Molecular Chameleon: Reversible pH- and Cation-Induced Control of the Optical Properties of Phthalocyanine-Based Complexes in the Visible and Near-Infrared Spectral Ranges.

    PubMed

    Safonova, Evgeniya A; Martynov, Alexander G; Nefedov, Sergey E; Kirakosyan, Gayane A; Gorbunova, Yulia G; Tsivadze, Aslan Yu

    2016-03-01

    A series of novel nonperipherally substituted tetra-15-crown-5-dibutoxyoxanthrenocyanines (H2, Mg, Zn), acting as chameleons with the unique properties of switchable absorption and emission in the near-infrared (NIR) spectral range have been synthesized and characterized by X-ray diffraction. The attachment of 15-crown-5-α-dibutoxyoxanthreno moieties to phthalocyanine is responsible for the high solubility of the resulting molecules and the red shift of the Q band to the NIR region and offers a unique possibility for postsynthetic modification of the optical properties of the molecules. Both aggregation of phthalocyanine and its participation in an acid-base equilibrium strongly alter their optical properties. For example, the absorption of complexes can be reversibly tuned from 686 up to 1028 nm because of the cation-induced formation of supramolecular dimers or subsequent protonation of meso-N atoms orf macrocycle, in contrast to peripherally substituted tetra-15-crown-5-phthalocyanines without oxanthrene moieties. The reversibility of these processes can be controlled by the addition of [2.2.2]cryptand or amines. All investigated compounds exhibit fluorescence with moderate quantum yield, which can also be switched between the ON and OFF states by the action of similar agents. PMID:26910047

  14. Photophysical study of the Ca 2+-chelator QUIN 2 ligand: effect of divalent and trivalent cations

    NASA Astrophysics Data System (ADS)

    Guardigli, M.; Sabbatini, N.

    1991-05-01

    The photophysical properties of complexes of the Ca 2+-chelator QUIN 2 ligand with divalent and trivalent cations have been studied. The absorption of the ligand is almost independent of the nature of the complexing cations, while the fluorescence emission strongly depends on the electric charge of the cations. Metal emission upon excitation in the ligand has been observed for the Eu 3+ complex, but not for the Tb 3+ complex.

  15. Efficacy of HGF carried by ultrasound microbubble-cationic nano-liposomes complex for treating hepatic fibrosis in a bile duct ligation rat model, and its relationship with the diffusion-weighted MRI parameters.

    PubMed

    Zhang, Shou-hong; Wen, Kun-ming; Wu, Wei; Li, Wen-yan; Zhao, Jian-nong

    2013-12-01

    Hepatic fibrosis is a major consequence of liver aggression. Finding novel ways for counteracting this damaging process, and for evaluating fibrosis with a non-invasive imaging approach, represent important therapeutic and diagnostic challenges. Hepatocyte growth factor (HGF) is an anti-fibrosis cell growth factor that induces apoptosis in activated hepatic stellate cells, reduces excessive collagen deposition, and stimulates hepatocyte regeneration. Thus, using HGF in gene therapy against liver fibrosis is an attractive approach. The aims of the present study were: (i) to explore the efficacy of treating liver fibrosis using HGF expression vector carried by a novel ultrasound microbubble delivery system; (ii) to explore the diagnostic interest of diffusion-weighted MRI (DWI-MRI) in evaluating liver fibrosis. We established a rat model of hepatic fibrosis. The rats were administered HGF linked to novel ultrasound micro-bubbles. Progression of hepatic fibrosis was evaluated by histopathology, hydroxyproline content, and DWI-MRI to determine the apparent diffusion coefficient (ADC). Our targeted gene therapy produced a significant anti-fibrosis effect, as shown by liver histology and significant reduction of hydroxyproline content. Moreover, using DWI-MRI, the b value (diffusion gradient factor) was equal to 300s/mm(2), and the ADC values significantly decreased as the severity of hepatic fibrosis increased. Using this methodology, F0-F2 could be distinguished from F3 and F4 (P<0.01). This is the first in vivo report of using an ultrasound microbubble-cationic nano-liposome complex for gene delivery. The data indicate that, this approach is efficient to counteract the fibrosis process. DWI-MRI appears a promising imaging technique for evaluating liver fibrosis. PMID:24012221

  16. Modulation of RGD sequence motifs regulates disintegrin recognition of alphaIIb beta3 and alpha5 beta1 integrin complexes. Replacement of elegantin alanine-50 with proline, N-terminal to the RGD sequence, diminishes recognition of the alpha5 beta1 complex with restoration induced by Mn2+ cation.

    PubMed Central

    Rahman, S; Aitken, A; Flynn, G; Formstone, C; Savidge, G F

    1998-01-01

    Several recent studies have demonstrated that the amino acid residues flanking the RGD sequence of high-affinity ligands modulate their specificity of interaction with integrin complexes. The present study has addressed the role of the residues flanking the RGD sequence in regulating the recognition by disintegrin of the alphaIIb beta3 and alpha5beta1 complexes by construction of a panel of recombinant molecules of Elegantin (the platelet aggregation inhibitor from the venom of Trimerasurus elegans) expressing specific RGD sequence motifs. Wild-type Elegantin (ARGDNP) and several variants including Eleg. AM (ARGDMP), Eleg. PM (PRGDMP) and Eleg. PN (PRGDNP) were expressed as glutathione S-transferase (GST) fusion proteins in Escherichia coli. The inhibitory efficacies of the panel of Elegantin variants were analysed in platelet adhesion assays with substrates immobilized with fibrinogen and fibronectin. Elegantin molecules containing an Ala residue N-terminal to the RGD sequence (wild-type Elegantin and Eleg. AM) showed strong inhibitory activity towards alphaIIbbeta3-dependent platelet adhesion on fibronectin, whereas a Pro residue in this position (Eleg. PM and Kistrin, the inhibitor from the venom of Calloselasma rhodostoma) engendered lower activity. The decreased activity could not be attributed to a decrease in the affinity of the disintegrin for the alphaIIb beta3 complex because both Eleg. AM and Eleg. PM had similar Kd (app) values. In contrast, Elegantin molecules into which a Met residue was introduced in place of the Asn residue C-terminal to the RGD sequence showed 10-13-fold elevated inhibitory activity towards platelet adhesion on fibrinogen and this was maintained with either a Pro or Ala residue N-terminal to the RGD sequence. In experiments with the alpha5 beta1 complex on K562 cells, the inhibitory efficacies of the panel of Elegantin molecules were analysed under two different cation conditions. First, in the presence of Ca2+/Mg2+, K562 cell

  17. Tuning the photophysical properties of cationic iridium(III) complexes containing cyclometallated 1-(2,4-difluorophenyl)-1H-pyrazole through functionalized 2,2'-bipyridine ligands: blue but not blue enough.

    PubMed

    Baranoff, Etienne; Bolink, Henk J; Constable, Edwin C; Delgado, Manuel; Häussinger, Daniel; Housecroft, Catherine E; Nazeeruddin, Mohammad K; Neuburger, Markus; Ortí, Enrique; Schneider, Gabriel E; Tordera, Daniel; Walliser, Roché M; Zampese, Jennifer A

    2013-01-28

    Four new heteroleptic iridium(III) complexes in the family [Ir(dfppz)(2)(N^N)](+), where Hdfppz = 1-(2,4-difluorophenyl)-1H-pyrazole and N^N = 6-phenyl-2,2'-bipyridine (1), 4,4'-(di-tert-butyl)-6-phenyl-2,2'-bipyridine (2), 4,4'-(di-tert-butyl)-6,6'-diphenyl-2,2'-bipyridine (3) and 4,4'-bis(dimethylamino)-2,2'-bipyridine (4), have been synthesized as the hexafluoridophosphate salts and fully characterized. Single crystal structures of ligand 3 and the precursor [Ir(2)(dfppz)(4)(μ-Cl)(2)] have been determined, along with the structures of the complexes 4{[Ir(dfppz)(2)(1)][PF(6)]}·3CH(2)Cl(2), [Ir(dfppz)(2)(3)][PF(6)]·CH(2)Cl(2) and [Ir(dfppz)(2)(4)][PF(6)]·CH(2)Cl(2). The role of inter- and intramolecular face-to-face π-stacking in the solid state is discussed. In the [Ir(dfppz)(2)(N^N)](+) (N^N = 1-3) cations, the phenyl substituent in ligands 1, 2 or 3 undergoes hindered rotation on the NMR timescale at 298 K in solution and the systems have been studied by variable temperature NMR spectroscopy. Acetonitrile solutions of [Ir(dfppz)(2)(N^N)][PF(6)] (N^N = 1-3) exhibit similar absorption spectra arising from ligand-based transitions; absorption intensity is enhanced on going to [Ir(dfppz)(2)(4)][PF(6)] and the spectrum extends further into the visible region. Acetonitrile solutions of the complexes are blue emitters with λ(em) = 517, 505, 501 and 493 nm for N^N = 1, 2, 3 and 4, respectively (λ(exc) = 280-310 nm). The redox behaviours of [Ir(dfppz)(2)(N^N)][PF(6)] (N^N = 1-3) are similar, and the introduction of the electron-donating NMe(2) substituents onto the N^N ligand shifts the metal-centred oxidation to less positive potentials. Theoretical calculations predict a mixed metal-to-ligand/ligand-to-ligand charge transfer (MLCT/LLCT) character for the emitting triplet state in agreement with the broad and unstructured character of the emission bands. The NMe(2) substituents enlarge the HOMO-LUMO gap and blue-shifts the emission of [Ir(dfppz)(2)(4)](+) that

  18. MLKL forms cation channels

    PubMed Central

    Xia, Bingqing; Fang, Sui; Chen, Xueqin; Hu, Hong; Chen, Peiyuan; Wang, Huayi; Gao, Zhaobing

    2016-01-01

    The mixed lineage kinase domain-like (MLKL) protein is a key factor in tumor necrosis factor-induced necroptosis. Recent studies on necroptosis execution revealed a commitment role of MLKL in membrane disruption. However, our knowledge of how MLKL functions on membrane remains very limited. Here we demonstrate that MLKL forms cation channels that are permeable preferentially to Mg2+ rather than Ca2+ in the presence of Na+ and K+. Moreover, the N-terminal domain containing six helices (H1-H6) is sufficient to form channels. Using the substituted cysteine accessibility method, we further determine that helix H1, H2, H3, H5 and H6 are transmembrane segments, while H4 is located in the cytoplasm. Finally, MLKL-induced membrane depolarization and cell death exhibit a positive correlation to its channel activity. The Mg2+-preferred permeability and five transmembrane segment topology distinguish MLKL from previously identified Mg2+-permeable channels and thus establish MLKL as a novel class of cation channels. PMID:27033670

  19. Controlling Cesium Cation Recognition via Cation Metathesis within and Ion Pair Receptor

    SciTech Connect

    Kim, Sung Kuk; Vargas-Zuniga, Gabriela; Hay, Benjamin; Young, Neil J; Delmau, Laetitia Helene; Lee, Prof. Chang-Hee; Kim, Jong Seung; Lynch, Vincent M.; Sessler, Jonathan L.

    2012-01-01

    Ion pair receptor 3 bearing an anion binding site and multiple cation binding sites has been synthesized and shown to function in a novel binding-release cycle that does not necessarily require displacement to effect release. The receptor forms stable complexes with the test cesium salts, CsCl and CsNO{sub 3}, in solution (10% methanol-d{sub 4} in chloroform-d) as inferred from {sup 1}H NMR spectroscopic analyses. The addition of KClO{sub 4} to these cesium salt complexes leads to a novel type of cation metathesis in which the 'exchanged' cations occupy different binding sites. Specifically, K{sup +} becomes bound at the expense of the Cs{sup +} cation initially present in the complex. Under liquid-liquid conditions, receptor 3 is able to extract CsNO{sub 3} and CsCl from an aqueous D{sub 2}O layer into nitrobenzene-d{sub 5} as inferred from {sup 1}H NMR spectroscopic analyses and radiotracer measurements. The Cs{sup +} cation of the CsNO{sub 3} extracted into the nitrobenzene phase by receptor 3 may be released into the aqueous phase by contacting the loaded nitrobenzene phase with an aqueous KClO{sub 4} solution. Additional exposure of the nitrobenzene layer to chloroform and water gives 3 in its uncomplexed, ion-free form. This allows receptor 3 to be recovered for subsequent use. Support for the underlying complexation chemistry came from single-crystal X-ray diffraction analyses and gas-phase energy-minimization studies.

  20. Combined delivery of the adiponectin gene and rosiglitazone using cationic lipid emulsions.

    PubMed

    Davaa, Enkhzaya; Kang, Bong-Seok; Han, Joo-Hui; Lee, Sang-Eun; Ng, Choon Lian; Myung, Chang-Seon; Park, Jeong-Sook

    2015-04-10

    For the combined delivery of an insulin-sensitizing adipokine; i.e., the ADN gene, and the potent PPARγ agonist rosiglitazone, cationic lipid emulsions were formulated using the cationic lipid DOTAP, helper lipid DOPE, castor oil, Tween 20 and Tween 80. The effect of drug loading on the physicochemical characteristics of the cationic emulsion/DNA complexes was investigated. Complex formation between the cationic emulsion and negatively charged plasmid DNA was confirmed and protection from DNase was observed. The in vitro transfection efficiency and cytotoxicity were evaluated in HepG2 cells. The particle sizes of the cationic emulsion/DNA complex were in the range 230-540 nm and those of the rosiglitazone-loaded cationic emulsion/DNA complex were in the range 220-340 nm. Gel retardation of the complexes was observed when the complexation weight ratios of the cationic lipid to plasmid DNA exceeded 4:1 for both the drug-free and rosiglitazone-loaded complexes. Both complexes stabilized plasmid DNA against DNase. The ADN expression level increased dose-dependently when cells were transfected with the cationic emulsion/DNA complexes. The rosiglitazone-loaded cationic emulsion/DNA complexes showed higher cellular uptake in HepG2 cells depending on the rosiglitazone loading, but not depending on the type of plasmid DNA type such as pVAX/ADN, pCAG/ADN, or pVAX. The drug-loaded cationic emulsion/plasmid DNA complexes were less cytotoxic than free rosiglitazone. Therefore, a cationic emulsion could potentially serve as a co-delivery system for rosiglitazone and the adiponectin gene. PMID:25681724

  1. Binding of monovalent metal cations by the p-sulfonatocalix[4]arene: experimental evidence for cation-pi interactions in water.

    PubMed

    Morel, Jean-Pierre; Morel-Desrosiers, Nicole

    2006-02-01

    Gibbs free energies, enthalpies and entropies for the binding of Na+, K+, Rb+, Cs+, Ag+, Tl+ and NH4+ by the p-sulfonatocalix[4]arene in water are determined by microcalorimetry. Whereas no significant heat effect is detected with Na+ or Ag+, suggesting that these cations are not complexed, weak but selective binding is observed with the other cations. The whole set of thermodynamic parameters, which demonstrate that the cations bind inside the cavity of the calixarene, evidence the importance of the cation-pi interactions for these complexes in water. PMID:16446803

  2. Electron exchange involving a sulfur-stabilized ruthenium radical cation.

    PubMed

    Shaw, Anthony P; Ryland, Bradford L; Norton, Jack R; Buccella, Daniela; Moscatelli, Alberto

    2007-07-01

    Half-sandwich Ru(II) amine, thiol, and thiolate complexes were prepared and characterized by X-ray crystallography. The thiol and amine complexes react slowly with acetonitrile to give free thiol or amine and the acetonitrile complex. With the thiol complex, the reaction is dissociative. The thiolate complex has been oxidized to its Ru(III) radical cation and the solution EPR spectrum of that radical cation recorded. Cobaltocene reduces the thiol complex to the thiolate complex. The 1H and 31P NMR signals of the thiolate complex in acetonitrile become very broad whenever the thiolate and thiol complexes are present simultaneously. The line broadening is primarily due to electron exchange between the thiolate complex and its radical cation; the latter is generated by an unfavorable redox equilibrium between the thiol and thiolate complexes. Pyramidal inversion of sulfur in the thiol complex is fast at room temperature but slow at lower temperatures; major and minor conformers of the thiol complex were observed by 31P NMR at -98 degrees C in CD2Cl2. PMID:17569530

  3. Flexible polyelectrolyte conformation in the presence of cationic and anionic surfactants

    NASA Astrophysics Data System (ADS)

    Passos, C. B.; Kuhn, P. S.; Diehl, A.

    2015-11-01

    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.

  4. Penetrating cations enhance uncoupling activity of anionic protonophores in mitochondria.

    PubMed

    Antonenko, Yuri N; Khailova, Ljudmila S; Knorre, Dmitry A; Markova, Olga V; Rokitskaya, Tatyana I; Ilyasova, Tatyana M; Severina, Inna I; Kotova, Elena A; Karavaeva, Yulia E; Prikhodko, Anastasia S; Severin, Fedor F; Skulachev, Vladimir P

    2013-01-01

    Protonophorous uncouplers causing a partial decrease in mitochondrial membrane potential are promising candidates for therapeutic applications. Here we showed that hydrophobic penetrating cations specifically targeted to mitochondria in a membrane potential-driven fashion increased proton-translocating activity of the anionic uncouplers 2,4-dinitrophenol (DNP) and carbonylcyanide-p-trifluorophenylhydrazone (FCCP). In planar bilayer lipid membranes (BLM) separating two compartments with different pH values, DNP-mediated diffusion potential of H(+) ions was enhanced in the presence of dodecyltriphenylphosphonium cation (C12TPP). The mitochondria-targeted penetrating cations strongly increased DNP- and carbonylcyanide m-chlorophenylhydrazone (CCCP)-mediated steady-state current through BLM when a transmembrane electrical potential difference was applied. Carboxyfluorescein efflux from liposomes initiated by the plastoquinone-containing penetrating cation SkQ1 was inhibited by both DNP and FCCP. Formation of complexes between the cation and CCCP was observed spectophotometrically. In contrast to the less hydrophobic tetraphenylphosphonium cation (TPP), SkQ1 and C12TPP promoted the uncoupling action of DNP and FCCP on isolated mitochondria. C12TPP and FCCP exhibited a synergistic effect decreasing the membrane potential of mitochondria in yeast cells. The stimulating action of penetrating cations on the protonophore-mediated uncoupling is assumed to be useful for medical applications of low (non-toxic) concentrations of protonophores. PMID:23626747

  5. Penetrating Cations Enhance Uncoupling Activity of Anionic Protonophores in Mitochondria

    PubMed Central

    Antonenko, Yuri N.; Khailova, Ljudmila S.; Knorre, Dmitry A.; Markova, Olga V.; Rokitskaya, Tatyana I.; Ilyasova, Tatyana M.; Severina, Inna I.; Kotova, Elena A.; Karavaeva, Yulia E.; Prikhodko, Anastasia S.; Severin, Fedor F.; Skulachev, Vladimir P.

    2013-01-01

    Protonophorous uncouplers causing a partial decrease in mitochondrial membrane potential are promising candidates for therapeutic applications. Here we showed that hydrophobic penetrating cations specifically targeted to mitochondria in a membrane potential-driven fashion increased proton-translocating activity of the anionic uncouplers 2,4-dinitrophenol (DNP) and carbonylcyanide-p-trifluorophenylhydrazone (FCCP). In planar bilayer lipid membranes (BLM) separating two compartments with different pH values, DNP-mediated diffusion potential of H+ ions was enhanced in the presence of dodecyltriphenylphosphonium cation (C12TPP). The mitochondria-targeted penetrating cations strongly increased DNP- and carbonylcyanide m-chlorophenylhydrazone (CCCP)-mediated steady-state current through BLM when a transmembrane electrical potential difference was applied. Carboxyfluorescein efflux from liposomes initiated by the plastoquinone-containing penetrating cation SkQ1 was inhibited by both DNP and FCCP. Formation of complexes between the cation and CCCP was observed spectophotometrically. In contrast to the less hydrophobic tetraphenylphosphonium cation (TPP), SkQ1 and C12TPP promoted the uncoupling action of DNP and FCCP on isolated mitochondria. C12TPP and FCCP exhibited a synergistic effect decreasing the membrane potential of mitochondria in yeast cells. The stimulating action of penetrating cations on the protonophore-mediated uncoupling is assumed to be useful for medical applications of low (non-toxic) concentrations of protonophores. PMID:23626747

  6. Coordination of trivalent metal cations to peptides: results from IRMPD spectroscopy and theory.

    PubMed

    Prell, James S; Flick, Tawnya G; Oomens, Jos; Berden, Giel; Williams, Evan R

    2010-01-21

    Structures of trivalent lanthanide metal cations La(3+), Ho(3+), and Eu(3+) with deprotonated Ala(n) (n = 2-5) or Leu-enk (Tyr-Gly-Gly-Phe-Leu) are investigated with infrared multiple photon dissociation (IRMPD) spectroscopy between 900 and 1850 cm(-1) and theory. In all of these complexes, a salt bridge is formed in which the metal cation coordinates to the carboxylate group of the peptide, resulting in a limited conformational space and many sharp IRMPD spectral bands. The IRMPD spectra clearly indicate that all carbonyl groups solvate the metal cation in each of the Ala(n) complexes. Due to strong vibrational coupling between the carbonyl groups, a sharp, high-energy amide I band due to in-phase stretching of all of the amide carbonyl groups bound to the metal cation is observed that is separated by approximately 50 cm(-1) from a strong, lower-energy amide I band. This extent of carbonyl coupling, which is sometimes observed in condensed-phase peptide and protein IR spectroscopy, has not been reported in IRMPD spectroscopy studies of other cationized peptide complexes. Intense bands due to carbonyl groups not associated with the metal cation are observed for Leu-enk complexes, indicating that a side chain group, such as the Tyr or Phe aromatic ring, prevents complete carbonyl coordination of the metal cation. Substitution of smaller lanthanide cations for La(3+) in these peptide complexes results only in minor structural changes consistent with the change in metal cation size. These are the first IRMPD spectra reported for lanthanide metal cationized peptides, and comparison to previously reported protonated and alkali metal or alkaline earth metal cationized peptide complexes reveals many trends consistent with the higher charge state of the lanthanide cations. PMID:19950916

  7. Dissecting the cation-cation interaction between two uranyl units.

    PubMed

    Tecmer, Paweł; Hong, Sung W; Boguslawski, Katharina

    2016-07-21

    We present a state-of-the-art computational study of the uranyl(vi) and uranyl(v) cation-cation interactions (dications) in aqueous solution. Reliable electronic structures of two interacting uranyl(vi) and uranyl(v) subunits as well as those of the uranyl(vi) and uranyl(v) clusters are presented for the first time. Our theoretical study elucidates the impact of cation-cation interactions on changes in the molecular structure as well as changes in vibrational and UV-Vis spectra of the bare uranyl(vi) and uranyl(v) moieties for different total spin-states and total charges of the dications. PMID:27335229

  8. Infrared spectroscopy of mass-selected metal carbonyl cations

    NASA Astrophysics Data System (ADS)

    Ricks, A. M.; Reed, Z. E.; Duncan, M. A.

    2011-04-01

    Metal carbonyl cations of the form M(CO)n+ are produced in a molecular beam by laser vaporization in a pulsed nozzle source. These ions, and their corresponding rare gas atom "tagged" analogs, M(CO)n(RG)m+, are studied with mass-selected infrared photodissociation spectroscopy in the carbonyl stretching region and with density functional theory computations. The number of infrared-active bands, their frequency positions, and their relative intensities provide distinctive patterns allowing determination of the geometries and electronic structures of these complexes. Cobalt penta carbonyl and manganese hexacarbonyl cations are compared to isoelectronic iron pentacarbonyl and chromium hexacarbonyl neutrals. Gold and copper provide examples of "non-classical" carbonyls. Seven-coordinate carbonyls are explored for the vanadium group metal cations (V +, Nb + and Ta +), while uranium cations provide an example of an eight-coordinate carbonyl.

  9. DFT study on the cycloreversion of thietane radical cations.

    PubMed

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

    2011-06-01

    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. PMID:21561127

  10. Amylose-Based Cationic Star Polymers for siRNA Delivery

    PubMed Central

    Nishimura, Tomoki; Umezaki, Kaori; Mukai, Sada-atsu; Sawada, Shin-ichi; Akiyoshi, Kazunari

    2015-01-01

    A new siRNA delivery system using a cationic glyco-star polymer is described. Spermine-modified 8-arm amylose star polymer (with a degree of polymerization of approximately 60 per arm) was synthesized by chemoenzymatic methods. The cationic star polymer effectively bound to siRNA and formed spherical complexes with an average hydrodynamic diameter of 230 nm. The cationic 8-arm star polymer complexes showed superior cellular uptake characteristics and higher gene silencing effects than a cationic 1-arm polymer. These results suggest that amylose-based star polymers are a promising nanoplatform for glycobiomaterials. PMID:26539548

  11. Cation–cation interactions and cation exchange in a series of isostructural framework uranyl tungstates

    SciTech Connect

    Balboni, Enrica; Burns, Peter C.

    2014-05-01

    The isotypical compounds (UO{sub 2}){sub 3}(WO{sub 6})(H{sub 2}O){sub 5} (1), Ag(UO{sub 2}){sub 3}(WO{sub 6})(OH)(H{sub 2}O){sub 3} (2), K(UO{sub 2}){sub 3}(WO{sub 6})OH(H{sub 2}O){sub 4} (3), Rb(UO{sub 2}){sub 3}(WO{sub 6})(OH)(H{sub 2}O){sub 3.5} (4), and Cs(UO{sub 2}){sub 3}(WO{sub 6})OH(H{sub 2}O){sub 3} (5) were synthesized, characterized, and their structures determined. Each crystallizes in space group Cc. (1): a=12.979 (3), b=10.238 (2), c=11.302 (2), β=102.044 (2); (2): a=13.148 (2), b=9.520 (1), c=11.083 (2), β=101.568 (2); (3): a=13.111 (8), b=9.930 (6), c=11.242 (7), β=101.024 (7); (4): a=12.940 (2), b=10.231 (2), c=11.259(2), β=102.205 (2); (5): a=12.983 (3), b=10.191 (3), c=11.263 (4), β=101.661 (4). Compounds 1–5 are a framework of uranyl and tungsten polyhedra containing cation–cation interactions. The framework has three symmetrically distinct U(VI) cations, one tungsten, sixteen to eighteen oxygen atoms, and in 2–5, one monovalent cation. Each atom occupies a general position. Each U(VI) cation is present as a typical (UO{sub 2}){sup 2+} uranyl ion in an overall pentagonal bipyramidal coordination environment. Each pentagonal bipyramid shares two equatorial edges with two other pentagonal bipyramids, forming a trimer. Trimers are connected into chains by edge-sharing with WO{sub 6} octahedra. Chains are linked through cation–cation interactions between two symmetrically independent uranyl ions. This yields a remarkably complex system of intersecting channels that extend along [0 0 1] and [−1 1 0]. The cation exchange properties of 2 and 3 were characterized at room temperature and at 140 °C. - Graphical abstract: Chains of uranium and tungsten polyhedra are connected into a three dimensional framework by cation–cation interactions occurring between two symmetrically independent uranyl pentagonal bipyramids. Monovalent cations present in channels within the structure can be exchanged by room temperature or mild hydrothermal

  12. Force Fields for Carbohydrate-Divalent Cation Interactions.

    PubMed

    Chen, Hsieh; Cox, Jason R; Panagiotopoulos, Athanassios Z

    2016-06-16

    We report molecular dynamics simulations to study intermolecular interactions for carbohydrate-divalent cation complexes. We observed that common force fields from literature with standard Lorentz-Berthelot combining rules are unable to reproduce the experimental stability constants for model carbohydrate monomer (α-d-Allopyranose) and alkali earth metal cation (Mg(2+), Ca(2+), Sr(2+), or Ba(2+)) complexes. A modified combining rule with rescaled effective cross-interaction radius between cations and the hydroxyl oxygens on the carbohydrates was introduced to reproduce the experimental stability constants, which the preferential carbohydrate-cation complexing structures through the ax-eq-ax sequence of O-1, O-2, and O-3 on α-d-Allopyranose were also observed. The effective radius scaling factor obtained from (α-d-Allopyranose)-Ca(2+) complexes was directly transferrable to the similar six-membered ring (α-d-Ribopyranose)-Ca(2+) complexes; however, reparameterization for the scaling factor may be necessary for the five-membered ring (α-d-Ribofuranose)-Ca(2+) complexes. PMID:27210229

  13. Alkali Metal Cation versus Proton and Methyl Cation Affinities: Structure and Bonding Mechanism

    PubMed Central

    Boughlala, Zakaria; Fonseca Guerra, Célia

    2016-01-01

    Abstract We have analyzed the structure and bonding of gas‐phase Cl−X and [HCl−X]+ complexes for X+= H+, CH3 +, Li+, and Na+, using relativistic density functional theory (DFT). We wish to establish a quantitative trend in affinities of the anionic and neutral Lewis bases Cl− and HCl for the various cations. The Cl−X bond becomes longer and weaker along X+ = H+, CH3 +, Li+, and Na+. Our main purpose is to understand the heterolytic bonding mechanism behind the intrinsic (i.e., in the absence of solvent) alkali metal cation affinities (AMCA) and how this compares with and differs from those of the proton affinity (PA) and methyl cation affinity (MCA). Our analyses are based on Kohn–Sham molecular orbital (KS‐MO) theory in combination with a quantitative energy decomposition analysis (EDA) that pinpoints the importance of the different features in the bonding mechanism. Orbital overlap appears to play an important role in determining the trend in cation affinities. PMID:27551660

  14. Alkali Metal Cation versus Proton and Methyl Cation Affinities: Structure and Bonding Mechanism.

    PubMed

    Boughlala, Zakaria; Fonseca Guerra, Célia; Bickelhaupt, F Matthias

    2016-06-01

    We have analyzed the structure and bonding of gas-phase Cl-X and [HCl-X](+) complexes for X(+)= H(+), CH3 (+), Li(+), and Na(+), using relativistic density functional theory (DFT). We wish to establish a quantitative trend in affinities of the anionic and neutral Lewis bases Cl(-) and HCl for the various cations. The Cl-X bond becomes longer and weaker along X(+) = H(+), CH3 (+), Li(+), and Na(+). Our main purpose is to understand the heterolytic bonding mechanism behind the intrinsic (i.e., in the absence of solvent) alkali metal cation affinities (AMCA) and how this compares with and differs from those of the proton affinity (PA) and methyl cation affinity (MCA). Our analyses are based on Kohn-Sham molecular orbital (KS-MO) theory in combination with a quantitative energy decomposition analysis (EDA) that pinpoints the importance of the different features in the bonding mechanism. Orbital overlap appears to play an important role in determining the trend in cation affinities. PMID:27551660

  15. Interaction of Hyaluronan with Cationic Nanoparticles.

    PubMed

    Bano, Fouzia; Carril, Mónica; Di Gianvincenzo, Paolo; Richter, Ralf P

    2015-08-01

    The polysaccharide hyaluronan (HA) is a main component of peri- and extracellular matrix, and an attractive molecule for materials design in tissue engineering and nanomedicine. Here, we study the morphology of complexes that form upon interaction of nanometer-sized amine-coated gold particles with this anionic, linear, and regular biopolymer in solution and grafted to a surface. We find that cationic nanoparticles (NPs) have profound effects on HA morphology on the molecular and supramolecular scale. Quartz crystal microbalance (QCM-D) shows that depending on their relative abundance, cationic NPs promote either strong compaction or swelling of films of surface-grafted HA polymers (HA brushes). Transmission electron and atomic force microscopy reveal that the NPs do also give rise to complexes of distinct morphologies-compact nanoscopic spheres and extended microscopic fibers-upon interaction with HA polymers in solution. In particular, stable and hydrated spherical complexes of single HA polymers with NPs can be prepared when balancing the ionizable groups on HA and NPs. The observed self-assembly phenomena could be useful for the design of drug delivery vehicles and a better understanding of the reorganization of HA-rich synthetic or biological matrices. PMID:26146006

  16. Methane activation by cobalt cluster cations, Co{sub n}{sup +} (n=2-16): Reaction mechanisms and thermochemistry of cluster-CH{sub x} (x=0-3) complexes

    SciTech Connect

    Citir, Murat; Liu Fuyi; Armentrout, P. B.

    2009-02-07

    The kinetic energy dependences of the reactions of Co{sub n}{sup +} (n=2-16) with CD{sub 4} are studied in a guided ion beam tandem mass spectrometer over the energy range of 0-10 eV. The main products are hydride formation, Co{sub n}D{sup +}, dehydrogenation to form Co{sub n}CD{sub 2}{sup +}, and double dehydrogenation yielding Co{sub n}C{sup +}. These primary products decompose to form secondary and higher order products, Co{sub n}CD{sup +}, Co{sub n-1}D{sup +}, Co{sub n-1}C{sup +}, Co{sub n-1}CD{sup +}, and Co{sub n-1}CD{sub 2}{sup +} at higher energies. Adduct formation of Co{sub n}CD{sub 4}{sup +} is also observed for the largest cluster cations, n{>=}10. In general, the efficiencies of the single and double dehydrogenation processes increase with cluster size, although the hexamer cation shows a reduced reactivity compared to its neighbors. All reactions exhibit thresholds, and cross sections for the various primary and secondary reactions are analyzed to yield reaction thresholds from which bond energies for cobalt cluster cations to D, C, CD, CD{sub 2}, and CD{sub 3} are determined. The relative magnitudes of these bond energies are consistent with simple bond order considerations. Bond energies for larger clusters rapidly reach relatively constant values, which are used to estimate the chemisorption energies of the C, CD, CD{sub 2}, and CD{sub 3} molecular fragments to cobalt surfaces.

  17. Study of complex formation of 5,5'-(2 E, 2' E)-2,2'-(ethane-1,2-diylidene)bis(hydrazine-1-yl-2-ylidene)bis(4-amino-4H-1,2,4-triazole-3-thiol) (HYT) macrocyclic ligand with Cd2+ cation in non-aqueous solution by spectroscopic and conductometric methods

    NASA Astrophysics Data System (ADS)

    Mallaekeh, Hassan; Shams, Alireza; Shaker, Mohammad; Bahramzadeh, Ehsan; Arefi, Donya

    2014-12-01

    In this paper the complexation reaction of the 5,5'-(2 E,2' E)-2,2'-(ethane-1,2-diylidene)bis(hydrazine-1-yl-2-ylidene)bis(4-amino-4H-1,2,4-triazole-3-thiol) ligand (HYT) with Cd2+ education was studied in some binary mixtures of methanol (MeOH), n-propanol (PrOH) and dimethyl-formamide (DMF) at different temperatures using the conductometry and spectrophotometry. The stability constants of the complex was determined using a GENPLOT computer program. The conductance data and absorbance-mole ratio plots show that in all solvent systems, the stoichiometry of the complex formed between (HYT) and Cd2+ cation is 1: 1. The obtained results show that the stability of (HYT)-Cd complex is sensitive to the mixed solvents composition. The values of thermodynamic parameters (Δ G ∘, Δ H ∘, and Δ S ∘) for formation of (HYT)-Cd complex were obtained from temperature dependence of the stability constant using the van't Hoff plots. The results show that in most cases, the complex are enthalpy destabilized but entropy stabilized and the complex formation is affected by pH, time, temperature and the nature of the solvent.

  18. Synthesis, spectroscopic and structural characterization of cobalt(II) complex with uracil-containing 2,6-diformylpyridine ligand: Theoretical studies on the ligand and pentagonal-bipyramidal [Co(L)(H 2O) 2] 2+ and [Zn(L)(H 2O) 2] 2+ cations

    NASA Astrophysics Data System (ADS)

    Koz, Gamze; Özdemir, Namık; Astley, Demet; Dinçer, Muharrem; Astley, Stephen T.

    2010-03-01

    The title complex, trans-diaqua{5,5'-[( E, E)-pyridine-2,6-diylbis(methylidynenitrilo)]bis-[pyrimidine-2,4(1 H,3 H)-dione]}cobalt(II) bis(hexafluorophosphate) dihydrate [Co(C 15H 11N 7O 4) (H 2O) 2]·2(PF 6)·2(H 2O), has been synthesized, and characterized by IR spectroscopy and single crystal X-ray diffraction. The compound crystallizes in the monoclinic space group P2 1/ c with a = 10.7301(4) Å, b = 12.0537(3) Å, c = 21.6030(9) Å and β = 109.392 (3)°. In the title complex, the Co 2+ centre is seven-coordinated in a slightly distorted pentagonal-bipyramidal geometry, with the two water O atoms located in the apical positions, and the pyridine N atom, the two imine N atoms and two carbonyl O atoms of the uracil groups located in the equatorial plane. The positions of fluorine atoms in the hexafluorophosphate groups were disordered. The charge is balanced by two PF 62- anions. In addition to the molecular geometry from X-ray experiment, theoretical studies have been carried out on the structures of the pentagonal-bipyramidal [Co(L)(H 2O) 2] 2+ and [Zn(L)(H 2O) 2] 2+ cations using the Hartree-Fock (HF) and density functional theory (DFT-B3LYP) methods in conjunction with effective core potential basis set (LANL2DZ) to clarify the solid state behaviour of these cations. Besides, frontier molecular orbitals (FMO) analysis and natural bond orbital (NBO) analysis of [Co(L)(H 2O) 2] 2+ cation are presented here together with vibrational frequencies and gauge including atomic orbital (GIAO) 1H and 13C NMR chemical shift values of the pentadentate ligand calculated at HF and DFT (B3LYP) levels with 6-31G(d) basis set.

  19. Cation-Dependent Compression Behavior in Low-Silica Zeolite-X

    SciTech Connect

    Lee,Y.; Lee, H.; Lee, D.; Shin, T.; Choi, J.; Kao, C.

    2007-01-01

    Under hydrostatic pressure, low-silica zeolite-X exhibits a range of compression behavior depending on its cation distribution as well as the pressure transmitting medium. This pressure response appears to be a complex phenomenon involving the interplay between selective overhydration, cation relocation, as well as the intrinsic framework distortion, and indicates that the apparent compressibility of LSX can be tailored via cation exchange and the choice of pressure medium.

  20. Nanoscale encapsulation: the structure of cations in hydrophobic microporous aluminosilicates

    SciTech Connect

    Wasserman, S.R.; Yuchs, S.E.; Giaquinta, D.; Soderholm, L.; Song, Kang

    1996-10-01

    Hydrophobic microporous aluminosilicates, created by organic surface modification of inherently hydrophilic materials such as zeolites and clays, are currently being investigated as storage media for hazardous cations. Use of organic monolayers to modify the surface of an aluminosilicate after introducing an ion into the zeolite/clay reduces the interaction of water with the material. Resulting systems are about 20 times more resistant to leaching of stored ion. XAS spectra from the encapsulated ion demonstrate that byproducts from the organic modifier can complex with the stored cation. This complexation can result in a decreased affinity of the cation for the aluminosilicate matrix. Changing the organic modifier eliminates this problem. XAS spectra also indicate that the reactivity and speciation of the encapsulated ion may change upon application of the hydrophobic layer.

  1. Cation Diffusion in Xenotime

    NASA Astrophysics Data System (ADS)

    Cherniak, D. J.

    2004-05-01

    Xenotime is an important mineral in metamorphic paragenesis, and useful in isotopic dating, garnet-xenotime thermometry, and monazite-xenotime thermometry, so diffusion data for xenotime of cations of geochronological and geochemical importance are of some interest. We report here on diffusion of the rare earth elements Sm, Dy and Yb in synthetic xenotime under dry conditions. The synthetic xenotime was grown via a Na2}CO{3}-MoO_{3 flux method. The source of diffusant for the experiments were REE phosphate powders, with experiments run with sources containing a single REE. Experiments were performed by placing source and xenotime in Pt capsules, and annealing capsules in 1 atm furnaces for times ranging from thirty minutes to a month, at temperatures from 1000 to 1400C. The REE distributions in the xenotime were profiled by Rutherford Backscattering Spectrometry (RBS). The following Arrhenius relations are obtained for diffusion in xenotime, normal to (101): DSm = 1.7x10-4 exp(-442 kJ mol-1/RT) m2}sec{-1 DDy = 3.5x10-7 exp(-365 kJ mol-1/RT) m2}sec{-1 DYb = 7.4x10-7 exp(-371 kJ mol-1/RT) m2}sec{-1. Diffusivities of these REE do not differ greatly in xenotime, in contrast to the findings noted for the REE in zircon (Cherniak et al., 1997), where the LREE diffuse more slowly, and with higher activation energies for diffusion, than the heavier rare earths. In zircon, these differences among diffusion of the rare earths are attributed to the relatively large size of the REE with respect to Zr, for which they substitute in the zircon lattice. With the systematic increase in ionic radius from the heavy to lighter REE, this size mismatch becomes more pronounced and diffusivities of the LREE are as consequence slower. Although xenotime is isostructural with zircon, the REE are more closely matched in size to Y, so in xenotime this effect appears much smaller and the REE diffuse at similar rates. In addition, the process of diffusion in xenotime likely involves simple REE+3

  2. Mercury release from deforested soils triggered by base cation enrichment.

    PubMed

    Farella, N; Lucotte, M; Davidson, R; Daigle, S

    2006-09-01

    The Brazilian Amazon has experienced considerable colonization in the last few decades. Family agriculture based on slash-and-burn enables millions of people to live in that region. However, the poor nutrient content of most Amazonian soils requires cation-rich ashes from the burning of the vegetation biomass for cultivation to be successful, which leads to forest ecosystem degradation, soil erosion and mercury contamination. While recent studies have suggested that mercury present in soils was transferred towards rivers upon deforestation, little is known about the dynamics between agricultural land-use and mercury leaching. In this context, the present study proposes an explanation that illustrates how agricultural land-use triggers mercury loss from soils. This explanation lies in the competition between base cations and mercury in soils which are characterized by a low adsorption capacity. Since these soils are naturally very poor in base cations, the burning of the forest biomass suddenly brings high quantities of base cations to soils, destabilizing the previous equilibrium amongst cations. Base cation enrichment triggers mobility in soil cations, rapidly dislocating mercury atoms. This conclusion comes from principal component analyses illustrating that agricultural land-use was associated with base cation enrichment and mercury depletion. The overall conclusions highlight a pernicious cycle: while soil nutrient enrichment actually occurs through biomass burning, although on a temporary basis, there is a loss in Hg content, which is leached to rivers, entering the aquatic chain, and posing a potential health threat to local populations. Data presented here reflects three decades of deforestation activities, but little is known about the long-term impact of such a disequilibrium. These findings may have repercussions on our understanding of the complex dynamics of deforestation and agriculture worldwide. PMID:16781764

  3. A Scale Model of Cation Exchange for Classroom Demonstration.

    ERIC Educational Resources Information Center

    Guertal, E. A.; Hattey, J. A.

    1996-01-01

    Describes a project that developed a scale model of cation exchange that can be used for a classroom demonstration. The model uses kaolinite clay, nails, plywood, and foam balls to enable students to gain a better understanding of the exchange complex of soil clays. (DDR)

  4. Cation Ordering in Layered Nickelates

    NASA Astrophysics Data System (ADS)

    Nelson-Cheeseman, Brittany; Zhou, Hua; Cammarata, Antonio; Hoffman, Jason; Balachandran, Prasanna; Rondinelli, James; Bhattacharya, Anand

    2013-03-01

    The single layer Ruddlesden-Popper nickelates present a model system to understand how the effects of digital dopant cation ordering may affect the properties of 2-dimensional conducting sheets. We investigate the effects of aliovalent A-site cation order on LaSrNiO4 films. Using molecular beam epitaxy, we interleave full layers of SrO and LaO in a series of chemically equivalent films, varying the pattern of SrO and LaO layers relative to the NiO2 layers. Through synchrotron surface x-ray diffraction and Coherant Bragg Rod Analysis (COBRA), we directly investigate the A-site cation order and the resulting atomic displacements for each ordering pattern. We correlate these results with theoretical calculations and transport measurements of the layered nickelate films.

  5. Adsorption of reovirus to clay minerals: effects of cation-exchange capacity, cation saturation, and surface area.

    PubMed Central

    Lipson, S M; Stotzky, G

    1983-01-01

    The adsorption of reovirus to clay minerals has been reported by several investigators, but the mechanisms defining this association have been studied only minimally. The purpose of this investigation was to elucidate the mechanisms involved with this interaction. More reovirus type 3 was adsorbed, in both distilled and synthetic estuarine water, by low concentrations of montmorillonite than by comparable concentrations of kaolinite containing a mixed complement of cations on the exchange complex. Adsorption to the clays was essentially immediate and was correlated with the cation-exchange capacity of the clays, indicating that adsorption was primarily to negatively charged sites on the clays. Adsorption was greater with low concentrations of clays in estuarine water than in distilled water, as the higher ionic strength of the estuarine water reduced the electrokinetic potential of both clay and virus particles. The addition of cations (as chloride salts) to distilled water enhanced adsorption, with divalent cations being more effective than monovalent cations and 10(-2) M resulting in more adsorption than 10(-3) M. Potassium ions suppressed reovirus adsorption to montmorillonite, probably by collapsing the clay lattices and preventing the expression of the interlayer-derived cation-exchange capacity. More virus was adsorbed by montmorillonite made homoionic to various mono-, di-, and trivalent cations (except by montmorillonite homoionic to potassium) than by comparable concentrations of kaolinite homoionic to the same cations. The sequence of the amount of adsorption to homoionic montmorillonite was Al greater than Ca greater than Mg greater than Na greater than K; the sequence of adsorption to kaolinite was Na greater than Al greater than Ca greater than Mg greater than K. The constant partition-type adsorption isotherms obtained when the clay concentration was maintained constant and the virus concentration was varied indicated that a fixed proportion of the

  6. Cation-π versus anion-π interactions: A theoretical NMR study

    NASA Astrophysics Data System (ADS)

    Ebrahimi, Ali; Khorassani, Mostafa Habibi; Masoodi, Hamid Reza

    2011-03-01

    The influences of cation-π and anion-π interactions on NMR data have been investigated in complexes of cations and anions with 1,3,5-trifluorobenzene (TFB). Cation-π interaction increases 1JC-F, 1JC-H and the chemical shifts of hydrogen and fluorine while it decreases 1JC-C. The changes are in reverse direction in the presence of anion-π interaction. The role of geometry and electronic effects on the NMR data was considered. The distance dependence of NMR parameters has been studied in these complexes. The NMR data have been investigated in isoelectronic complexes.

  7. Coordination Chemistry of Alkali and Alkaline-Earth Cations with Macrocyclic Ligands.

    ERIC Educational Resources Information Center

    Dietrich, Bernard

    1985-01-01

    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,…

  8. NUTRIENT LEACHING FROM CONIFER NEEDLES IN RELATION TO FOLIAR APOPLAST CATION EXCHANGE CAPACITY

    EPA Science Inventory

    Limited evidence to date suggests that acidic precipitation promotes leaching of nutrient cations from conifer foliage. n order to evaluate the relative contribution of the apoplast cation exchange complex and symplast nutrient pools to the leached ions, the magnitude of potentia...

  9. Synthesis, structure and luminescence studies of Eu(III), Tb(III), Sm(III), Dy(III) cationic complexes with acetylacetone and bis(5-(pyridine-2-yl)-1,2,4-triazol-3-yl)propane☆

    PubMed Central

    Gusev, Alexey N.; Hasegawa, Miki; Shimizu, Tomohito; Fukawa, Tomonori; Sakurai, Shoya; Nishchymenko, Galyna A.; Shul’gin, Victor F.; Meshkova, Svetlana B.; Linert, Wolfgang

    2013-01-01

    Studies concerning synthesis, structure and luminescence of eight-coordinate Eu, Tb, Sm and Dy complexes of the type [Ln(acac)2(L)]Cl (Hacac = pentanedione-2,4 and L = bis(5-(pyridine-2-yl)-1,2,4-triazol-3-yl)propane) are reported in detail. The obtained complexes were investigated by various means including elemental- and thermogravimetric analysis, IR- and electron transition spectroscopy. The structure of the Tb complex was determined by single-crystal X-ray crystallography: Tb is eight-coordinate, and L acting only as a tetradentate chelate together with two bidentate acac ligands. Photophysical studies of the complexes were carried out. The Tb(III) and Eu(III) complexes show strong emissions both in solid state and solution. The intensity of the luminescence of Dy(III) and Sm(III) are relatively weak. The factors determining the intensity of the photoluminescence are discussed. PMID:24068839

  10. Does cation break the cyano bond? A critical evaluation of nitrile-cation interaction.

    PubMed

    Woi, Pei Meng; Bakar, Maizathul Akmam A; Rosli, Ahmad Nazmi; Lee, Vannajan Sanghiran; Ahmad, Mohd Rais; Zain, Sharifuddin; Alias, Yatimah

    2014-05-01

    DFT and G4 results reveal that cations display the following trends in imparting its positive charge to acrylonitrile; H⁺ > Li⁺ > Na⁺ > K⁺ for group I and Be²⁺ > Mg²⁺ > Ca²⁺ for group II. Solvation by water molecules and interaction with cation make the cyano bond more polarized and exhibits ketene-imine character. Bond order in nitrile-cation complexes has been predicted based on the s character of the covalent bond orbitals. Mulliken, CHELPG, and NPA charges are in good agreement in predicting positive charge buildup and GIAO nuclear deshileding on C1. G4 enthalpies show that Mg²⁺ is more strongly bound to acrylonitrile than to acetonitrile by 3 kcal mol⁻¹, and the proton affinity of the former is higher by 0.8 kcal mol⁻¹. G4 enthalpies of reductions support prior experimental observation that metalated conjugated nitriles show enhanced reactivity toward weak nucleophiles to afford Michael addition products. PMID:24770548

  11. Versatile cation transport in imidazolium based polymerized ionic liquids

    NASA Astrophysics Data System (ADS)

    Evans, Christopher; Segalman, Rachel

    Polymerized ionic liquids (PIL) with tethered imidazolium groups are able to conduct a diverse array of cations relevant for energy applications. The well-known complexation of imidazolium with transition metals is exploited to bind ions such as H +, Li+, Cu2+, and Ni2+ by doping the neutral PIL with the appropriate Cation-TFSI- salt. Conductivities were first determined via AC impedance indicating that H+ salts lead to the highest conductivity (due to low ion mass and potential Grotthus mechanism) followed by Cu2+, Li+, Ag+, and Ni2+. The equilibrium constant for imidazolium complexation is larger for Cu2+ relative to Li-, Ag-, and Ni-imidazolium complexes leading to greater salt dissociation and higher conductivities. For LiTFSI and CuTFSI2 salts, metallic lithium or copper electrodes were employed in battery cells to pass a steady DC current and confirm that the cations are in fact carrying current. Interestingly, the divalent Cu2+ also ionically crosslinks the polymer leading to a plateau in the viscosity. Thus, divalent ions provide an unique route to high conductivity, high modulus polymeric electrolytes. Future studies involving ZnTFSI2 and MgTFSI2 for battery applications are proposed to examine how versatile the PIL platform is for cation transport.

  12. Gold carbenes, gold-stabilized carbocations, and cationic intermediates relevant to gold-catalysed enyne cycloaddition.

    PubMed

    Harris, R J; Widenhoefer, R A

    2016-08-21

    Cationic gold complexes in which gold is bound to a formally divalent carbon atom, typically formulated as gold carbenes or α-metallocarbenium ions, have been widely invoked in a range of gold-catalyzed transformations, most notably in the gold-catalyzed cycloisomerization of 1,n-enynes. Although the existence of gold carbene complexes as intermediates in gold-catalyzed transformations is supported by a wealth of indirect experimental data and by computation, until recently no examples of cationic gold carbenes/α-metallocarbenium ions had been synthesized nor had any cationic intermediates generated via gold-catalyzed enyne cycloaddition been directly observed. Largely for this reason, there has been considerable debate regarding the electronic structure of these cationic complexes, in particular the relative contributions of the carbene (LAu(+)[double bond, length as m-dash]CR2) and α-metallocarbenium (LAu-CR2(+)) forms, which is intimately related to the extent of d → p backbonding from gold to the C1 carbon atom. However, over the past ∼ seven years, a number of cationic gold carbene complexes have been synthesized in solution and generated in the gas phase and cationic intermediates have been directly observed in the gold-catalyzed cycloaddition of enynes. Together, these advances provide insight into the nature and electronic structure of gold carbene/α-metallocarbenium complexes and the cationic intermediates generated via gold-catalyzed enyne cycloaddition. Herein we review recent advances in this area. PMID:27146712

  13. Layered Molecule-Based Magnets Formed by Decamethylmetallocenium Cations and Two-Dimensional Bimetallic Complexes [ MIIRu III(ox) 3] -( MII=;Mn, Fe, Co, Cu and Zn; ox=oxalate)

    NASA Astrophysics Data System (ADS)

    Coronado, Eugenio; Galán-Mascarós, José R.; Gómez-García, Carlos J.; Martínez-Agudo, José M.; Martínez-Ferrero, Eugenia; Waerenborgh, Joao C.; Almeida, Manuel

    2001-07-01

    A new series of hybrid organometallic-inorganic layered magnets with formula [ZIIICp*2] [MIIRuIII(ox)3] (ZIII=Co and Fe; MII=Mn, Fe, Co, Cu, and Zn; ox=oxalate: Cp*=pentamethylcyclopentadienyl) has been prepared. All of these compounds are isostructural to the previously reported [ZIIICp*2] [MIIMIII(ox)3] (MIII=Cr, Fe) series and crystallize in the monoclinic space group C2/m, as found by powder X-ray diffraction analysis. They are novel examples of magnetic materials formed by bimetallic oxalate-based extended layers separated by layers of organometallic cations. The magnetic properties of all these compounds have been investigated (ac and dc magnetic susceptibilities and field dependence of the isothermal magnetization at 2 K). In particular, it has been found that FeII and CoII derivatives behave as magnets with ordering temperatures of 12.8 and 2.8 K, respectively, while no long-range magnetic ordering has been detected down to 2 K in the MnII and CuII derivatives. The magnetic ordering in the FeII derivatives has been confirmed through Mössbauer spectroscopy. This technique has also made it possible to observe the spin polarization of the paramagnetic [FeCp*2]+ units caused by the internal magnetic field created by the bimetallic layers in the ordered state.

  14. Nanoheterostructure Cation Exchange: Anionic Framework Conservation

    SciTech Connect

    Jain, Prashant K.; Amirav, Lilac; Aloni, Shaul; Alivisatos, A. Paul

    2010-05-11

    In ionic nanocrystals the cationic sub-lattice can be replaced with a different metal ion via a fast, simple, and reversible place-exchange, allowing post-synthetic modification of the composition of the nanocrystal, while preserving its size and shape. Here, we demonstrate for the first time that during such an exchange, the anionic framework of the crystal is preserved. When applied to nanoheterostructures, this phenomenon ensures that compositional interfaces within the heterostructure are conserved throughout the transformation. For instance, a morphology composed of a CdSe nanocrystal embedded in a CdS rod (CdSe/CdS) was exchanged to a PbSe/PbS nanorod via a Cu2Se/Cu2S structure. During every exchange cycle, the seed size and position within the nanorod were preserved, as evident by excitonic features, Z-contrast imaging, and elemental line-scans. Anionic framework conservation extends the domain of cation exchange to the design of more complex and unique nanostructures.

  15. A Cucurbituril Derivative That Exhibits Cation-Modulated Self-Assembly.

    PubMed

    Ustrnul, Lukas; Babiak, Michal; Kulhanek, Petr; Sindelar, Vladimir

    2016-07-15

    Cucurbiturils are the most potent artificial receptors known for many organic molecules in water. However, little is known about their supramolecular chemistry in organic solvents. Here we present a new cucurbituril derivative, 1, and investigate its supramolecular properties in methanol. The macrocycle resembles a five-membered cucurbituril in which four glycoluril units are replaced with propanediurea. Macrocycle 1 can bind to one cation such as potassium or anilinium via each of its opposed portals. The stability of these complexes in methanol at nanomolar concentrations exceeds that of complexes between metal cations and crown ethers. Moreover, macrocycle 1 forms a self-assembled tetrameric aggregate in the solid state and in methanol. The tetramer is stabilized by the addition of up to 1 equiv of a cation but is fully disassembled in the presence of 2 equiv of the cation. Cations can thus be used to tune the aggregation of 1 in solution. PMID:27308961

  16. In situ remediation process using divalent metal cations

    DOEpatents

    Brady, Patrick V.; Khandaker, Nadim R.; Krumhansl, James L.; Teter, David M.

    2004-12-14

    An in situ process for treating ambient solid materials (e.g., soils, aquifer solids, sludges) by adding one or more divalent metal cations to the ambient solid material. The added divalent metal cations, such as Cu.sup.2+ or Zn.sup.2+, combine with metal oxide/hydroxides (e.g., ferric oxide/hydroxide or aluminum oxide/hydroxide) already present in the ambient solid material to form an effective sorbent material having a large number of positively-charged surface complexes that binds and immobilizes anionic contaminant species (e.g., arsenic or chromate). Divalent metal cations can be added, for example, by injecting an aqueous solution of CuSO.sub.4 into an aquifer contaminated with arsenic or chromate. Also, sludges can be stabilized against leaching of anionic contaminants through the addition of divalent metal cations. Also, an inexpensive sorbent material can be easily formed by mixing divalent metal cations with soil that has been removed from the ground.

  17. Ab initio study of the phenol-water cation radical

    NASA Astrophysics Data System (ADS)

    Hobza, Pavel; Burcl, Rudolf; Špirko, Vladimír; Dopfer, Otto; Müller-Dethlefs, Klaus; Schlag, Edward W.

    1994-07-01

    The phenol-water cation radical has been investigated by ab initio theory using the spin-restricted open-shell Hartree-Fock and spin-restricted open-shell second-order Møller-Plesset theories with 3-21G*(O) and 6-31G* basis sets. The full geometrical optimization was performed for several hydrogen-bonded structures and one hemibonded structure. Clearly, the most stable structure has been found for Cs symmetry with the linear hydrogen bond between the proton of the OH group of the phenol cation radical and the oxygen of the water, and the water hydrogens pointing away from the phenyl ring. For this structure harmonic (and for some intermolecular modes anharmonic) vibrational frequencies have been computed for various isotopic complexes. The computed shifts of phenol-localized intramolecular modes on complexation and on deuteration as well as the calculated intermolecular frequencies of the different isotopic complexes allow for an assignment of vibrational frequencies observed in the experimental zero-kinetic-energy (ZEKE) photoelectron spectra. Five out of a possible six intermolecular vibrations and several intramolecular modes have been assigned, including the 18b vibration which shows a strong blue shift in frequency upon complexation. Structure and properties of the phenol-water cation radical are compared with those of the corresponding neutral complex.

  18. Cationic electrodepositable coating composition comprising lignin

    DOEpatents

    Fenn, David; Bowman, Mark P; Zawacky, Steven R; Van Buskirk, Ellor J; Kamarchik, Peter

    2013-07-30

    A cationic electrodepositable coating composition is disclosed. The present invention in directed to a cationic electrodepositable coating composition comprising a lignin-containing cationic salt resin, that comprises (A) the reaction product of: lignin, an amine, and a carbonyl compound; (B) the reaction product of lignin, epichlorohydrin, and an amine; or (C) combinations thereof.

  19. Gaseous protein cations are amphoteric

    SciTech Connect

    Stephenson, J.L. Jr.; McLuckey, S.A.

    1997-02-19

    Singly- and multiply-protonated ubiquitin molecules are found to react with iodide anions, and certain other anions, by attachment of the anion, in competition with proton transfer to the anion. The resulting adduct ions are relatively weakly bound and dissociate upon collisional activation by loss of the neutral acid derived from the anion. Adduct ions that behave similarly can also be formed via ion/molecule reactions involving the neutral acid. The ion/molecule reaction phenomenology, however, stands in contrast with that expected based on the reaction site(s) being charged. Reaction rates increase inversely with charge state and the total number of neutral molecules that add to the protein cations increases inversely with cation charge. These observations are inconsistent with the formation of proton-bound clusters but are fully consistent with the formation of ion pairs or dipole/dipole bonding involving the neutral acid and neutral basic sites in the protein. The ion/ion reactions can be interpreted on the basis of conjugate acid/base chemistry in which the anion, which is a strong gaseous base, reacts with a protonated site, which is a strong gaseous acid. Adduct ions can also be formed via ion/molecule reaction which, on the basis of microscopic reversibility, implies that the neutral acid interacts with neutral basic sites on the protein cation. 26 refs., 10 figs., 1 tab.

  20. Monte Carlo simulation of DNA fragment hydration in the presence of alkaline cations using novel atom-atom potential functions.

    PubMed

    Teplukhin, A V; Malenkov, G G; Poltev, V I

    1998-10-01

    The set of atom-atom potential functions specially adjusted to simulation of nucleic acid fragment hydration (Poltev, Grokhlina & Malenkov, J. Biomol. Struct. Dyn. 2, 413, 1984) is extended by including alkaline cation interactions. The choice of new potential functions was realized using experimental data on crystal hydrates of nucleotides and related compounds as well as thermodynamic data on ion solutions. The extended set of potential functions allows to reproduce many features of interactions between alkaline cations and nucleic acid fragments in water solutions. The sites of preferential cation localization near bases and phosphate groups were obtained and examined. The potential functions reproduce the dissociation tendency of cation-phosphate group and cation-base complexes in aqueous medium. Pathways of cation dissociations from nucleic acid components have been studied, and metastable water-bridged positions of cations near bases and phosphate group have been revealed. PMID:9833668

  1. Hyperconjugation in diethyl ether cation versus diethyl sulfide cation.

    PubMed

    Morita, Masato; Matsuda, Yoshiyuki; Endo, Tomoya; Mikami, Naohiko; Fujii, Asuka; Takahashi, Kaito

    2015-09-28

    Ionization of a molecule can greatly alter its electronic structure as well as its geometric structure. In this collaborative experimental and theoretical study, we examined variance in hyperconjugation upon ionization of diethyl ether (DEE) and diethyl sulfide (DES). We obtained the experimental gas phase vibrational spectra of DEE, DES, DEE(+), DES(+), DEE(+)-Ar, and DES(+)-Ar in the wavenumber region of 2500 to 3600 cm(-1). For DEE(+) and DEE(+)-Ar, we observed a greatly red shifted CH stretching peak at 2700 cm(-1), while the lowest CH stretching peaks for DEE, DES, DES(+) and DES(+)-Ar were observed around 2850 cm(-1). For DEE(+), we calculated a drastic red shifted CH stretching peak at 2760 cm(-1), but for DEE, DES, and DES(+) the lowest CH stretching peaks were calculated to be at 2860, 2945, and 2908 cm(-1), respectively. In addition, for DEE, the minima (maxima) geometry in the neutral state becomes a maxima (minima) geometry in the cationic state, while similar minima geometries are seen in neutral and cationic states of DES. These experimental and theoretical findings were rationalized through the natural bond orbital analysis by quantifying the hyperconjugation between the σCH orbital and the ionized singly occupied p orbital of the oxygen (sulfur) in DEE(+) (DES(+)). This study showed how orientation with the ionized orbital can greatly affect the neighboring CH bond strength and its polarity, as well as the geometry of the system. Furthermore, this change in the CH bond strength between DEE(+) and DES(+) is quantified from the energies for intramolecular proton transfer in the two cations. PMID:26300267

  2. Cation coordination in oxychloride glasses

    NASA Astrophysics Data System (ADS)

    Johnson, J. A.; Holland, D.; Bland, J.; Johnson, C. E.; Thomas, M. F.

    2003-02-01

    Glasses containing mixtures of cations and anions of nominal compositions [Sb2O3]x - [ZnCl2]1-x where x = 0.25, 0.50, 0.75, and 1.00, have been studied by means of neutron diffraction and Raman and Mössbauer spectroscopy. There is preferential bonding within the system with the absence of Sb-Cl bonds. Antimony is found to be threefold coordinated to oxygen, and zinc fourfold coordinated. The main contributing species are of the form [Sb(OSb)2(OZn)] and [Zn(ClZn)2(OSb)2].

  3. Hydrogen-bonded pillars of alternating chiral complex cations and anions: 1. Synthesis, characterization, X-ray structure and thermal stability of catena-{[Co(H(2)oxado)(3)][Cr(C(2)O(4))(3)].5H(2)O} and of its precursor (H(3)oxado)[Co(H(2)oxado)(3)](SO(4))(2).2H(2)O.

    PubMed

    Bélombé, M M; Nenwa, J; Mbiangué, Y A; Majoumo-Mbé, F; Lönnecke, P; Hey-Hawkins, E

    2009-06-21

    Compound (H(3)oxado)[Co(H(2)oxado)(3)](SO(4))(2).2H(2)O () (H(3)oxado(+) = oxamide dioximemonoximium) reacted metathetically with Ba(6)(H(2)O)(17)[Cr(C(2)O(4))(3)](4).7H(2)O in water to give the one-dimensional complex salt {[Co(H(2)oxado)(3)][Cr(C(2)O(4))(3)].5H(2)O}(infinity) () (H(2)oxado = oxamide dioxime). Compounds and were characterized by elemental analysis, FTIR, UV-Vis and by single crystal X-ray structure determination. The structure of consists of infinite pillars of alternating chiral complex cations and anions linked together along [100] by electrostatic and longitudinal O-HO interactions, with an average intrachain CoCr separation of 4.94 A. Equatorial N-HO bridges cross-link neighboring pillars (which are of opposite chirality) and consolidate a three-dimensional lattice framework which delineates elliptic nanochannels parallel to the a axis, encapsulating highly disordered water molecules. The thermal stability of both compounds was assessed by TGA, and the effective magnetic moment of , checked at room temperature, revealed considerable spin-orbit coupling. PMID:19488450

  4. Synthesis and structure of new compounds with Zn-Ga bonds: insertion of the gallium(I) bisimidinate Ga(DDP) into Zn-X (X = CH3, Cl) and the homoleptic complex cation [Zn(GaCp*)4]2+.

    PubMed

    Kempter, Andreas; Gemel, Christian; Cadenbach, Thomas; Fischer, Roland A

    2007-10-29

    Insertion reactions of the low-valent group 13 bisimidinate ligand Ga(DDP) {DDP = 2-[(2,6-diisopropylphenyl)amino]-4-[(2,6-diisopropylphenyl)imino]-2-pentene} into Zn-Me and Zn-Cl bonds are reported. The reaction of ZnMe2 with 2 equiv of Ga(DDP) yields the double-insertion product [{(DDP)GaMe}2Zn] (1), whereas the insertion of Ga(DDP) into the Zn-Cl bond of ZnCl2 in tetrahydrofuran (THF) leads to the monoinsertion product [{(DDP)GaCl}ZnCl(THF)2] (2). Treatment of 2 with Na[BArF] results in the salt [{THF.Ga(DDP)}Zn(THF)(mu-Cl)]2[BArF]2 (3), with two Cl atoms bridging the Zn centers. The structural features of the Zn-Ga-bonded compounds 1-3 were compared with related complexes and in particular with the compound [Zn(GaCp*)4][BArF]2 (4), which was synthesized by the reaction of ZnMe2, [H(OEt2)2][BArF], and GaCp* in fluorobenzene. The complex cation [Zn(GaCp*)4]2+ of 4 relates to previously reported d10 analogues [M(GaCp*)4] (M = Ni, Pd, Pt). All new compounds were fully characterized by elemental analysis, NMR spectroscopy, and single-crystal X-ray diffraction analysis. PMID:17918829

  5. Examination of the effect of the annealing cation on higher order structures containing guanine or isoguanine repeats

    PubMed Central

    Pierce, Sarah E.; Wang, Junmei; Jayawickramarajah, Janarthanan; Hamilton, Andrew D.; Brodbelt, Jennifer S.

    2010-01-01

    Isoguanine (2-oxo-6-amino-guanine), a natural but non-standard base, exhibits unique self-association properties compared to its isomer, guanine, and results in formation of different higher order DNA structures. In this work, the higher order structures formed by oligonucleotides containing guanine repeats or isoguanine repeats after annealing in solutions containing various cations are evaluated by electrospray ionization mass spectrometry (ESI-MS) and circular dichroism (CD) spectroscopy. The guanine-containing strand (G9) consistently formed quadruplexes upon annealing, whereas the isoguanine strand (Ig9) formed both pentaplexes and quadruplexes depending on the annealing cation. Quadruplex formation with G9 showed some dependence on the identity of the cation present during annealing with high relative quadruplex formation detected with six of ten cations. Analogous annealing experiments with Ig9 resulted in complex formation with all ten cations, and the majority of the resulting complexes were pentaplexes. CD results indicated most of the original complexes survived the desalting process necessary for ESI-MS analysis. In addition, several complexes, especially the pentaplexes, were found to be capable of cation exchange with ammonium ions. Ab initio calculations were conducted for isoguanine tetrads and pentads coordinated with all ten cations to predict the most energetically stable structures of the complexes in the gas phase. The observed preference of forming quadruplexes versus pentaplexes as a function of the coordinated cation can be interpreted by the calculated reaction energies of both the tetrads and pentads in combination with the distortion energies of tetrads. PMID:19746468

  6. Antiviral effect of cationic compounds on bacteriophages

    PubMed Central

    Ly-Chatain, Mai H.; Moussaoui, Saliha; Vera, Annabelle; Rigobello, Véronique; Demarigny, Yann

    2013-01-01

    The antiviral activity of several cationic compounds – cetyltrimethylammonium bromide (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 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. PMID:23487495

  7. Derivatisation of buforin IIb, a cationic henicosapeptide, to afford its complexation to platinum(ii) resulting in a novel platinum(ii)-buforin IIb conjugate with anti-cancer activity.

    PubMed

    Parker, J P; Devocelle, M; Morgan, M P; Marmion, C J

    2016-08-16

    Herein we report the synthesis of buforin IIb, its novel malonate derivative malBuf and its Pt(ii) complex cis-[Pt(NH3)2(malBuf-2H)]. We decided to harness the cell targeting, cell-penetrating and anti-proliferative effects of buforin IIb to help target a cytotoxic dose of a Pt DNA binding species, {Pt(NH3)2} to cancer cells whilst also delivering a peptide with potent anti-cancer properties. Preliminary in vitro data shows cis-[Pt(NH3)2(malBuf-2H)] to be more cytotoxic against the cisplatin resistant ovarian cancer cell line (A2780cisR) relative to buforin IIb, cisplatin and cis-[Pt(NH3)2(malonate)]. PMID:27292799

  8. Water Adsorption on Free Cobalt Cluster Cations.

    PubMed

    Kiawi, Denis M; Bakker, Joost M; Oomens, Jos; Buma, Wybren Jan; Jamshidi, Zahra; Visscher, Lucas; Waters, L B F M

    2015-11-01

    Cationic cobalt clusters complexed with water Con(+)-H2O (n = 6-20) are produced through laser ablation and investigated via infrared multiple photon dissociation (IR-MPD) spectroscopy in the 200-1700 cm(-1) spectral range. All spectra exhibit a resonance close to the 1595 cm(-1) frequency of the free water bending vibration, indicating that the water molecule remains intact upon adsorption. For n = 6, the frequency of this band is blue-shifted, but it gradually converges to the free water value with increasing cluster size. In the lower-frequency range (200-650 cm(-1)) the spectra contain several bands which show a very regular frequency evolution, suggesting that the exact cluster geometry has little effect on the water-surface interaction. Density functional theory (DFT) calculations are carried out at the OPBE/TZP level for three representative sizes (n = 6, 9, 13) and indicate that the vibrations responsible for the resonances correspond to bending and torsional modes between the cluster and water moieties. The potential energy surfaces describing these interactions are very shallow, making the calculated harmonic frequencies and IR intensities very sensitive to small geometrical perturbations. We conclude that harmonic frequency calculations on (local) minima structures provide insufficient information for these types of cluster complexes and need to be complemented with calculations that provide a more extensive sampling of the potential energy surface. PMID:26447780

  9. Interactions of Monovalent Organic Cations with Pillared Clays.

    PubMed

    Mishael; Rytwo; Nir; Crespin; Annabi-Bergaya; Van Damme H

    1999-01-01

    Interactions between an acid-activated pillared clay and several organic cations including dyes (methylene blue, MB; crystal violet, CV; acriflavin, AF) and benzyl derivatives (benzyltrimethylammonium, BTMA; benzyltriethylammonium, BTEA) were studied by adsorption measurements and X-ray diffraction. When the dyes were adsorbed from low ionic strength solutions, adsorption was irreversible but saturated at levels below the cation exchange capacity (CEC) of the clay (0.6 meq/g). The difference with CEC value was largest for CV. This mode of adsorption was interpreted in terms of interlayer adsorption with steric hindrance in the pillared galleries. On the other hand, when the dyes were adsorbed from high ionic strength solutions, adsorption levels well beyond the CEC of the clay could be reached, in particular for MB and CV. This was interpreted in terms of a second adsorption mode, involving formation of molecular aggregates on the outer surface of the clay, as evidenced by X-ray diffraction. The behavior of the cationic benzyl derivatives was markedly different, with an adsorption level always below the CEC and a decrease of adsorption as the ionic strength was increased, as expected for non-complex-forming cations. Copyright 1999 Academic Press. PMID:9878144

  10. Cation-specific effects on enzymatic catalysis driven by interactions at the tunnel mouth.

    PubMed

    Štěpánková, Veronika; Paterová, Jana; Damborský, Jiří; Jungwirth, Pavel; Chaloupková, Radka; Heyda, Jan

    2013-05-30

    Cationic specificity which follows the Hofmeister series has been established for the catalytic efficiency of haloalkane dehalogenase LinB by a combination of molecular dynamics simulations and enzyme kinetic experiments. Simulations provided a detailed molecular picture of cation interactions with negatively charged residues on the protein surface, particularly at the tunnel mouth leading to the enzyme active site. On the basis of the binding affinities, cations were ordered as Na(+) > K(+) > Rb(+) > Cs(+). In agreement with this result, a steady-state kinetic analysis disclosed that the smaller alkali cations influence formation and productivity of enzyme-substrate complexes more efficiently than the larger ones. A subsequent systematic investigation of two LinB mutants with engineered charge in the cation-binding site revealed that the observed cation affinities are enhanced by increasing the number of negatively charged residues at the tunnel mouth, and vice versa, reduced by decreasing this number. However, the cation-specific effects are overwhelmed by strong electrostatic interactions in the former case. Interestingly, the substrate inhibition of the mutant LinB L177D in the presence of chloride salts was 7 times lower than that of LinB wild type in glycine buffer. Our work provides new insight into the mechanisms of specific cation effects on enzyme activity and suggests a potential strategy for suppression of substrate inhibition by the combination of protein and medium engineering. PMID:23627286

  11. Orientation preferences of backbone secondary amide functional groups in peptide nucleic acid complexes: quantum chemical calculations reveal an intrinsic preference of cationic D-amino acid-based chiral PNA analogues for the P-form.

    PubMed

    Topham, Christopher M; Smith, Jeremy C

    2007-02-01

    Geometric descriptions of nonideal interresidue hydrogen bonding and backbone-base water bridging in the minor groove are established in terms of polyamide backbone carbonyl group orientation from analyses of residue junction conformers in experimentally determined peptide nucleic acid (PNA) complexes. Two types of interresidue hydrogen bonding are identified in PNA conformers in heteroduplexes with nucleic acids that adopt A-like basepair stacking. Quantum chemical calculations on the binding of a water molecule to an O2 base atom in glycine-based PNA thymine dimers indicate that junctions modeled with P-form backbone conformations are lower in energy than a dimer comprising the predominant conformation observed in A-like helices. It is further shown in model systems that PNA analogs based on D-lysine are better able to preorganize in a conformation exclusive to P-form helices than is glycine-based PNA. An intrinsic preference for this conformation is also exhibited by positively charged chiral PNA dimers carrying 3-amino-D-alanine or 4-aza-D-leucine residue units that provide for additional rigidity by side-chain hydrogen bonding to the backbone carbonyl oxygen. Structural modifications stabilizing P-form helices may obviate the need for large heterocycles to target DNA pyrimidine bases via PNA.DNA-PNA triplex formation. Quantum chemical modeling methods are used to propose candidate PNA Hoogsteen strand designs. PMID:17071666

  12. Anti-inflammatory activity of cationic lipids.

    PubMed

    Filion, M C; Phillips, N C

    1997-10-01

    1. The effect of liposome phospholipid composition has been assumed to be relatively unimportant because of the presumed inert nature of phospholipids. 2. We have previously shown that cationic liposome formulations used for gene therapy inhibit, through their cationic component, the synthesis by activated macrophages of the pro-inflammatory mediators nitric oxide (NO) and tumour necrosis factor-alpha (TNF-alpha). 3. In this study, we have evaluated the ability of different cationic lipids to reduce footpad inflammation induced by carrageenan and by sheep red blood cell challenge. 4. Parenteral (i.p. or s.c) or local injection of the positively charged lipids dimethyldioctadecylammomium bromide (DDAB), dioleyoltrimethylammonium propane (DOTAP), dimyristoyltrimethylammonium propane (DMTAP) or dimethylaminoethanecarbamoyl cholesterol (DC-Chol) significantly reduced the inflammation observed in both models in a dose-dependent manner (maximum inhibition: 70-95%). 5. Cationic lipids associated with dioleyol- or dipalmitoyl-phosphatidylethanolamine retained their anti-inflammatory activity while cationic lipids associated with dipalmitoylphosphatidylcholine (DPPC) or dimyristoylphosphatidylglycerol (DMPG) showed no anti-inflammatory activity, indicating that the release of cationic lipids into the macrophage cytoplasm is a necessary step for anti-inflammatory activity. The anti-inflammatory activity of cationic lipids was abrogated by the addition of dipalmitoylphosphatidylethanolamine-poly(ethylene)glycol-2000 (DPPE-PEG2000) which blocks the interaction of cationic lipids with macrophages. 6. Because of the significant role of protein kinase C (PKC) in the inflammatory process we have determined whether the cationic lipids used in this study inhibit PKC activity. The cationic lipids significantly inhibited the activity of PKC but not the activity of a non-related protein kinase, PKA. The synthesis of interleukin-6 (IL-6), which is not dependent on PKC activity for its

  13. Selone-stabilized aryltellurenyl cations.

    PubMed

    Yadav, Sangeeta; Raju, Saravanan; Singh, Harkesh B; Butcher, Ray J

    2016-05-28

    Controlled bromination of a diarylditelluride, R2Te2 (R = 2,6-dimethylphenyl) (6) in dichloromethane led to the formation of a Te(II)-Te(IV) mixed-valent tellurenyl bromide, RBr2TeTeR (7). A further reaction of 7 with 1,3-dibutylbenzimidazolin-2-selone, C15H22N2Se (L) (9), produced the first selone adduct of the 2,6-dimethylphenyltellurenyl cation with the 2,6-dimethylphenyltellurium dibromide anion, [(2,6-Me2C6H3)Te(L)](+)[(2,6-Me2C6H3)TeBr2](-) (10). The red colored cationic adduct 10 is not stable in acetonitrile and disproportionated to give the selone adduct of 2,6-dimethylphenyltellurenyl bromide, [(2,6-Me2C6H3)Te(L)Br] (11b) and bis(2,6-dimethylphenyl)tellurium dibromide, [(2,6-Me2C6H3)2TeBr2], (13). The metathesis reaction of 11b with AgBF4 produced a stable dark red colored selone adduct of the 2,6-dimethylphenyltellurenyl cation with the BF4(-) anion, [(2,6-Me2C6H3)Te(L)](+)BF4(-) (15). The selone adducts of aryltellurenyl halides, i.e. [(2,6-Me2C6H3)Te(L)X] (X = Cl, Br, I) (11a-11c), have been synthesized by a one-pot reaction of 6 with an equimolar mixture of 9 and 1,3-dibutylbenzimidazolin-2-dihaloselones, C15H22N2SeX2 (14a-14c). Triphenylphosphine (PPh3), when treated with [(2,6-Me2C6H3)Te(L)X] (11a-11c), substitutes selone from the adduct to afford the triphenylphosphine adducts of aryltellurenyl halides, [(2,6-Me2C6H3)Te(PPh3)X] (16a-16c). PMID:27111528

  14. Effect of Mechanical Agitation on Cationic Liposome Transport across an Unstirred Water Layer in Caco-2 Cells.

    PubMed

    Kono, Yusuke; Iwasaki, Ayu; Matsuoka, Kenta; Fujita, Takuya

    2016-01-01

    To develop an effective oral delivery system for plasmid DNA (pDNA) using cationic liposomes, it is necessary to clarify the characteristics of uptake and transport of cationic liposome/pDNA complexes into the intestinal epithelium. In particular, evaluation of the involvement of an unstirred water layer (UWL), which is a considerable permeability barrier, in cationic liposome transport is very important. Here, we investigated the effects of a UWL on the transfection efficiency of cationic liposome/pDNA complexes into a Caco-2 cell monolayer. When Caco-2 cells were transfected with cationic liposome/pDNA complexes in shaking cultures to reduce the thickness of the UWL, gene expression was significantly higher in Caco-2 cells compared with static cultures. We also found that this enhancement of gene expression by shaking was not attributable to activation of transcription factors such as activator protein-1 and nuclear factor-kappaB (NF-κB). In addition, the increase in gene expression by mechanical agitation was observed at all charge ratios (1.5, 2.3, 3.1, 4.5) of cationic liposome/pDNA complexes. Transport experiments using Transwells demonstrated that mechanical agitation increased the uptake of cationic liposome/pDNA complexes by Caco-2 cells, whereas transport of the complexes across a Caco-2 cell monolayer did not occurr. Moreover, the augmentation of the gene expression of cationic liposome/pDNA complexes by shaking was observed in Madin-Darby canine kidney cells. These results indicate that a UWL greatly affects the uptake and transfection efficiency of cationic liposome/pDNA complexes into an epithelial monolayer in vitro. PMID:27476939

  15. Cation-poor complex metallic alloys in Ba(Eu)–Au–Al(Ga) systems: Identifying the keys that control structural arrangements and atom distributions at the atomic level

    DOE PAGESBeta

    Smetana, Volodymyr; Steinberg, Simon; Mudryk, Yaroslav; Pecharsky, Vitalij; Miller, Gordon J.; Mudring, Anja -Verena

    2015-10-19

    Four complex intermetallic compounds BaAu6±xGa6±y (x = 1, y = 0.9) (I), BaAu6±xAl6±y (x = 0.9, y = 0.6) (II), EuAu6.2Ga5.8 (III), and EuAu6.1Al5.9 (IV) have been synthesized, and their structures and homogeneity ranges have been determined by single crystal and powder X-ray diffraction. Whereas I and II originate from the NaZn13-type structure (cF104–112, Fm3C), III (tP52, P4/nbm) is derived from the tetragonal Ce2Ni17Si9-type, and IV (oP104, Pbcm) crystallizes in a new orthorhombic structure type. Both I and II feature formally anionic networks with completely mixed site occupation by Au and triel (Tr = Al, Ga) atoms, while a successivemore » decrease of local symmetry from the parental structures of I and II to III and, ultimately, to IV correlates with increasing separation of Au and Tr on individual crystallographic sites. Density functional theory-based calculations were employed to determine the crystallographic site preferences of Au and the respective triel element to elucidate reasons for the atom distribution (“coloring scheme”). Chemical bonding analyses for two different “EuAu6Tr6” models reveal maximization of the number of heteroatomic Au–Tr bonds as the driving force for atom organization. The Fermi levels fall in broad pseudogaps for both models allowing some electronic flexibility. Spin-polarized band structure calculations on the “EuAu6Tr6” models hint to singlet ground states for europium and long-range magnetic coupling for both EuAu6.2Ga5.8 (III) and EuAu6.1Al5.9 (IV). This is substantiated by experimental evidence because both compounds show nearly identical magnetic behavior with ferromagnetic transitions at TC = 6 K and net magnetic moments of 7.35 μB/f.u. at 2 K. As a result, the effective moments of 8.3 μB/f.u., determined from Curie–Weiss fits, point to divalent oxidation states for europium in both III and IV.« less

  16. Cation-coupled bicarbonate transporters.

    PubMed

    Aalkjaer, Christian; Boedtkjer, Ebbe; Choi, Inyeong; Lee, Soojung

    2014-10-01

    Cation-coupled HCO3(-) transport was initially identified in the mid-1970s when pioneering studies showed that acid extrusion from cells is stimulated by CO2/HCO3(-) and associated with Na(+) and Cl(-) movement. The first Na(+)-coupled bicarbonate transporter (NCBT) was expression-cloned in the late 1990s. There are currently five mammalian NCBTs in the SLC4-family: the electrogenic Na,HCO3-cotransporters NBCe1 and NBCe2 (SLC4A4 and SLC4A5 gene products); the electroneutral Na,HCO3-cotransporter NBCn1 (SLC4A7 gene product); the Na(+)-driven Cl,HCO3-exchanger NDCBE (SLC4A8 gene product); and NBCn2/NCBE (SLC4A10 gene product), which has been characterized as an electroneutral Na,HCO3-cotransporter or a Na(+)-driven Cl,HCO3-exchanger. Despite the similarity in amino acid sequence and predicted structure among the NCBTs of the SLC4-family, they exhibit distinct differences in ion dependency, transport function, pharmacological properties, and interactions with other proteins. In epithelia, NCBTs are involved in transcellular movement of acid-base equivalents and intracellular pH control. In nonepithelial tissues, NCBTs contribute to intracellular pH regulation; and hence, they are crucial for diverse tissue functions including neuronal discharge, sensory neuron development, performance of the heart, and vascular tone regulation. The function and expression levels of the NCBTs are generally sensitive to intracellular and systemic pH. Animal models have revealed pathophysiological roles of the transporters in disease states including metabolic acidosis, hypertension, visual defects, and epileptic seizures. Studies are being conducted to understand the physiological consequences of genetic polymorphisms in the SLC4-members, which are associated with cancer, hypertension, and drug addiction. Here, we describe the current knowledge regarding the function, structure, and regulation of the mammalian cation-coupled HCO3(-) transporters of the SLC4-family. PMID:25428855

  17. Cation-Coupled Bicarbonate Transporters

    PubMed Central

    Aalkjaer, Christian; Boedtkjer, Ebbe; Choi, Inyeong; Lee, Soojung

    2016-01-01

    Cation-coupled HCO3− transport was initially identified in the mid-1970s when pioneering studies showed that acid extrusion from cells is stimulated by CO2/HCO3− and associated with Na+ and Cl− movement. The first Na+-coupled bicarbonate transporter (NCBT) was expression-cloned in the late 1990s. There are currently five mammalian NCBTs in the SLC4-family: the electrogenic Na,HCO3-cotransporters NBCe1 and NBCe2 (SLC4A4 and SLC4A5 gene products); the electroneutral Na,HCO3-cotransporter NBCn1 (SLC4A7 gene product); the Na+-driven Cl,HCO3-exchanger NDCBE (SLC4A8 gene product); and NBCn2/NCBE (SLC4A10 gene product), which has been characterized as an electroneutral Na,HCO3-cotransporter or a Na+-driven Cl,HCO3-exchanger. Despite the similarity in amino acid sequence and predicted structure among the NCBTs of the SLC4-family, they exhibit distinct differences in ion dependency, transport function, pharmacological properties, and interactions with other proteins. In epithelia, NCBTs are involved in transcellular movement of acid-base equivalents and intracellular pH control. In nonepithelial tissues, NCBTs contribute to intracellular pH regulation; and hence, they are crucial for diverse tissue functions including neuronal discharge, sensory neuron development, performance of the heart, and vascular tone regulation. The function and expression levels of the NCBTs are generally sensitive to intracellular and systemic pH. Animal models have revealed pathophysiological roles of the transporters in disease states including metabolic acidosis, hypertension, visual defects, and epileptic seizures. Studies are being conducted to understand the physiological consequences of genetic polymorphisms in the SLC4-members, which are associated with cancer, hypertension, and drug addiction. Here, we describe the current knowledge regarding the function, structure, and regulation of the mammalian cation-coupled HCO3− transporters of the SLC4-family. PMID:25428855

  18. Cation-poor complex metallic alloys in Ba(Eu)–Au–Al(Ga) systems: Identifying the keys that control structural arrangements and atom distributions at the atomic level

    SciTech Connect

    Smetana, Volodymyr; Steinberg, Simon; Mudryk, Yaroslav; Pecharsky, Vitalij; Miller, Gordon J.; Mudring, Anja -Verena

    2015-10-19

    Four complex intermetallic compounds BaAu6±xGa6±y (x = 1, y = 0.9) (I), BaAu6±xAl6±y (x = 0.9, y = 0.6) (II), EuAu6.2Ga5.8 (III), and EuAu6.1Al5.9 (IV) have been synthesized, and their structures and homogeneity ranges have been determined by single crystal and powder X-ray diffraction. Whereas I and II originate from the NaZn13-type structure (cF104–112, Fm3C), III (tP52, P4/nbm) is derived from the tetragonal Ce2Ni17Si9-type, and IV (oP104, Pbcm) crystallizes in a new orthorhombic structure type. Both I and II feature formally anionic networks with completely mixed site occupation by Au and triel (Tr = Al, Ga) atoms, while a successive decrease of local symmetry from the parental structures of I and II to III and, ultimately, to IV correlates with increasing separation of Au and Tr on individual crystallographic sites. Density functional theory-based calculations were employed to determine the crystallographic site preferences of Au and the respective triel element to elucidate reasons for the atom distribution (“coloring scheme”). Chemical bonding analyses for two different “EuAu6Tr6” models reveal maximization of the number of heteroatomic Au–Tr bonds as the driving force for atom organization. The Fermi levels fall in broad pseudogaps for both models allowing some electronic flexibility. Spin-polarized band structure calculations on the “EuAu6Tr6” models hint to singlet ground states for europium and long-range magnetic coupling for both EuAu6.2Ga5.8 (III) and EuAu6.1Al5.9 (IV). This is substantiated by experimental evidence because both compounds show nearly identical magnetic behavior with ferromagnetic transitions at TC = 6 K and net magnetic moments of 7.35 μB/f.u. at 2 K. As a result, the effective moments

  19. Method for encapsulating and isolating hazardous cations, medium for encapsulating and isolating hazardous cations

    DOEpatents

    Wasserman, Stephen R.; Anderson, Kenneth B.; Song, Kang; Yuchs, Steven E.; Marshall, Christopher L.

    1998-01-01

    A method for encapsulating hazardous cations is provided comprising supplying a pretreated substrate containing the cations; contacting the substrate with an organo-silane compound to form a coating on the substrate; and allowing the coating to cure. A medium for containing hazardous cations is also provided, comprising a substrate having ion-exchange capacity and a silane-containing coating on the substrate.

  20. Oxoferryl porphyrin cation radicals in model systems: Evidence for variable metal-radical spin coupling

    NASA Astrophysics Data System (ADS)

    Bill, E.; Bominaar, E. L.; Ding, X.-Q.; Trautwein, A. X.; Winkler, H.; Mandon, D.; Weiss, R.; Gold, A.; Jayaraj, K.; Toney, G. E.

    1990-07-01

    Magnetic properties of frozen solutions of highly oxidized iron porphyrin complexes were investigated by EPR and Mössbauer spectroscopy. The Mössbauer spectra, recorded at low temperatures in various magnetic fields, were analyzed on the basis of spin Hamiltonian simulations. Spin coupling between ferryl iron (FeIV) and porphyrin cation radical was taken into account explicitly. Hyperfine and spin-coupling parameters are given for several complexes, together with zero-field parameters. One of the complexes exhibits weak spin coupling, it is the first model system exhibiting properties comparable to those of the oxoferryl cation radical enzyme Horse Radish Peroxidase I.

  1. Association between cationic liposomes and low molecular weight hyaluronic acid.

    PubMed

    Gasperini, Antonio A M; Puentes-Martinez, Ximena E; Balbino, Tiago Albertini; Rigoletto, Thais de Paula; Corrêa, Gabriela de Sá Cavalcanti; Cassago, Alexandre; Portugal, Rodrigo Villares; de La Torre, Lucimara Gaziola; Cavalcanti, Leide P

    2015-03-24

    This work presents a study of the association between low molecular weight hyaluronic acid (16 kDa HA) and cationic liposomes composed of egg phosphatidylcholine (EPC), 1,2-dioleoyl-sn-glycero-3-phosphoethanolamine (DOPE), and 1,2-dioleoyl-3-trimethylammonium-propane (DOTAP). The cationic liposome/HA complexes were evaluated to determine their mesoscopic structure, average size, zeta potential, and morphology as a function of the amount of HA in the system. Small angle X-ray scattering results revealed that neighboring cationic liposomes either stick together after a partial coating of low concentration HA or disperse completely in excess of HA, but they never assemble as multilamellar vesicles. Cryo-transmission electron microscopy images confirm the existence of unilamellar vesicles and large aggregates of unilamellar vesicles for HA fractions up to 80% (w/w). High concentrations of HA (> 20% w/w) proved to be efficient for coating extruded liposomes, leading to particle complexes with sizes in the nanoscale range and a negative zeta potential. PMID:25730494

  2. Novel cationic SLN containing a synthesized single-tailed lipid as a modifier for gene delivery

    NASA Astrophysics Data System (ADS)

    Yu, Wangyang; Liu, Chunxi; Ye, Jiesheng; Zou, Weiwei; Zhang, Na; Xu, Wenfang

    2009-05-01

    Cationic solid lipid nanoparticles (SLN) can bind DNA directly via ionic interaction and mediate in vitro gene transfection. However, toxicity is still an obstacle, which is strongly dependent on the cationic lipid used. In the present study, a novel single-tailed cationic lipid, 6-lauroxyhexyl lysinate (LHLN), was synthesized and used as a modifier to prepare stable SLN-DNA complexes by a nanoprecipitation method. The commonly used cationic lipid cetyltrimethylammonium bromide (CTAB) modified SLN-DNA formulation served as a contrast. These two formulations were characterized and compared in terms of morphology, particle size, surface charge, DNA binding capacity, release profile, cytotoxicity, and transfection efficiency. The LHLN SLN-DNA complexes had a similar spherical morphology, a relatively narrow particle size distribution and a more remarkable DNA loading capability compared to the CTAB ones. Most importantly, LHLN modified SLN had a higher gene transfection efficiency than the naked DNA and CTAB ones, which was approximately equal to that of Lipofectamine-DNA complexes, and a lower cytotoxicity compared with CTAB-SLN and Lipofectamine 2000. Thus, the novel cationic SLN can achieve efficient transfection of plasmid DNA, and to some extent reduce the cytotoxicity, which might overcome some drawbacks of the conventional cationic nanocarriers in vivo and may become a promising non-viral gene therapy vector.

  3. Association Mechanisms of Unsaturated C2 Hydrocarbons with Their Cations: Acetylene and Ethylene

    NASA Technical Reports Server (NTRS)

    Bera, Partha P.; Head-Gordon, Martin; Lee, Timothy J.

    2013-01-01

    The ion-molecule association mechanism of acetylene and ethylene with their cations is investigated by ab initio quantum chemical methods to understand the structures, association energies, and the vibrational and electronic spectra of the products. Stable puckered cyclic isomers are found as the result of first forming less stable linear and bridge isomers. The puckered cyclic complexes are calculated to be strongly bound, by 87, 35 and 56 kcal/mol for acetylene-acetylene cation, ethylene-ethylene cation and acetylene-ethylene cation, respectively. These stable complexes may be intermediates that participate in further association reactions. There are no association barriers, and no significant inter-conversion barriers, so the initial linear and bridge encounter complexes are unlikely to be observable. However, the energy gap between the bridged and cyclic puckered isomers greatly differs from complex to complex: it is 44 kcal/mol in C4H4 +, but only 6 kcal/mol in C4H8 +. The accurate CCSD(T) calculations summarized above are also compared against less computationally expensive MP2 and density functional theory (DFT) calculations for structures, relative energies, and vibrational spectra. Calculated vibrational spectra are compared against available experiments for cyclobutadiene cation. Electronic spectra are also calculated using time-dependent DFT.

  4. Advancements in Anion Exchange Membrane Cations

    SciTech Connect

    Sturgeon, Matthew R.; Long, Hai; Park, Andrew M.; Pivovar, Bryan S.

    2015-10-15

    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.

  5. Tripodal Receptors for Cation and Anion Sensors

    PubMed Central

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

    2006-01-01

    This review discusses different types of artificial tripodal receptors for the selective recognition and sensing of cations and anions. Examples on the relationship between structure and selectivity towards cations and anions are described. Furthermore, their applications as potentiometric ion sensing are emphasised, along with their potential applications in optical sensors or optodes.

  6. Separation of alkali, alkaline earth and rare earth cations by liquid membranes containing macrocyclic carriers. Third progress report, September 1, 1980-April 1, 1981

    SciTech Connect

    Christensen, J.J.

    1981-04-15

    The overall objective of this project is to study the use of liquid membrane systems employing macrocyclic ligand carriers in making separations among metal cations. During the third year of the project, work continued in the development of a mathematical model to describe cation transport. The model was originally developed to describe the relationship between cation transport rate (J/sub M/) and the cation-macrocycle stability constant (K). The model was tested by determining the rates of transport of alkali and alkaline earth cations through chloroform membranes containing carrier ligands where the stability constants for their reaction with cations in methanol were known. From the results, it is clear that the model correctly describes the dependence of J/sub M/ on log K. The model also correctly describes the effect of cation concentration and carrier concentration on cation transport rates, as detailed in the previous progress report. During the third year of the project, the transport model was expanded so as to apply to competitive transport of cations from mixtures of two cations in the source aqueous phase. Data were collected under these conditions and the ability of the model to predict the flux of each cation was tested. Representative data of this type are presented along with corresponding data which were obtained when each cation was transported by the same carrier from a source phase containing only that cation. Comparison of transport rates determined under the two experimental conditions indicates that the relationship between the two sets of data is complex. To date, a few of these data involving transport from binary cation mixtures have been tested against the transport model. It was found that the model correctly predicts the cation fluxes from cation mixtures. These preliminary results indicate that the transport model can successfully predict separation factors when cation mixtures are used.

  7. Organo-Lewis acid as cocatalyst for cationic homogeneous Ziegler-Natta olefin polymerizations

    DOEpatents

    Marks, Tobin J.; Chen, You-Xian

    2001-01-01

    Organo-Lewis acids of the formula BR'R".sub.2 wherein B is boron, R' is fluorinated biphenyl, and R" is a fluorinated phenyl, fluorinated biphenyl, or fluorinated polycyclic fused ring group, and cationic metallocene complexes formed therewith. Such complexes are useful as polymerization catalysts.

  8. Organo-Lewis acid as cocatalyst for cationic homogeneous Ziegler-Natta olefin polymerizations

    DOEpatents

    Marks, Tobin J.; Chen, You-Xian

    2002-01-01

    Organo-Lewis acids of the formula BR'R".sub.2 wherein B is boron, R' is fluorinated biphenyl, and R" is a fluorinated phenyl, fluorinated biphenyl, or fluorinated polycyclic fused ring group, and cationic metallocene complexes formed therewith. Such complexes are useful as polymerization catalysts.

  9. Structural variation in cation-assisted assembly of high-nuclearity Mn arsonate and phosphonate wheels.

    PubMed

    Chimamkpam, Theresa O; Clérac, Rodolphe; Mitcov, Dmitri; Twamley, Brendan; Venkatesan, Munuswamy; Schmitt, Wolfgang

    2016-01-28

    Comproportionation reactions between MnCl2 and KMnO4 in the presence of arsonate or phosphonate ligands promote the cation-assisted assembly of high-nuclearity, wheel-shaped or toroidal {Mn8} () and {Mn24} () complexes; the closely corresponding reaction systems provide insights into the complexation behaviour of homologous phosphonate/arsonate ligand species. PMID:26740231

  10. The perforin pore facilitates the delivery of cationic cargos.

    PubMed

    Stewart, Sarah E; Kondos, Stephanie C; Matthews, Antony Y; D'Angelo, Michael E; Dunstone, Michelle A; Whisstock, James C; Trapani, Joseph A; Bird, Phillip I

    2014-03-28

    Cytotoxic lymphocytes eliminate virally infected or neoplastic cells through the action of cytotoxic proteases (granzymes). The pore-forming protein perforin is essential for delivery of granzymes into the cytoplasm of target cells; however the mechanism of this delivery is incompletely understood. Perforin contains a membrane attack complex/perforin (MACPF) domain and oligomerizes to form an aqueous pore in the plasma membrane; therefore the simplest (and best supported) model suggests that granzymes passively diffuse through the perforin pore into the cytoplasm of the target cell. Here we demonstrate that perforin preferentially delivers cationic molecules while anionic and neutral cargoes are delivered inefficiently. Furthermore, another distantly related pore-forming MACPF protein, pleurotolysin (from the oyster mushroom), also favors the delivery of cationic molecules, and efficiently delivers human granzyme B. We propose that this facilitated diffusion is due to conserved features of oligomerized MACPF proteins, which may include an anionic lumen. PMID:24558045

  11. The role of helper lipids in cationic liposome-mediated gene transfer.

    PubMed Central

    Hui, S W; Langner, M; Zhao, Y L; Ross, P; Hurley, E; Chan, K

    1996-01-01

    In the procedure for cationic liposome-mediated transfection, the cationic lipid is usually mixed with a "helper lipid" to increase its transfection potency. The importance of helper lipids, including dioleoylphosphatidylcholine (DOPC) and phosphatidylethanolamine (dioleoyl PE), DO was examined. Freeze-fracture electron microscopy of DNA:cationic complexes containing the pSV-beta-GAL plasmid DNA, the cationic lipid dioleoyl trimethylammonium propane, and these helper lipids showed that the most efficient mixtures were aggregates of ensheathed DNA and fused liposomes. PE-containing complexes aggregated rapidly when added to culture media containing polyanions, whereas PC-containing complexes did not. However, more granules of PC-containing complexes were formed on cell surfaces after the complexes were added to Chinese hamster ovary (CHO) cells in transfection media. Pronase treatment inhibited transfection, whereas dilute poly-L-lysine enhanced transfection, indicating that the attachment of DNA:liposome complexes to cell surfaces was mediated by electrostatic interaction. Fluorescence spectroscopy studies confirmed that more PC-containing complexes than PE-containing complexes were associated with CHO cells, and that more PC-containing complexes were located in a low pH environment (likely to be within endosomes) with time. Cytochalasin-B had a stronger inhibitory effect on PC-containing liposome-mediated than on PE-containing liposome-mediated transfection. Confocal microscopic recording of the fluorescently label lipid and DNA uptake process indicated that many granules of DNA:cationic liposome complexes were internalized as a whole, whereas some DNA aggregates were left out on the cell surfaces after liposomes of the complexes fused with the plasma membranes. For CHO cells, endocytosis seems to be the main uptake pathway of DNA:cationic liposome complexes. More PC-containing granules than PE-containing granules were formed on cell surfaces by cytoskeleton

  12. A novel Ag+ cation sensor based on polyamidoamine dendrimer modified with 1,8-naphthalimide derivatives

    NASA Astrophysics Data System (ADS)

    Dodangeh, Mohammad; Gharanjig, Kamaladin; Arami, Mokhtar

    2016-02-01

    In this study, 4-amino-1,8-naphthalimide-conjugated polyamidoamine dendrimer was synthesized and characterized and its potentiality as a cation sensor was investigated. 4-Amino-1,8-naphthalic anhydride reacted with polyamidoamine dendrimer and the product was characterized using FTIR, 1H NMR, 13C NMR and melting point analysis method. The synthesized compound was applied to detect various cations in water media and N,N-dimethylformamide (DMF) via monitoring the quenching of the fluorescence intensity. Furthermore, various metal cations including Cu2 +, Ni2 +, Zn2 +, Pb2 +,Ca2 +, Ba2 +, Cd2 +, Hg2 +, Fe2 +, Fe3 + and Ag+ were tested. The complexes formed between the synthesized compound and metal cations in solution and their effects on Photoinduced Electron Transfer (PET) process were investigated regarding the potential application of the newly-synthesized dendrimer as a colorimetric and fluorescent sensor for such cations. The results clearly confirmed that the 1,8-naphthalimide groups surrounding the central dendrimer core showed strong green fluorescence emission at 553 nm. This effect considerably decreased with the introduction of all cations, except Ag+ where the fluorescence quenching effect was remarkable and more dominant. Therefore, it can be concluded that the synthesized dye has the potentiality of being a highly sensitive and selective fluorescence sensor for Ag+ cation.

  13. Closed-Shell Polycyclic Aromatic Hydrocarbon Cations: A New Category of Interstellar Polycyclic Aromatic Hydrocarbons

    NASA Technical Reports Server (NTRS)

    Hudgins, Douglas M.; Bauschlicher, Charles W., Jr.; Allamandola, Louis J.; DeVincenzi, Donald (Technical Monitor)

    2001-01-01

    Density functional theory has been employed to calculate the harmonic frequencies and intensities of a range of polycyclic aromatic hydrocarbon (PAH) cations that explore both size and electronic structure effects of the infrared spectroscopic properties of these species. The sample extends the size range of PAH species considered to more than 50 carbon atoms and includes several representatives from each of two heretofore unexplored categories of PAH cations: (1) fully benzenoid PAH cations whose carbon skeleton is composed of an odd number of carbon atoms (C(sub odd) PAHs); and (2) protonated PAH cations (HPAH+). Unlike the radical electronic structures of the PAH cations that have been the subject of previous theoretical and experimental work, the species in these two classes have a closed-shell electronic configuration. The calculated spectra of circumcoronene, C54H18 in both neutral and (radical) cationic form are also reported and compared with those of the other species. Overall, the C(sub odd) PAHs spectra are dominated by strong CC stretching modes near 1600 cm(exp -1) and display spectra that are remarkably insensitive to molecular size. The HPAH+ species evince a more complex spectrum consistent with the added contributions of aliphatic modes and their generally lower symmetry. Finally, for both classes of closed-shell cations, the intensity of the aromatic CH stretching modes is found to increase with molecular size far out of proportion with the number of CH groups, approaching a value more typical of neutral PAHs for the largest species studied.

  14. Transport of Sulfide-Reduced Graphene Oxide in Saturated Quartz Sand: Cation-Dependent Retention Mechanisms.

    PubMed

    Xia, Tianjiao; Fortner, John D; Zhu, Dongqiang; Qi, Zhichong; Chen, Wei

    2015-10-01

    We describe how the reduction of graphene oxide (GO) via environmentally relevant pathways affects its transport behavior in porous media. A pair of sulfide-reduced GOs (RGOs), prepared by reducing 10 mg/L GO with 0.1 mM Na2S for 3 and 5 days, respectively, exhibited lower mobility than did parent GO in saturated quartz sand. Interestingly, decreased mobility cannot simply be attributed to the increased hydrophobicity and aggregation upon GO reduction because the retention mechanisms of RGOs were highly cation-dependent. In the presence of Na(+) (a representative monovalent cation), the main retention mechanism was deposition in the secondary energy minimum. However, in the presence of Ca(2+) (a model divalent cation), cation bridging between RGO and sand grains became the most predominant retention mechanism; this was because sulfide reduction markedly increased the amount of hydroxyl groups (a strong metal-complexing moiety) on GO. When Na(+) was the background cation, increasing pH (which increased the accumulation of large hydrated Na(+) ions on grain surface) and the presence of Suwannee River humic acid (SRHA) significantly enhanced the transport of RGO, mainly due to steric hindrance. However, pH and SRHA had little effect when Ca(2+) was the background cation because neither affected the extent of cation bridging that controlled particle retention. These findings highlight the significance of abiotic transformations on the fate and transport of GO in aqueous systems. PMID:26348539

  15. Studying the Chemistry of Cationized Triacylglycerols Using Electrospray Ionization Mass Spectrometry and Density Functional Theory Computations

    NASA Astrophysics Data System (ADS)

    Grossert, J. Stuart; Herrera, Lisandra Cubero; Ramaley, Louis; Melanson, Jeremy E.

    2014-08-01

    Analysis of triacylglycerols (TAGs), found as complex mixtures in living organisms, is typically accomplished using liquid chromatography, often coupled to mass spectrometry. TAGs, weak bases not protonated using electrospray ionization, are usually ionized by adduct formation with a cation, including those present in the solvent (e.g., Na+). There are relatively few reports on the binding of TAGs with cations or on the mechanisms by which cationized TAGs fragment. This work examines binding efficiencies, determined by mass spectrometry and computations, for the complexation of TAGs to a range of cations (Na+, Li+, K+, Ag+, NH4 +). While most cations bind to oxygen, Ag+ binding to unsaturation in the acid side chains is significant. The importance of dimer formation, [2TAG + M]+ was demonstrated using several different types of mass spectrometers. From breakdown curves, it became apparent that two or three acid side chains must be attached to glycerol for strong cationization. Possible mechanisms for fragmentation of lithiated TAGs were modeled by computations on tripropionylglycerol. Viable pathways were found for losses of neutral acids and lithium salts of acids from different positions on the glycerol moiety. Novel lactone structures were proposed for the loss of a neutral acid from one position of the glycerol moiety. These were studied further using triple-stage mass spectrometry (MS3). These lactones can account for all the major product ions in the MS3 spectra in both this work and the literature, which should allow for new insights into the challenging analytical methods needed for naturally occurring TAGs.

  16. Cation distributions on rapidly solidified cobalt ferrite

    NASA Technical Reports Server (NTRS)

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

    1990-01-01

    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.

  17. Antibacterial properties of cationic steroid antibiotics.

    PubMed

    Savage, Paul B; Li, Chunhong; Taotafa, Uale; Ding, Bangwei; Guan, Qunying

    2002-11-19

    Cationic steroid antibiotics have been developed that display broad-spectrum antibacterial activity. These compounds are comprised of steroids appended with amine groups arranged to yield facially amphiphilic morphology. Examples of these antibiotics are highly bactericidal, while related compounds effectively permeabilize the outer membranes of Gram-negative bacteria sensitizing these organisms to hydrophobic antibiotics. Cationic steroid antibiotics exhibit various levels of eukaryote vs. prokaryote cell selectivity, and cell selectivity can be increased via charge recognition of prokaryotic cells. Studies of the mechanism of action of these antibiotics suggest that they share mechanistic aspects with cationic peptide antibiotics. PMID:12445638

  18. Preparation, characterization, and efficient transfection of cationic liposomes and nanomagnetic cationic liposomes

    PubMed Central

    Samadikhah, Hamid Reza; Majidi, Asia; Nikkhah, Maryam; Hosseinkhani, Saman

    2011-01-01

    Purpose Cationic liposomes (CLs) are composed of phospholipid bilayers. One of the most important applications of these particles is in drug and gene delivery. However, using CLs to deliver therapeutic nucleic acids and drugs to target organs has some problems, including low transfection efficiency in vivo. The aim of this study was to develop novel CLs containing magnetite to overcome the deficiencies. Materials and methods CLs and magnetic cationic liposomes (MCLs) were prepared using the freeze-dried empty liposome method. Luciferase-harboring vectors (pGL3) were transferred into liposomes and the transfection efficiencies were determined by luciferase assay. Firefly luciferase is one of most popular reporter genes often used to measure the efficiency of gene transfer in vivo and in vitro. Different formulations of liposomes have been used for delivery of different kinds of gene reporters. Lipoplex (liposome–plasmid DNA complexes) formation was monitored by gel retardation assay. Size and charge of lipoplexes were determined using particle size analysis. Chinese hamster ovary cells were transfected by lipoplexes (liposome-pGL3); transfection efficiency and gene expression level was evaluated by luciferase assay. Results High transfection efficiency of plasmid by CLs and novel nanomagnetic CLs was achieved. Moreover, lipoplexes showed less cytotoxicity than polyethyleneimine and Lipofectamine™. Conclusion Novel liposome compositions (1,2-dipalmitoyl-sn-glycero-3-phosphocholine [DPPC]/dioctadecyldimethylammonium bromide [DOAB] and DPPC/cholesterol/DOAB) with high transfection efficiency can be useful in gene delivery in vitro. MCLs can also be used for targeted gene delivery, due to magnetic characteristic for conduction of genes or drugs to target organs. PMID:22072865

  19. Structural Chemistry of Cation-Reacted Bacteriogenic UO2

    NASA Astrophysics Data System (ADS)

    Schofield, E.; Bargar, J.; Bernier-Latmani, R.; Sharp, J.; Veeramani, H.; Clark, D.; Conradson, S.; Mehta, A.

    2007-12-01

    The chemical stability of bacteriogenic uraninite, "UO2", is one of the seminal issues governing its success as an in-situ immobilization strategy in contaminated subsurface locations. Little detail is known about the structure and reactivity of this material, but based on comparison to its closest abiotic analog, UO2+x (0 < x < 0.25), we expect that it is complex and disordered, likely to exhibit non-stoichiometry, and capable of structurally incorporating common ground water cations and U(VI). Such fundamental changes in mineralogy are expected to substantially impact its stability in ground water. In this study, the product of microbial U(VI) reduction under varying conditions of pH, carbonate and divalent cation concentration was investigated. To facilitate x-ray scattering and oxidation kinetics measurements, cleaning methods were investigated to separate the biooxide and organic components. The local and long-range atomic and nano-scale structures of the wet oxides have been measured using EXAFS, WAXS, XPS and TEM. The lattice parameter of the nanoparticulate phase is seen to be consistent with bulk UO2. The first oxygen shell is distorted, indicating a nonstoichiometric composition. A significant change in the lattice parameter and local structure is produced when bacteriogenic UO2 is reacted with divalent cations and NaOH. These findings suggest that bacteriogenic UO2 and its reactivity can be modified by groundwater composition.

  20. Influence of cations on noncovalent interactions between 6-propionyl-2-dimethylaminonaphthalene (PRODAN) and dissolved fulvic and humic acids.

    PubMed

    Gadad, Praveen; Nanny, Mark A

    2008-12-01

    The influence of cations (Na(+), Ca(2+) and Mg(2+)) on noncovalent interactions between 6-propionyl-2-dimethylaminonaphthalene (PRODAN) and dissolved fulvic acids (FAs) (Norman landfill leachate fulvic acid (NLFA) and Suwannee River fulvic acid (SRFA)) and dissolved humic acids (HAs) (Suwannee River humic acid (SRHA) and Leonardite humic acid (LHA)) was examined using steady-state fluorescence spectroscopy at pH 4, 7 and 10 as a function of cation concentration (up to 25-100mM). Regardless of pH and cation concentration, PRODAN quenching by FA was unaffected by cations. However, interactions between PRODAN and HA decreased in the presence of cations at pH 7 and 10. Cation concentrations below the HA charge density resulted in the greatest decrease of PRODAN quenching, while very little additional decrease in PRODAN quenching occurred at cation concentrations above the HA charge density. This suggests that as the HA carboxylic acid functional groups form inner sphere complexes with divalent cations, intramolecular interactions result in a contraction of the HA molecular structure, thereby preventing PRODAN from associating with the condensed aromatic, electron accepting moieties inherent within HA molecules and responsible for PRODAN quenching. However, once the HA carboxylic acid functional groups are fully titrated with divalent cations, PRODAN quenching is no longer significantly influenced by the further addition of cations, even though these additional cations facilitate intermolecular interactions between the HA molecules to form supramolecular HA aggregates that can continue to increase in size. Regardless of FA and HA type, pH, cation type and concentration, the lack of blue-shifted fluorescence emission spectra indicated that micelle-like hydrophobic regions, amenable to PRODAN partitioning, were not formed by intra- and intermolecular interactions of FA and HA. PMID:18849058

  1. Cation-cation clusters in ionic liquids: Cooperative hydrogen bonding overcomes like-charge repulsion

    PubMed Central

    Knorr, Anne; Ludwig, Ralf

    2015-01-01

    Direct spectroscopic evidence for H-bonding between like-charged ions is reported for the ionic liquid, 1-(2-hydroxyethyl)-3-methylimidazolium tetrafluoroborate. New infrared bands in the OH frequency range appear at low temperatures indicating the formation of H-bonded cation-cation clusters similar to those known for water and alcohols. Supported by DFT calculations, these vibrational bands can be assigned to attractive interaction between the hydroxyl groups of the cations. The repulsive Coulomb interaction is overcome by cooperative hydrogen bonding between ions of like charge. The transition energy from purely cation-anion interacting configurations to those including cation-cation H-bonds is determined to be 3–4 kJmol−1. The experimental findings and DFT calculations strongly support the concept of anti-electrostatic hydrogen bonds (AEHBs) as recently suggested by Weinhold and Klein. The like-charge configurations are kinetically stabilized with decreasing temperatures. PMID:26626928

  2. Infrared Photodissociation Spectroscopy of Metal Oxide Carbonyl Cations.

    NASA Astrophysics Data System (ADS)

    Brathwaite, Antonio D.; Duncan, Michael A.

    2013-06-01

    Mass selected metal oxide-carbonyl cations of the form MO_{m}(CO)_{n}^{+} are studied via infrared laser photodissociation spectroscopy, in the 600-2300cm^{1} region. Insight into the structure and bonding of these complexes is obtained from the number of infrared active bands, their relative intensities and their frequency positions. Density functional theory calculations are carried out in support of the experimental data. Insight into the bonding of CO ligands to metal oxides is obtained and the effect of oxidation on the carbonyl stretching frequency is revealed.

  3. Test procedure for cation exchange chromatography

    SciTech Connect

    Cooper, T.D.

    1994-08-24

    The purpose of this test plan is to demonstrate the synthesis of inorganic antimonate ion exchangers and compare their performance against the standard organic cation exchangers. Of particular interest is the degradation rate of both inorganic and organic cation exchangers. This degradation rate will be tracked by determining the ion exchange capacity and thermal stability as a function of time, radiation dose, and chemical reaction.

  4. Method for encapsulating and isolating hazardous cations, medium for encapsulating and isolating hazardous cations

    DOEpatents

    Wasserman, S.R.; Anderson, K.B.; Song, K.; Yuchs, S.E.; Marshall, C.L.

    1998-04-28

    A method for encapsulating hazardous cations is provided comprising supplying a pretreated substrate containing the cations; contacting the substrate with an organo-silane compound to form a coating on the substrate; and allowing the coating to cure. A medium for containing hazardous cations is also provided, comprising a substrate having ion-exchange capacity and a silane-containing coating on the substrate. 3 figs.

  5. Structure to Function Correlations of Cationic Lipid Carriers for Gene Therapy

    NASA Astrophysics Data System (ADS)

    Slack, Nelle L.; Lin, Alison J.; George, Cyril X.; Ahmad, Ayesha; Samuel, Charles E.; Safinya, Cyrus R.

    1998-03-01

    The use of cationic lipids as carriers of genes (stretches of DNA) for delivery in cells is a promising alternative to viral-carriers for gene therapy. However, there exists a lack of knowledge regarding interactions and structures of cationic lipid:DNA (CL:DNA) complexes which is essential for the development of the optimal cationic lipid carrier. We are using x-ray diffraction and biological assays to elucidate the solution structures of CL:DNA complexes and how these structures affect transfection efficiencies. We determine transfection efficiencies by X-Gal assays which measure protein synthesized as a result of reporter gene expression. We have found that cationic liposomes complexed with supercoiled plasmid DNA in solution self-assemble into a lamellar( J. Raedler, I. Koltover, T. Salditt, C. R. Safinya, Science 275, 810 (1997).) or hexagonal phase depending on the composition of the cationic and neutral lipid. We present correlation data between solution structures and transfection efficiencies based on x-ray and X-Gal results. Supported by NSF-DMR-9624091, PRF-31352-AC7, and Los Alamos-STB/UC: 96-108.

  6. Recognition of metal cations by biological systems.

    PubMed

    Truter, M R

    1975-11-01

    Recognition of metal cations by biological systems can be compared with the geochemical criteria for isomorphous replacement. Biological systems are more highly selective and much more rapid. Methods of maintaining an optimum concentration, including storage and transfer for the essential trace elements, copper and iron, used in some organisms are in part reproducible by coordination chemists while other features have not been reporduced in models. Poisoning can result from a foreign metal taking part in a reaction irreversibly so that the recognition site or molecule is not released. For major nutrients, sodium, potassium, magnesium and calcium, there are similarities to the trace metals in selective uptake but differences qualitatively and quantitatively in biological activity. Compounds selective for potassium replace all the solvation sphere with a symmetrical arrangement of oxygen atoms; those selective for sodium give an asymmetrical environment with retention of a solvent molecule. Experiments with naturally occurring antibiotics and synthetic model compounds have shown that flexibility is an important feature of selectivity and that for transfer or carrier properties there is an optimum (as opposed to a maximum) metal-ligand stability constant. Thallium is taken up instead of potassium and will activate some enzymes; it is suggested that the poisonous characteristics arise because the thallium ion may bind more strongly than potassium to part of a site and then fail to bind additional atoms as required for the biological activity. Criteria for the design of selective complexing agents are given with indications of those which might transfer more than one metal at once. PMID:1815

  7. Complex oxides: Intricate disorder

    DOE PAGESBeta

    Uberuaga, Blas Pedro

    2016-05-01

    In this study, complex oxides such as pyrochlores have a myriad of potential technological applications, including as fast ion conductors and radiation-tolerant nuclear waste forms. They are also of interest for their catalytic and spin ice properties. Many of these functional properties are enabled by the atomic structure of the cation sublattices. Pyrochlores (A2B2O7) contain two different cations (A and B), typically a 3+ rare earth and a 4+ transition metal such as Hf, Zr, or Ti. The large variety of chemistries that can form pyrochlores leads to a rich space in which to search for exotic new materials. Furthermore,more » how cations order or disorder on their respective sublattices for a given chemical composition influences the functional properties of the oxide. For example, oxygen ionic conductivity is directly correlated with the level of cation disorder — the swapping of A and B cations1. Further, the resistance of these materials against amorphization has also been connected with the ability of the cations to disorder2, 3. These correlations between cation structure and functionality have spurred great interest in the structure of the cation sublattice under irradiation, with significant focus on the disordering mechanisms and disordered structure. Previous studies have found that, upon irradiation, pyrochlores often undergo an order-to-disorder transformation, in which the resulting structure is, from a diffraction point of view, indistinguishable from fluorite (AO2) (ref. 3). Shamblin et al. now reveal that the structure of disordered pyrochlore is more complicated than previously thought4.« less

  8. Divalent cation shrinks DNA but inhibits its compaction with trivalent cation

    NASA Astrophysics Data System (ADS)

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

    2016-05-01

    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.

  9. Can betaine pyridinium derivatives be used to control the photoejection of cation?

    PubMed

    Aloïse, S; Ruan, Y; Hamdi, I; Tiwari, A K; Buntinx, G; Azarias, C; Perrier, A; Leray, I

    2016-06-01

    Using a combination of advanced DFT/TDDFT calculations together with ultrafast and stationary spectroscopies we have investigated the photochemistry and cationic complexation ability of 1-pyridinio-benzimidazolate (PyB) and analogs substituted by 15-aza-5-crown (PyB-Aza) or dimethyl-amino groups (PyB-DiMe). Focusing on PyB-Aza, the first aim was to assess the competitive complexation of the imidazole bridge vs. the macrocycle. In acetonitrile, it was found by absorption and emission that the imidazole moiety binds efficiently through lateral electrostatic interaction of high charge density cations and especially Ca(2+) to form a 1 : 1, metal : ligand (M : L) complex. Modulation of the complexation toward para substitution of the phenyl ring with a donor group is reported with values ranging from log K = 3.4 to 6.8. Complexation values are properly predicted by DFT calculations. From a photochemical point of view, for the same series, the trend is parallel to the rate of the photo-release process, found to be less than 200 femtosecond (fs), the fastest photorelease characteristic time reported so far. Unlike photoinduced charge transfer molecules linked with an aza-crown group, the mechanism appears simpler with no participation of loose complexes due to the macrocavity effect. Relaxation mechanisms after cation ejection are discussed as well. Finally, even if any photoinduced translocation of cation is reported for the PyB-Aza molecule between two complexation sites, a discussion about the use of betaine pyridinium as a molecular tool for the smart manipulation of cation systems is initiated. PMID:27212223

  10. A Hexameric Cationic Copper(II) Metallacrown as a Pertechnetate and Perrhenate Scavenger.

    PubMed

    Rodríguez-Hermida, Sabina; Lago, Ana Belén; Pino-Cuevas, Arantxa; Hagenbach, Adelheid; Cañadillas-Delgado, Laura; Carballo, Rosa; Abram, Ulrich; Vázquez-López, Ezequiel M

    2016-01-26

    Materials based on the cationic copper(II) hexanuclear 18-membered metallacrown [18-MCCuII-N(2ph)-6](6+) (2phH=2-piconyl hydrazide) and tetrafluoroborate, perchlorate, nitrate, sulfate, and perrhenate anions were prepared by an easy method in aqueous medium. Single-crystal X-ray characterization of six members of this new family of complexes showed that the anions are attached to the metallacrown by direct coordination to a copper cation or by hydrogen-bonding interaction with the center of the hexamer. The stable cationic nature of the complexes and their ability to bind different anions allows them to adsorb and immobilize environmentally relevant anions such as MO4(-) (M=Tc, Re). The MO4(-) trapping capacities suggest that these materials would be useful in the treatment of oxoanionic contaminants in water. PMID:26671639

  11. Structure and Reactivity of the Distonic and Aromatic Radical Cations of Tryptophan

    NASA Astrophysics Data System (ADS)

    Piatkivskyi, Andrii; Osburn, Sandra; Jaderberg, Kendall; Grzetic, Josipa; Steill, Jeffrey D.; Oomens, Jos; Zhao, Junfang; Lau, Justin Kai-Chi; Verkerk, Udo H.; Hopkinson, Alan C.; Siu, K. W. Michael; Ryzhov, Victor

    2013-04-01

    In this work, we regiospecifically generate and compare the gas-phase properties of two isomeric forms of tryptophan radical cations—a distonic indolyl N-radical (H3N+ - TrpN•) and a canonical aromatic π (Trp•+) radical cation. The distonic radical cation was generated by nitrosylating the indole nitrogen of tryptophan in solution followed by collision-induced dissociation (CID) of the resulting protonated N-nitroso tryptophan. The π-radical cation was produced via CID of the ternary [CuII(terpy)(Trp)] •2+ complex. CID spectra of the two isomeric species were found to be very different, suggesting no interconversion between the isomers. In gas-phase ion-molecule reactions, the distonic radical cation was unreactive towards n-propylsulfide, whereas the π radical cation reacted by hydrogen atom abstraction. DFT calculations revealed that the distonic indolyl radical cation is about 82 kJ/mol higher in energy than the π radical cation of tryptophan. The low reactivity of the distonic nitrogen radical cation was explained by spin delocalization of the radical over the aromatic ring and the remote, localized charge (at the amino nitrogen). The lack of interconversion between the isomers under both trapping and CID conditions was explained by the high rearrangement barrier of ca.137 kJ/mol. Finally, the two isomers were characterized by infrared multiple-photon dissociation (IRMPD) spectroscopy in the ~1000-1800 cm-1 region. It was found that some of the main experimental IR features overlap between the two species, making their distinction by IRMPD spectroscopy in this region problematic. In addition, DFT theoretical calculations showed that the IR spectra are strongly conformation-dependent.

  12. Cationic lipid nanodisks as an siRNA delivery vehicle.

    PubMed

    Ghosh, Mistuni; Ren, Gang; Simonsen, Jens B; Ryan, Robert O

    2014-06-01

    The term nanodisk (ND) describes reconstituted high-density lipoprotein particles that contain one or more exogenous bioactive agents. In the present study, ND were assembled from apolipoprotein A-I, the zwitterionic glycerophospholipid 1,2-dimyristoyl-sn-glycero-3-phosphocholine (DMPC), and the synthetic cationic lipid 1,2-dimyristoyl-3-trimethylammonium-propane (DMTAP). ND formulated at a DMPC:DMTAP ratio of 70:30 (by weight) were soluble in aqueous media. The particles generated were polydisperse, with diameters ranging from ∼20 to <50 nm. In nucleic acid binding studies, agarose gel retardation assays revealed that a synthetic 23-mer double-stranded oligonucleotide (dsOligo) bound to DMTAP containing ND but not to ND formulated with DMPC alone. Sucrose density gradient ultracentrifugation studies provided additional evidence for stable dsOligo binding to DMTAP-ND. Incubation of cultured hepatoma cells with DMTAP-ND complexed with a siRNA directed against glyceraldehyde 3-phosphate dehydrogenase showed 60% knockdown efficiency. Thus, incorporation of synthetic cationic lipid (i.e., DMTAP) to ND confers an ability to bind siRNA and the resulting complexes possess target gene knockdown activity in a cultured cell model. PMID:24840721

  13. The adsorption of helium atoms on coronene cations

    NASA Astrophysics Data System (ADS)

    Kurzthaler, Thomas; Rasul, Bilal; Kuhn, Martin; Lindinger, Albrecht; Scheier, Paul; Ellis, Andrew M.

    2016-08-01

    We report the first experimental study of the attachment of multiple foreign atoms to a cationic polycyclic aromatic hydrocarbon (PAH). The chosen PAH was coronene, C24H12, which was added to liquid helium nanodroplets and then subjected to electron bombardment. Using mass spectrometry, coronene cations decorated with helium atoms were clearly seen and the spectrum shows peaks with anomalously high intensities ("magic number" peaks), which represent ion-helium complexes with added stability. The data suggest the formation of a rigid helium layer consisting of 38 helium atoms that completely cover both faces of the coronene ion. Additional magic numbers can be seen for the further addition of 3 and 6 helium atoms, which are thought to attach to the edge of the coronene. The observation of magic numbers for the addition of 38 and 44 helium atoms is in good agreement with a recent path integral Monte Carlo prediction for helium atoms on neutral coronene. An understanding of how atoms and molecules attach to PAH ions is important for a number of reasons including the potential role such complexes might play in the chemistry of the interstellar medium.

  14. Cationic gadolinium chelate for magnetic resonance imaging of cartilaginous defects.

    PubMed

    Nwe, Kido; Huang, Ching-Hui; Qu, Feini; Warden-Rothman, Robert; Zhang, Clare Y; Mauck, Robert L; Tsourkas, Andrew

    2016-05-01

    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. PMID:26853708

  15. Cationic zinc organyls as precatalysts for hydroamination reactions.

    PubMed

    Chilleck, Maren A; Hartenstein, Larissa; Braun, Thomas; Roesky, Peter W; Braun, Beatrice

    2015-02-01

    The cationic zinc triple-decker complex [Zn2 Cp*3 ](+) [BAr(F) 4 ](-) (BAr(F) 4 =B(3,5-(CF3 )2 C6 H3 )4 ) exhibits catalytic activity in intra- and intermolecular hydroamination reactions in the absence of a cocatalyst. These hydroaminations presumably proceed through the activation of the C-C multiple bond of the alkene or alkyne by a highly electrophilic zinc species, which is formed upon elimination of the Cp* ligands. The reaction of [Zn2 Cp*3 ](+) [BAr(F) 4 ](-) with henylacetylene gives the hydrocarbonation product (Cp*)(Ph)CCH2 , which might be formed via a similar reaction pathway. Additionally, several other structurally well-defined cationic zinc organyls have been examined as precatalysts for intermolecular hydroamination reactions without the addition of a cocatalyst. These studies reveal that the highest activity is achieved in the absence of any donor ligands. The neutral complex [ZnCp(2S) 2 ] (Cp(2S) =C5 Me4 (CH2 )2 SMe) shows a remarkably high catalytic activity in the presence of a Brønsted acid. PMID:25522205

  16. 63Cu NQR spectra of dicoordinated Cu(I) cations with imidazole and pyrazole ligands

    NASA Astrophysics Data System (ADS)

    Khajenhouri, Fereidoun; Motallebi, Shahrock; Lucken, Edwin A. C.

    1995-02-01

    The 63Cu NQR spectra of five dicoordinated complex cations of Cu(I) with substituted imidazoles as ligands and six analogous complexes with substituted pyrazoles as ligands are reported. The structures of four of these complexes have been previously determined and the relationship of their 63Cu resonance frequency to the average CuN bond length is compared to that of the analogous lutidine or collidine complexes. It is concluded that there are probably significant differences between the electronic structures of the pyridine complexes and those of the pyrazole or imidazole series.

  17. Cation-pi interactions as a mechanism in technical lignin adsorption to cationic surfaces.

    PubMed

    Pillai, Karthik V; Renneckar, Scott

    2009-04-13

    The assembly of dissolved technical lignins in aqueous and organic medium has been studied at the solid-liquid interface. Adsorption of alkali lignin onto gold coated crystals treated with a cationic polymer was determined using a quartz crystal microbalance with dissipation monitoring. Complete coverage of the cationic surface with alkali lignin occurred at low solution concentration, revealing a high affinity coefficient under both alkali and neutral conditions. With additional adsorption studies from organosolv lignin in organic solvent and spectroscopic analysis of mixtures of cationic polymer and alkali lignin, a noncovalent interaction between lignin's aromatic rings and the cation of the quaternary ammonium group was shown to exist. The work underscores how polyphenolic biopolymers can strongly interact with cations through noncovalent interactions to control molecular architecture. PMID:19226174

  18. Ortho-7 bound to the active-site gorge of free and OP-conjugated acetylcholinesterase: cation-π interactions.

    PubMed

    Pathak, Arup Kumar; Bandyopadhyay, Tusar

    2016-01-01

    Despite the immense importance of cation-π interactions prevailing in bispyridinium drug acetylcholinesterase (AChE) complexes, a precise description of cation-π interactions at molecular level has remained elusive. Here, we consider a bispyridinium drug, namely, ortho-7 in three different structures of AChE, with and without complexation with organophosphorus (OP) compounds for detailed investigation using all atom molecular dynamics simulation. By quantum mechanical calculations, Y72, W86, Y124, W286, Y337, and Y341 aromatic residues of the enzyme are investigated for possible cation-π interactions with ortho-7. The cation-π interactions in each of the protein-drug complexes are studied using distance, angle, a suitable functional form of them, and electrostatic criteria. The variation of cation-π functional is remarkably consistent with that of the Columbic variation. It is clearly observed that cation-π interactions for some of the residues in the catalytic active site (CAS) and peripheral anionic site (PAS) of the enzyme are either enhanced or reduced based on the nature of OP conjugation (i.e., nerve gas, tabun or pesticide, fenamiphos) when compared with the OP-free enzyme. The strength of cation-π interaction is strongly dependent on the type OP conjugation. The effect of conjugation at CAS is also seen to influence the cation-π interaction at the PAS region. The variation of cation-π interactions on the type of conjugating OP compounds might be suggestive of a reason as to why wide spectrum drug against any OP poisoning is yet to arrive in the market. PMID:26270602

  19. Cation-π vs anion-π interactions: a complete π-orbital analysis

    NASA Astrophysics Data System (ADS)

    Garau, Carolina; Frontera, Antonio; Quiñonero, David; Ballester, Pablo; Costa, Antoni; Deyà, Pere M.

    2004-11-01

    A complete orbital analysis of two isoelectronic complexes of trifluorobenzene (TFB), TFB ⋯ F - and TFB ⋯ Na +, as models for anion-π and cation-π interactions, respectively, has been performed at the MP2/6-31++G** level of theory. There are important orbital differences between both interactions, which are discussed in detail herein.

  20. Cationically polymerizable monomers derived from renewable sources

    SciTech Connect

    Crivello, J.V.

    1991-10-01

    The objective of this project is to make use of products obtained from renewable plant sources as monomers for the direct production of polymers which can be used for a wide range of plastic applications. In this report is described progress in the synthesis and polymerization of cationically polymerizable monomers and oligomers derived from botanical oils, terpenes, natural rubber, and lignin. Nine different botanical oils were obtained from various sources, characterized and then epoxidized. Their photopolymerization was carried out using cationic photoinitiators and the mechanical properties of the resulting polymers characterized. Preliminary biodegradation studies are being conducted on the photopolymerized films from several of these oils. Limonene was cationically polymerized to give dimers and the dimers epoxidized to yield highly reactive monomers suitable for coatings, inks and adhesives. The direct phase transfer epoxidation of squalene and natural rubber was carried out. The modified rubbers undergo facile photocrosslinking in the presence of onium salts to give crosslinked elastomers. 12 refs., 3 figs., 10 tabs.

  1. Solution of trivalent cations into uranium dioxide

    NASA Astrophysics Data System (ADS)

    Middleburgh, S. C.; Parfitt, D. C.; Grimes, R. W.; Dorado, B.; Bertolus, M.; Blair, P. R.; Hallstadius, L.; Backman, K.

    2012-01-01

    The accommodation of trivalent oxides (M 2O 3) in uranium dioxide has been investigated using atomic scale simulation. Calculations suggest that all trivalent oxides studied preferentially enter UO 2 by associating the substitutional ion with an oxygen vacancy, larger cations forming the cluster {2MU':VOrad rad }×. Solution into hyper-stoichiometric UO 2+ x was accompanied by the formation of the {MU':UUrad }× cluster and smaller solution energies than into stoichiometric UO 2. Solubility is a particularly strong function of hyper-stoichiometry for smaller cations such as Cr 3+, which has implications for the use of Cr 2O 3 as a grain enlarger but not so for larger cations such s Gd 3+.

  2. Cationic Lipid-Based Nucleic Acid Vectors.

    PubMed

    Jubeli, Emile; Goldring, William P D; Pungente, Michael D

    2016-01-01

    The delivery of nucleic acids into cells remains an important laboratory cell culture technique and potential clinical therapy, based upon the initial cellular uptake, then translation into protein (in the case of DNA), or gene deletion by RNA interference (RNAi). Although viral delivery vectors are more efficient, the high production costs, limited cargo capacity, and the potential for clinical adverse events make nonviral strategies attractive. Cationic lipids are the most widely applied and studied nonviral vectors; however, much remains to be solved to overcome limitations of these systems. Advances in the field of cationic lipid-based nucleic acid (lipoplex) delivery rely upon the development of robust and reproducible lipoplex formulations, together with the use of cell culture assays. This chapter provides detailed protocols towards the formulation, delivery, and assessment of in vitro cationic lipid-based delivery of DNA. PMID:27436310

  3. Cationically polymerizable monomers derived from renewable sources

    SciTech Connect

    Crivello, J.V.

    1992-10-01

    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.

  4. ABSORPTION METHOD FOR SEPARATING METAL CATIONS

    DOEpatents

    Tompkins, E.R.; Parker, G.W.

    1959-03-10

    An improved method is presented for the chromatographic separation of fission products wherein a substantial reduction in liquid volume is obtained. The process consists in contacting a solution containing fission products with a body of ion-exchange adsorbent to effect adsorption of fission product cations. The loaded exchange resin is then contacted with a small volume of a carboxylic acid eluant, thereby recovering the fission products. The fission product carrying eluate is acidified without increasing its volume to the volume of the original solution, and the acidified eluate is then used as a feed solution for a smaller body of ion-exchange resin effecting readsorption of the fission product cations.

  5. Biogenic and synthetic polyamines bind cationic dendrimers.

    PubMed

    Mandeville, Jean-Sebastian; Bourassa, Phillipe; Thomas, Thekkumkattil John; Tajmir-Riahi, Heidar-Ali

    2012-01-01

    Biogenic polyamines are essential for cell growth and differentiation, while polyamine analogues exert antitumor activity in multiple experimental model systems, including breast and lung cancer. Dendrimers are widely used for drug delivery in vitro and in vivo. We report the bindings of biogenic polyamines, spermine (spm), and spermidine (spmd), and their synthetic analogues, 3,7,11,15-tetrazaheptadecane.4HCl (BE-333) and 3,7,11,15,19-pentazahenicosane.5HCl (BE-3333) to dendrimers of different compositions, mPEG-PAMAM (G3), mPEG-PAMAM (G4) and PAMAM (G4). FTIR and UV-visible spectroscopic methods as well as molecular modeling were used to analyze polyamine binding mode, the binding constant and the effects of polyamine complexation on dendrimer stability and conformation. Structural analysis showed that polyamines bound dendrimers through both hydrophobic and hydrophilic contacts with overall binding constants of K(spm-mPEG-G3) = 7.6 × 10(4) M(-1), K(spm-mPEG-PAMAM-G4) = 4.6 × 10(4) M(-1), K(spm-PAMAM-G4) = 6.6 × 10(4) M(-1), K(spmd-mPEG-G3) = 1.0 × 10(5) M(-1), K(spmd-mPEG-PAMAM-G4) = 5.5 × 10(4) M(-1), K(spmd-PAMAM-G4) = 9.2 × 10(4) M(-1), K(BE-333-mPEG-G3) = 4.2 × 10(4) M(-1), K(Be-333-mPEG-PAMAM-G4) = 3.2 × 10(4) M(-1), K(BE-333-PAMAM-G4) = 3.6 × 10(4) M(-1), K(BE-3333-mPEG-G3) = 2.2 × 10(4) M(-1), K(Be-3333-mPEG-PAMAM-G4) = 2.4 × 10(4) M(-1), K(BE-3333-PAMAM-G4) = 2.3 × 10(4) M(-1). Biogenic polyamines showed stronger affinity toward dendrimers than those of synthetic polyamines, while weaker interaction was observed as polyamine cationic charges increased. The free binding energies calculated from docking studies were: -3.2 (spermine), -3.5 (spermidine) and -3.03 (BE-3333) kcal/mol, with the following order of binding affinity: spermidine-PAMAM-G-4>spermine-PAMMAM-G4>BE-3333-PAMAM-G4 consistent with spectroscopic data. Our results suggest that dendrimers can act as carrier vehicles for delivering antitumor polyamine analogues to target tissues

  6. UV/Vis Action Spectroscopy and Structures of Tyrosine Peptide Cation Radicals in the Gas Phase.

    PubMed

    Viglino, Emilie; Shaffer, Christopher J; Tureček, František

    2016-06-20

    We report the first application of UV/Vis photodissociation action spectroscopy for the structure elucidation of tyrosine peptide cation radicals produced by oxidative intramolecular electron transfer in gas-phase metal complexes. Oxidation of Tyr-Ala-Ala-Ala-Arg (YAAAR) produces Tyr-O radicals by combined electron and proton transfer involving the phenol and carboxyl groups. Oxidation of Ala-Ala-Ala-Tyr-Arg (AAAYR) produces a mixture of cation radicals involving electron abstraction from the Tyr phenol ring and N-terminal amino group in combination with hydrogen-atom transfer from the Cα positions of the peptide backbone. PMID:27159034

  7. Reversible precipitation of casein micelles with a cationic hydroxyethylcellulose.

    PubMed

    Ausar, Salvador F; Bianco, Ismael D; Castagna, Leonardo F; Alasino, Roxana V; Narambuena, Claudio F; Leiva, Ezequiel P M; Beltramo, Dante M

    2005-11-16

    The cationic hydroxyethylcellulose Polyquaternium 10 (PQ10) was found to produce a dose-dependent destabilization of casein micelles from whole or skim milk without affecting the stability of most of the whey proteins. The anionic phosphate residues on caseins were not determinant in the observed interaction since the destabilization was also observed with dephosphorylated caseins to the same extent. However, the precipitation process was completely inhibited by rising NaCl concentration, indicating an important role of electrostatic interactions. Furthermore, the addition of 150 mM NaCl solubilized preformed PQ10-casein complexes, rendering a stable casein suspension without a disruption of the internal micellar structure as determined by dynamic light scattering. This casein preparation was found to contain most of the Ca2+ and only 10% of the lactose originally present in milk and remained as a stable suspension for at least 4 months at 4 degrees C. The final concentration of PQ10 determined both the size of the casein-polymer aggregates and the amount of milkfat that coprecipitates. The presence of PQ10 in the aggregates did not inhibit the activity of rennet or gastrointestinal proteases and lipases, nor did it affect the growth of several fermentative bacteria. The cationic cellulose PQ10 may cause a reversible electrostatic precipitation of casein micelles without disrupting their internal structure. The reversibility of the interaction described opens the possibility of using this cationic polysaccharide to concentrate and resuspend casein micelles from whole or skim milk in the production of new fiber-enriched lactose-reduced calcium-caseinate dairy products. PMID:16277399

  8. Cationic Pd(II)-catalyzed C–H activation/cross-coupling reactions at room temperature: synthetic and mechanistic studies

    PubMed Central

    Nishikata, Takashi; Abela, Alexander R; Huang, Shenlin

    2016-01-01

    Summary Cationic palladium(II) complexes have been found to be highly reactive towards aromatic C–H activation of arylureas at room temperature. A commercially available catalyst [Pd(MeCN)4](BF4)2 or a nitrile-free cationic palladium(II) complex generated in situ from the reaction of Pd(OAc)2 and HBF4, effectively catalyzes C–H activation/cross-coupling reactions between aryl iodides, arylboronic acids and acrylates under milder conditions than those previously reported. The nature of the directing group was found to be critical for achieving room temperature conditions, with the urea moiety the most effective in promoting facile coupling reactions at an ortho C–H position. This methodology has been utilized in a streamlined and efficient synthesis of boscalid, an agent produced on the kiloton scale annually and used to control a range of plant pathogens in broadacre and horticultural crops. Mechanistic investigations led to a proposed catalytic cycle involving three steps: (1) C–H activation to generate a cationic palladacycle; (2) reaction of the cationic palladacycle with an aryl iodide, arylboronic acid or acrylate, and (3) regeneration of the active cationic palladium catalyst. The reaction between a cationic palladium(II) complex and arylurea allowed the formation and isolation of the corresponding palladacycle intermediate, characterized by X-ray analysis. Roles of various additives in the stepwise process have also been studied. PMID:27340491

  9. Cation Selectivity in Biological Cation Channels Using Experimental Structural Information and Statistical Mechanical Simulation.

    PubMed

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

    2015-01-01

    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. PMID:26460827

  10. Method for encapsulating and isolating hazardous cations, medium for encapsulating and isolating hazardous cations

    SciTech Connect

    Wasserman, S.R.; Anderson, K.B.; Song, K.; Yuchs, S.E.; Marshall, C.L.

    1996-12-31

    The problems associated with the disposal of toxic metals in an environmentally acceptable manner continues to plague industry. Such metals as nickel, vanadium, molybdenum, cobalt, iron, and antimony present physiological and ecological challenges that are best addressed through minimization of exposure and dispersion. A method for encapsulating hazardous cations is provided comprising supplying a pretreated substrate containing the cations; contacting the substrate with an organo-silane compound to form a coating on the substrate; and allowing the coating to cure. A medium for containing hazardous cations is also provided, comprising a substrate having ion-exchange capacity and a silane-containing coating on the substrate.

  11. Cation Selectivity in Biological Cation Channels Using Experimental Structural Information and Statistical Mechanical Simulation

    PubMed Central

    Finnerty, Justin John

    2015-01-01

    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. PMID:26460827

  12. Restructuring of a Peat in Interaction with Multivalent Cations: Effect of Cation Type and Aging Time

    PubMed Central

    Kunhi Mouvenchery, Yamuna; Jaeger, Alexander; Aquino, Adelia J. A.; Tunega, Daniel; Diehl, Dörte; Bertmer, Marko; Schaumann, Gabriele Ellen

    2013-01-01

    It is assumed to be common knowledge that multivalent cations cross-link soil organic matter (SOM) molecules via cation bridges (CaB). The concept has not been explicitly demonstrated in solid SOM by targeted experiments, yet. Therefore, the requirements for and characteristics of CaB remain unidentified. In this study, a combined experimental and molecular modeling approach was adopted to investigate the interaction of cations on a peat OM from physicochemical perspective. Before treatment with salt solutions of Al3+, Ca2+ or Na+, respectively, the original exchangeable cations were removed using cation exchange resin. Cation treatment was conducted at two different values of pH prior to adjusting pH to 4.1. Cation sorption is slower (>>2 h) than deprotonation of functional groups (<2 h) and was described by a Langmuir model. The maximum uptake increased with pH of cation addition and decreased with increasing cation valency. Sorption coefficients were similar for all cations and at both pH. This contradicts the general expectations for electrostatic interactions, suggesting that not only the interaction chemistry but also spatial distribution of functional groups in OM determines binding of cations in this peat. The reaction of contact angle, matrix rigidity due to water molecule bridges (WaMB) and molecular mobility of water (NMR analysis) suggested that cross-linking via CaB has low relevance in this peat. This unexpected finding is probably due to the low cation exchange capacity, resulting in low abundance of charged functionalities. Molecular modeling demonstrates that large average distances between functionalities (∼3 nm in this peat) cannot be bridged by CaB-WaMB associations. However, aging strongly increased matrix rigidity, suggesting successive increase of WaMB size to connect functionalities and thus increasing degree of cross-linking by CaB-WaMB associations. Results thus demonstrated that the physicochemical structure of OM is decisive for Ca

  13. Viscoelastic cationic polymers containing the urethane linkage

    NASA Technical Reports Server (NTRS)

    Rembaum, A. (Inventor)

    1972-01-01

    A method for the synthesis and manufacturing of elastomeric compositions and articles containing quaternary nitrogen centers and condensation residues along the polymeric backbone of the centers is presented. Linear and cross-linked straight chain and block polymers having a wide damping temperature range were synthesized. Formulae for the viscoelastic cationic polymers are presented.

  14. NMR studies of cation transport across membranes

    SciTech Connect

    Shochet, N.R.

    1985-01-01

    /sup 23/Na NMR Studies of cation transport across membranes were conducted both on model and biological membranes. Two ionophores, the carrier monensin and the channel-former gramicidin, were chosen to induce cation transport in large unilamellar phosphatidylcholine vesicles. The distinction between the NMR signals arising from the two sides of the membrane was achieved by the addition of an anionic paramagnetic shift reagent to the outer solution. The kinetics of the cation transport across the membrane was observed simultaneously monitoring the changes in the /sup 23/Na NMR signals of both compartments. Two mathematical models were developed for the estimation of the transport parameters of the monensin- and gramicidin-induced cation transport. The models were able to fit the experimental data very well. A new method for the estimation of the volume trapped inside the vesicles was developed. The method uses the relative areas of the intra- and extravesicular NMR signals arising from a suspension of vesicles bathed in the same medium they contain, as a measure for the relative volumes of these compartments. Sodium transport across biological membranes was studied by /sup 23/ NMR, using suspensions of cultured nerve cells. The sodium influx through voltage-gated channels was studied using the channel modifier batrachotoxin in combination with scorpion toxin.

  15. ADSORPTION OF ORGANIC CATIONS TO NATURAL MATERIALS

    EPA Science Inventory

    The factors that control the extent of adsorption of amphiphilic organic cations on environmental and pristine surfaces have been studied. he sorbents were kaolinite, montmorillonite, two aquifer materials, and a soil; solutions contained various concentrations of NaCl and CaC12,...

  16. Dynamics of poly(4-hydroxystyrene) radical cation

    NASA Astrophysics Data System (ADS)

    Okamoto, Kazumasa; Kozawa, Takahiro; Tagawa, Seiichi

    2008-03-01

    Poly(4-hydroxystyrene) (PHS) has been used in KrF excimer laser (248 nm) lithography as a backbone polymer, and is also a promising material for EUV or electron beam lithography. Analysis of the intermediate species is important for the control of reactions in resist materials. Since the size of integrated circuits fabricated for mass production will decrease below 30 nm and the size error must also be decreased to the molecular level, the elucidation of proton dynamics at the molecular level is also important for reducing the deviation of the resist pattern size. In this study, the dynamics of PHS radical cations were studied, because PHS radical cation is main source of proton. The transient absorption of PHS was observed in the near-infrared region (NIR) in p-dioxane solutions by pulse radiolysis. The intramolecular PHS dimer radical cation (M2 +.) were observed, whereas p-cresol shows no distinct CR band. Although the radical cations of phenol derivatives are known to be easily deprotonated, it was found that M2 +. formation prevents deprotonation by its charge resonance stabilization.

  17. ADSORPTION OF ORGANIC CATIONS TO NATURAL MATERIALS

    EPA Science Inventory

    The factors that control the extent of adsorption of amphiphilic organic cations on environmental and pristine surfaces have been studied. The sorbents were kaolinite, montmorillonite, two aquifer materials, and a soil; solutions contained various concentrations of NaCl and CaCl,...

  18. Process and apparatus for the production of Bi-213 cations

    DOEpatents

    Horwitz, E.P.; Hines, J.J.; Chiarizia, R.; Dietz, M.

    1998-12-29

    A process for producing substantially impurity-free Bi-213 cations is disclosed. An aqueous acid feed solution containing Ac-225 cations is contacted with an ion exchange medium to bind the Ac-225 cations and form an Ac-225-laden ion exchange medium. The bound Ac-225 incubates on the ion exchange medium to form Bi-213 cations by radioactive decay. The Bi-213 cations are then recovered from the Ac-225-laden ion exchange medium to form a substantially impurity-free aqueous Bi-213 cation acid solution. An apparatus for carrying out this process is also disclosed. 7 figs.

  19. Process and apparatus for the production of BI-213 cations

    DOEpatents

    Horwitz, E. Philip; Hines, John J.; Chiarizia, Renato; Dietz, Mark

    1998-01-01

    A process for producing substantially impurity-free Bi-213 cations is disclosed. An aqueous acid feed solution containing Ac-225 cations is contacted with an ion exchange medium to bind the Ac-225 cations and form an Ac-225-laden ion exchange medium. The bound Ac-225 incubates on the ion exchange medium to form Bi-213 cations by radioactive decay. The Bi-213 cations are then recovered from the Ac-225-laden ion exchange medium to form a substantially impurity-free aqueous Bi-213 cation acid solution. An apparatus for carrying out this process is also disclosed.

  20. Intermolecular forces between low generation PAMAM dendrimer condensed DNA helices: role of cation architecture.

    PubMed

    An, Min; Parkin, Sean R; DeRouchey, Jason E

    2014-01-28

    In recent years, dendriplexes, complexes of cationic dendrimers with DNA, have become attractive DNA delivery vehicles due to their well-defined chemistries. To better understand the nature of the forces condensing dendriplexes, we studied low generation poly(amidoamine) (PAMAM) dendrimer-DNA complexes and compared them to comparably charged linear arginine peptides. Using osmotic stress coupled with X-ray scattering, we have investigated the effect of molecular chain architecture on DNA-DNA intermolecular forces that determine the net attraction and equilibrium interhelical distance within these polycation condensed DNA arrays. In order to compact DNA, linear cations are believed to bind in DNA grooves and to interact with the phosphate backbone of apposing helices. We have previously shown a length dependent attraction resulting in higher packaging densities with increasing charge for linear cations. Hyperbranched polycations, such as polycationic dendrimers, presumably would not be able to bind to DNA and correlate their charges in the same manner as linear cations. We show that attractive and repulsive force amplitudes in PAMAM-DNA assemblies display significantly different trends than comparably charged linear arginines resulting in lower DNA packaging densities with increasing PAMAM generation. The salt and pH dependencies of packaging in PAMAM dendrimer-DNA and linear arginine-DNA complexes were also investigated. Significant differences in the force curve behaviour and salt and pH sensitivities suggest that different binding modes may be present in DNA condensed by dendrimers when compared to linear polycations. PMID:24651934

  1. Dendritic Cells Stimulated by Cationic Liposomes.

    PubMed

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

    2016-01-01

    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. PMID:27398454

  2. Silica-based cationic bilayers as immunoadjuvants

    PubMed Central

    Lincopan, Nilton; Santana, Mariana RA; Faquim-Mauro, Eliana; da Costa, Maria Helena B; Carmona-Ribeiro, Ana M

    2009-01-01

    Background Silica particles cationized by dioctadecyldimethylammonium bromide (DODAB) bilayer were previously described. This work shows the efficiency of these particulates for antigen adsorption and presentation to the immune system and proves the concept that silica-based cationic bilayers exhibit better performance than alum regarding colloid stability and cellular immune responses for vaccine design. Results Firstly, the silica/DODAB assembly was characterized at 1 mM NaCl, pH 6.3 or 5 mM Tris.HCl, pH 7.4 and 0.1 mg/ml silica over a range of DODAB concentrations (0.001–1 mM) by means of dynamic light scattering for particle sizing and zeta-potential analysis. 0.05 mM DODAB is enough to produce cationic bilayer-covered particles with good colloid stability. Secondly, conditions for maximal adsorption of bovine serum albumin (BSA) or a recombinant, heat-shock protein from Mycobacterium leprae (18 kDa-hsp) onto DODAB-covered or onto bare silica were determined. At maximal antigen adsorption, cellular immune responses in vivo from delayed-type hypersensitivity reactions determined by foot-pad swelling tests (DTH) and cytokines analysis evidenced the superior performance of the silica/DODAB adjuvant as compared to alum or antigens alone whereas humoral response from IgG in serum was equal to the one elicited by alum as adjuvant. Conclusion Cationized silica is a biocompatible, inexpensive, easily prepared and possibly general immunoadjuvant for antigen presentation which displays higher colloid stability than alum, better performance regarding cellular immune responses and employs very low, micromolar doses of cationic and toxic synthetic lipid. PMID:19152701

  3. Tree species affect cation exchange capacity (CEC) and cation binding properties of organic matter in acid forest soils.

    PubMed

    Gruba, Piotr; Mulder, Jan

    2015-04-01

    Soil organic matter (SOM) in forest soil is of major importance for cation binding and acid buffering, but its characteristics may differ among soils under different tree species. We investigated acidity, cation exchange properties and Al bonding to SOM in stands of Scots pine, pedunculate oak, Norway spruce, European beech and common hornbeam in southern Poland. The content of total carbon (Ct) was by far the major contributor to total cation exchange capacity (CECt) even in loamy soils and a strong relationship between Ct and CECt was found. The slope of the regression of CECt to Ct increased in the order hornbeam≈oakcomplexed and more adsorbed H+ than SOM from oak soils. Such differences in Al and H bonding are not only important for pH buffering and metal solubility controls, but also for stabilization of SOM via saturation of functional groups by Al and H. PMID:25596350

  4. Sequential Anion and Cation Exchange Reactions for Complete Material Transformations of Nanoparticles with Morphological Retention.

    PubMed

    Hodges, James M; Kletetschka, Karel; Fenton, Julie L; Read, Carlos G; Schaak, Raymond E

    2015-07-20

    Ion exchange reactions of colloidal nanocrystals provide access to complex products that are synthetically challenging using traditional hot-injection methods. However, such reactions typically achieve only partial material transformations by employing either cation or anion exchange processes. It is now shown that anion and cation exchange reactions can be coupled together and applied sequentially in one integrated pathway that leads to complete material transformations of nanocrystal templates. Although the product nanocrystals do not contain any of the original constituent elements, the original morphology is retained, thereby fully decoupling morphology and composition control. The sequential anion/cation exchange process was applied to pseudo-spherical CdO nanocrystals and ZnO tetrapods, producing fully transformed and shape-controlled nanocrystals of copper and silver sulfides and selenides. Furthermore, hollow core-shell tetrapod ZnS@CdS heterostructures were readily accessible. PMID:26110653

  5. Redox potential tuning by redox-inactive cations in nature's water oxidizing catalyst and synthetic analogues.

    PubMed

    Krewald, Vera; Neese, Frank; Pantazis, Dimitrios A

    2016-04-20

    The redox potential of synthetic oligonuclear transition metal complexes has been shown to correlate with the Lewis acidity of a redox-inactive cation connected to the redox-active transition metals of the cluster via oxo or hydroxo bridges. Such heterometallic clusters are important cofactors in many metalloenzymes, where it is speculated that the redox-inactive constituent ion of the cluster serves to optimize its redox potential for electron transfer or catalysis. A principal example is the oxygen-evolving complex in photosystem II of natural photosynthesis, a Mn4CaO5 cofactor that oxidizes water into dioxygen, protons and electrons. Calcium is critical for catalytic function, but its precise role is not yet established. In analogy to synthetic complexes it has been suggested that Ca(2+) fine-tunes the redox potential of the manganese cluster. Here we evaluate this hypothesis by computing the relative redox potentials of substituted derivatives of the oxygen-evolving complex with the cations Sr(2+), Gd(3+), Cd(2+), Zn(2+), Mg(2+), Sc(3+), Na(+) and Y(3+) for two sequential transitions of its catalytic cycle. The theoretical approach is validated with a series of experimentally well-characterized Mn3AO4 cubane complexes that are structural mimics of the enzymatic cluster. Our results reproduce perfectly the experimentally observed correlation between the redox potential and the Lewis acidities of redox-inactive cations for the synthetic complexes. However, it is conclusively demonstrated that this correlation does not hold for the oxygen evolving complex. In the enzyme the redox potential of the cluster only responds to the charge of the redox-inactive cations and remains otherwise insensitive to their precise identity, precluding redox-tuning of the metal cluster as a primary role for Ca(2+) in biological water oxidation. PMID:26762578

  6. Fluoride ion recognition by chelating and cationic boranes.

    PubMed

    Hudnall, Todd W; Chiu, Ching-Wen; Gabbaï, François P

    2009-02-17

    Because of the ubiquity of fluoride ions and their potential toxicity at high doses, researchers would like to design receptors that selectively detect this anion. Fluoride is found in drinking water, toothpaste, and osteoporosis drugs. In addition, fluoride ions also can be detected as an indicator of uranium enrichment (via hydrolysis of UF(6)) or of the chemical warfare agent sarin, which releases the ion upon hydrolysis. However, because of its high hydration enthalpy, the fluoride anion is one of the most challenging targets for anion recognition. Among the various recognition strategies that are available, researchers have focused a great deal of attention on Lewis acidic boron compounds. These molecules typically interact with fluoride anions to form the corresponding fluoroborate species. In the case of simple triarylboranes, the fluoroborates are formed in organic solvents but not in water. To overcome this limitation, this Account examines various methods we have pursued to increase the fluoride-binding properties of boron-based receptors. We first considered the use of bifunctional boranes, which chelate the fluoride anion, such as 1,8-diborylnaphthalenes or heteronuclear 1-boryl-8-mercurio-naphthalenes. In these molecules, the neighboring Lewis acidic atoms can cooperatively interact with the anionic guest. Although the fluoride binding constants of the bifunctional compounds exceed those of neutral monofunctional boranes by several orders of magnitude, the incompatibility of these systems with aqueous media limits their utility. More recently, we have examined simple triarylboranes whose ligands are decorated by cationic ammonium or phosphonium groups. These cationic groups increase the electrophilic character of these boranes, and unlike their neutral analogs, they are able to complex fluoride in aqueous media. We have also considered cationic boranes, which form chelate complexes with fluoride anions. Our work demonstrates that Coulombic and chelate

  7. Role of Reverse Divalent Cation Diffusion in Forward Osmosis Biofouling.

    PubMed

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

    2015-11-17

    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. PMID:26503882

  8. Excited state dynamics of the astaxanthin radical cation

    NASA Astrophysics Data System (ADS)

    Amarie, Sergiu; Förster, Ute; Gildenhoff, Nina; Dreuw, Andreas; Wachtveitl, Josef

    2010-07-01

    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.

  9. Weakly Charged Cationic Nanoparticles Induce DNA Bending and Strand Separation

    SciTech Connect

    Railsback, Justin; Singh, Abhishek; Pearce, Ryan; McKnight, Timothy E; Collazo, Ramon; Sitar, Zlatko; Yingling, Yaroslava; Melechko, Anatoli Vasilievich

    2012-01-01

    The understanding of interactions between double stranded (ds) DNA and charged nanoparticles will have a broad bearing on many important applications from drug delivery [ 1 4 ] to DNAtemplated metallization. [ 5 , 6 ] Cationic nanoparticles (NPs) can bind to DNA, a negatively charged molecule, through a combination of electrostatic attraction, groove binding, and intercalation. Such binding events induce changes in the conformation of a DNA strand. In nature, DNA wraps around a cylindrical protein assembly (diameter and height of 6 nm) [ 7 ] with an 220 positive charge, [ 8 ] creating the complex known as chromatin. Wrapping and bending of DNA has also been achieved in the laboratory through the binding of highly charged species such as molecular assemblies, [ 9 , 10 ] cationic dendrimers, [ 11 , 12 ] and nanoparticles. [ 13 15 ] The charge of a nanoparticle plays a crucial role in its ability to induce DNA structural changes. If a nanoparticle has a highly positive surface charge density, the DNA is likely to wrap and bend upon binding to the nanoparticle [ 13 ] (as in the case of chromatin). On the other hand, if a nanoparticle is weakly charged it will not induce dsDNA compaction. [ 9 , 10 , 15 ] Consequently, there is a transition zone from extended to compact DNA conformations which depends on the chemical nature of the nanoparticle and occurs for polycations with charges between 5 and 10. [ 9 ] While the interactions between highly charged NPs and DNA have been extensively studied, the processes that occur within the transition zone are less explored.

  10. Crystal structure of the channelrhodopsin light-gated cation channel

    PubMed Central

    Kato, Hideaki E.; Zhang, Feng; Yizhar, Ofer; Ramakrishnan, Charu; Nishizawa, Tomohiro; Hirata, Kunio; Ito, Jumpei; Aita, Yusuke; Tsukazaki, Tomoya; Hayashi, Shigehiko; Hegemann, Peter; Maturana, Andrés D.; Ishitani, Ryuichiro; Deisseroth, Karl; Nureki, Osamu

    2014-01-01

    Channelrhodopsins (ChRs) are light-gated cation channels derived from algae that have shown experimental utility in optogenetics; for example, neurons expressing ChRs can be optically controlled with high temporal precision within systems as complex as freely moving mammals. Although ChRs have been broadly applied to neuroscience research, little is known about the molecular mechanisms by which these unusual and powerful proteins operate. Here we present the crystal structure of a ChR (a C1C2 chimaera between ChR1 and ChR2 from Chlamydomonas reinhardtii) at 2.3 Å resolution. The structure reveals the essential molecular architecture of ChRs, including the retinal-binding pocket and cation conduction pathway. This integration of structural and electrophysiological analyses provides insight into the molecular basis for the remarkable function of ChRs, and paves the way for the precise and principled design of ChR variants with novel properties. PMID:22266941

  11. Mixed-valent neptunium(IV/V) compound with cation-cation-bound six-membered neptunyl rings.

    PubMed

    Jin, Geng Bang

    2013-11-01

    A new mixed-valent neptunium(IV/V) compound has been synthesized by evaporation of a neptunium(V) acidic solution. The structure of the compound features cation-cation-bound six-membered neptunyl(V) rings. These rings are further connected by Np(IV) ions through cation-cation interactions (CCIs) into a three-dimensional neptunium cationic open framework. This example illustrates the possibility of isolating neptunyl(V) CCI oligomers in inorganic systems using other cations to compete with Np(V) in bonding with the neptunyl oxygen. PMID:24187926

  12. Eosinophil granule cationic proteins regulate the classical pathway of complement.

    PubMed Central

    Weiler, J M; Edens, R E; Bell, C S; Gleich, G J

    1995-01-01

    Major basic protein, the primary constituent of eosinophil granules, regulates the alternative and classical pathways of complement. Major basic protein and other eosinophil granule cationic proteins, which are important in mediating tissue damage in allergic disease, regulate the alternative pathway by interfering with C3b interaction with factor B to assemble an alternative pathway C3 convertase. In the present study, eosinophil peroxidase, eosinophil cationic protein and eosinophil-derived neurotoxin, as well as major basic protein, were examined for capacity to regulate the classical pathway. Eosinophil peroxidase, eosinophil cationic protein and major basic protein inhibited formation of cell-bound classical pathway C3 convertase (EAC1,4b,2a), causing 50% inhibition of complement-mediated lysis at about 0.19, 0.75 and 0.5 micrograms/10(7) cellular intermediates, respectively. Eosinophil-derived neurotoxin had no activity on this pathway of complement. The eosinophil granule proteins were examined for activity on the formation of the membrane attack complex. Major basic protein and eosinophil cationic protein had no activity on terminal lysis. In contrast, eosinophil peroxidase inhibited lysis of EAC1,4b,2a,3b,5b, but had only minimal activity on later events in complement lysis. These polycations were then examined to determine the site(s) at which they regulated the early classical pathway. Eosinophil granule polycationic proteins: (1) reduced the Zmax at all time points but had only minimal effect on the Tmax during the formation of the classical pathway C3 convertase (EAC1,4b,2a); (2) inhibited formation of EAC1,4b,2a proportional to C4 but independent of C2 concentration; (3) inhibited fluid phase formation of C1,4b,2a, as reflected by a decrease in C1-induced consumption of C2 over time; and (4) inhibited C1 activity over time without a direct effect on either C4 or C2. These observations suggest that polycations regulate the early classical pathway by

  13. Active-Site Monovalent Cations Revealed in a 1.55 Å Resolution Hammerhead Ribozyme Structure

    PubMed Central

    Anderson, Michael; Schultz, Eric P.; Martick, Monika; Scott, William G.

    2013-01-01

    We have obtained a 1.55 Å crystal structure of a hammerhead ribozyme derived from Schistosoma mansoni in conditions that permit detailed observations of Na+ ion binding in the ribozyme's active site. At least two such Na+ ions are observed. The first Na+ ion binds to the N7 of G10.1 and the adjacent A9 phosphate in a manner identical to that previously observed for divalent cations. A second Na+ ion binds to the Hoogsteen face of G12, the general base in the hammerhead cleavage reaction, thereby potentially dissipating the negative charge of the catalytically active enolate form of the nucleotide base. A potential but more ambiguous third site bridges the A9 and scissile phosphates in a manner consistent with previous predictions. Hammerhead ribozymes have been observed to be active in the presence of high concentrations of monovalent cations, including Na+, but the mechanism by which monovalent cations substitute for divalent cations in hammerhead catalysis remains unclear. Our results enable us to suggest that Na+ directly and specifically substitutes for divalent cations in the hammerhead active site. The detailed geometry of the pre-catalytic active site complex is also revealed with a new level of precision, thanks to the quality of the electron density maps obtained from what is currently the highest resolution ribozyme structure in the protein data bank. PMID:23711504

  14. Cationic-modified cyclodextrin nanosphere/anionic polymer as flocculation/sorption systems.

    PubMed

    Xiao, Huining; Cezar, Norlito

    2005-03-15

    Simultaneous removal of dissolved and colloidal substances has been a challenging task. The cationic-modified beta-cyclodextrin nanospheres synthesized in this work, in conjunction with a water-soluble polyacrylamide-based anionic polymer, potentially provide a novel approach to address the problem. The cyclodextrin was rendered cationic using (2,3-epoxypropyl)trimethylammonium chloride as a reagent. The cationicity of the modified cyclodextrin and the reaction between cyclodextrin and the reagent were characterized by electrophoresis measurement, polyelectrolyte titration, and NMR. As a dual-component flocculation system, the cationic cyclodextrin/anionic polymer significantly induced clay flocculation, lowering the relative turbidity of the clay suspension over a wide pH range. Meanwhile, as a nanospherical absorbent, the modified cyclodextrins exhibited strong affinity toward aromatic compounds via inclusion complex formation in the hydrophobic cavities, which was monitored by UV spectroscopy. These systems facilitated the simultaneous removal of dissolved and colloidal substances, which was unachievable previously. In addition, the interaction between anionic polymers and the clay particles pretreated with cationic cyclodextrin was investigated in order to reveal the flocculation mechanism. PMID:15721912

  15. Anti-angiogenic therapy via cationic liposome-mediated systemic siRNA delivery.

    PubMed

    Tagami, Tatsuaki; Suzuki, Takuya; Matsunaga, Mariko; Nakamura, Kazuya; Moriyoshi, Naoto; Ishida, Tatsuhiro; Kiwada, Hiroshi

    2012-01-17

    siRNA has been touted as a therapeutic molecule against genetic diseases, which include cancers. But several challenging issues remain in order to achieve efficient systemic siRNA delivery and a sufficient therapeutic effect for siRNA in vivo. Cationic liposome shows promise as a carrier for nucleic acids, as it can selectively bind to angiogenic tumor blood vessels. In this way, anti-angiogenic therapy via cationic liposome-mediated systemic siRNA delivery could be achieved in cancer therapy. In the present study, we proved our assumption by preparing various kinds of polyethylene glycol (PEG)-coated siRNA/cationic liposome complexes (siRNA-lipoplexes) and screening the avidity of these siRNA-lipoplexes upon angiogenic tumor blood vessels by means of a murine dorsal air sac (DAS) model. The lipoplex, having a lipid composition of DC-6-14/POPC/CHOL/DOPE/mPEG(2000)-DSPE=20/30/30/20/5 (molar ratio) and a charge ratio of cationic liposome and siRNA=3.81 (+/-), showed a higher binding index to newly formed blood vessels. Systemic injection with the lipoplex containing siRNA for the Argonaute2 gene (apoptosis-inducible siRNA) resulted in significant anti-tumor effect without severe side effects in mice with Lewis lung carcinoma. Our results indicate that the PEGylated cationic liposome-mediated systemic delivery of cytotoxic siRNA achieves anti-angiogenesis, resulting in the suppression of tumor growth. PMID:22101286

  16. Synthesis, Electronic Structure, and Reactivity Studies of a 4-Coordinate Square Planar Germanium(IV) Cation.

    PubMed

    Fang, Huayi; Jing, Huize; Zhang, Aixi; Ge, Haonan; Yao, Zhengmin; Brothers, Penelope J; Fu, Xuefeng

    2016-06-22

    A tetra-coordinate, square planar germanium(IV) cation [(TPFC)Ge](+) (TPFC = tris(pentafluorophenyl)corrole) was synthesized quantitatively by the reaction of (TPFC)Ge-H with [Ph3C](+)[B(C6F5)4](¯). The highly reactive [(TPFC)Ge](+) cation reacted with benzene to form phenyl complex (TPFC)Ge-C6H5 through an electrophilic pathway. The key intermediate, a σ-type germylium-benzene adduct, [(TPFC)Ge(η(1)-C6H6)](+), was isolated and characterized by single-crystal X-ray diffraction. Deprotonation of [(TPFC)Ge(η(1)-C6H6)](+) cation led to the formation of (TPFC)Ge-C6H5. [(TPFC)Ge](+) also reacted with ethylene and cyclopropane in benzene at room temperature to form (TPFC)Ge-CH2CH2C6H5 and (TPFC)Ge-CH2CH2CH2C6H5, respectively. The observed electrophilic reactivity is ascribed to the highly exposed cationic germanium center with novel frontier orbitals comprising two vacant sp-hybridized orbitals that are not conjugated to π-system. The three electron-withdrawing pentafluorophenyl groups on the corrole ligand also enhance the electrophilicity of the cationic germanium corrole. PMID:27243114

  17. A novel Ag⁺ cation sensor based on polyamidoamine dendrimer modified with 1,8-naphthalimide derivatives.

    PubMed

    Dodangeh, Mohammad; Gharanjig, Kamaladin; Arami, Mokhtar

    2016-02-01

    In this study, 4-amino-1,8-naphthalimide-conjugated polyamidoamine dendrimer was synthesized and characterized and its potentiality as a cation sensor was investigated. 4-Amino-1,8-naphthalic anhydride reacted with polyamidoamine dendrimer and the product was characterized using FTIR, (1)H NMR, (13)C NMR and melting point analysis method. The synthesized compound was applied to detect various cations in water media and N,N-dimethylformamide (DMF) via monitoring the quenching of the fluorescence intensity. Furthermore, various metal cations including Cu(2+), Ni(2+), Zn(2+), Pb(2+),Ca(2+), Ba(2+), Cd(2+), Hg(2+), Fe(2+), Fe(3+) and Ag(+) were tested. The complexes formed between the synthesized compound and metal cations in solution and their effects on Photoinduced Electron Transfer (PET) process were investigated regarding the potential application of the newly-synthesized dendrimer as a colorimetric and fluorescent sensor for such cations. The results clearly confirmed that the 1,8-naphthalimide groups surrounding the central dendrimer core showed strong green fluorescence emission at 553 nm. This effect considerably decreased with the introduction of all cations, except Ag(+) where the fluorescence quenching effect was remarkable and more dominant. Therefore, it can be concluded that the synthesized dye has the potentiality of being a highly sensitive and selective fluorescence sensor for Ag(+) cation. PMID:26529637

  18. A uranium-based UO2(+)-Mn2+ single-chain magnet assembled trough cation-cation interactions.

    PubMed

    Mougel, Victor; Chatelain, Lucile; Hermle, Johannes; Caciuffo, Roberto; Colineau, Eric; Tuna, Floriana; Magnani, Nicola; de Geyer, Arnaud; Pécaut, Jacques; Mazzanti, Marinella

    2014-01-13

    Single-chain magnets (SCMs) are materials composed of magnetically isolated one-dimensional (1D) units exhibiting slow relaxation of magnetization. The occurrence of SCM behavior requires the fulfillment of stringent conditions for exchange and anisotropy interactions. Herein, we report the synthesis, the structure, and the magnetic characterization of the first actinide-containing SCM. The 5f-3d heterometallic 1D chains [{[UO2(salen)(py)][M(py)4](NO3)}]n, (M=Cd (1) and M=Mn (2); py=pyridine) are assembled trough cation-cation interaction from the reaction of the uranyl(V) complex [UO2(salen)py][Cp*2Co] (Cp*=pentamethylcyclopentadienyl) with Cd(NO3)2 or Mn(NO3)2 in pyridine. The infinite UMn chain displays a high relaxation barrier of 134±0.8 K (93±0.5 cm(-1)), probably as a result of strong intra-chain magnetic interactions combined with the high Ising anisotropy of the uranyl(V) dioxo group. It also exhibits an open magnetic hysteresis loop at T<6 K, with an impressive coercive field of 3.4 T at 2 K. PMID:24311434

  19. Cation-Induced Coiling of Vanadium Pentoxide Nanobelts

    PubMed Central

    2010-01-01

    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. PMID:21076706

  20. N-Acetylglycine Cation Tautomerization Enabled by the Peptide Bond.

    PubMed

    Kocisek, Jaroslav; Piekarski, Dariusz Grzegorz; Delaunay, Rudy; Huber, Bernd A; Adoui, Lamri; Martín, Fernando; Alcamí, Manuel; Rousseau, Patrick; Domaracka, Alicja; Kopyra, Janina; Díaz-Tendero, Sergio

    2015-09-17

    We present a combined experimental and theoretical study of the ionization of N-acetylglycine molecules by 48 keV O(6+) ions. We focus on the single ionization channel of this interaction. In addition to the prompt fragmentation of the N-acetylglycine cation, we also observe the formation of metastable parent ions with lifetimes in the microsecond range. On the basis of density functional theory calculations, we assign these metastable ions to the diol tautomer of N-acetylglycine. In comparison with the simple amino acids, the tautomerization rate is higher because of the presence of the peptide bond. The study of a simple biologically relevant molecule containing a peptide bond allows us to demonstrate how increasing the complexity of the structure influences the behavior of the ionized molecule. PMID:26243533

  1. Supramolecular Explorations: Exhibiting the Extent of Extended Cationic Cyclophanes.

    PubMed

    Dale, Edward J; Vermeulen, Nicolaas A; Juríček, Michal; Barnes, Jonathan C; Young, Ryan M; Wasielewski, Michael R; Stoddart, J Fraser

    2016-02-16

    Acting as hosts, cationic cyclophanes, consisting of π-electron-poor bipyridinium units, are capable of entering into strong donor-acceptor interactions to form host-guest complexes with various guests when the size and electronic constitution are appropriately matched. A synthetic protocol has been developed that utilizes catalytic quantities of tetrabutylammonium iodide to make a wide variety of cationic pyridinium-based cyclophanes in a quick and easy manner. Members of this class of cationic cyclophanes with boxlike geometries, dubbed Ex(n)Boxm(4+) for short, have been prepared by altering a number of variables: (i) n, the number of "horizontal" p-phenylene spacers between adjoining pyridinium units, to modulate the "length" of the cavity; (ii) m, the number of "vertical" p-phenylene spacers, to modulate the "width" of the cavity; and (iii) the aromatic linkers, namely, 1,4-di- and 1,3,5-trisubstituted units for the construction of macrocycles (ExBoxes) and macrobicycles (ExCages), respectively. This Account serves as an exploration of the properties that emerge from these structural modifications of the pyridinium-based hosts, coupled with a call for further investigation into the wealth of properties inherent in this class of compounds. By variation of only the aforementioned components, the role of these cationic receptors covers ground that spans (i) synthetic methodology, (ii) extraction and sequestration, (iii) catalysis, (iv) molecular electronics, (v) physical organic chemistry, and (vi) supramolecular chemistry. Ex(1)Box(4+) (or simply ExBox(4+)) has been shown to be a multipurpose receptor capable of binding a wide range of polycyclic aromatic hydrocarbons (PAHs), while also being a suitable component in switchable mechanically interlocked molecules. Additionally, the electronic properties of some host-guest complexes allow the development of artificial photosystems. Ex(2)Box(4+) boasts the ability to bind both π-electron-rich and -poor aromatic

  2. Use of grape seed and its natural polyphenol extracts as a natural organic coagulant for removal of cationic dyes.

    PubMed

    Jeon, Jong-Rok; Kim, Eun-Ju; Kim, Young-Mo; Murugesan, Kumarasamy; Kim, Jae-Hwan; Chang, Yoon-Seok

    2009-11-01

    Natural organic coagulants (NOCs) such as chitosan and Moringa oleifera seeds have been extensively characterized for potential application in water treatment as an alternative to metal-based coagulants. However, the action of both chitosan and M. oleifera seeds is mainly restricted to anionic organic pollutants because of their cationic functional groups affording poor cationic pollutant coagulation by electrostatic repulsion. In this study, we employed ethanolic grape seed extract (GSE) and grape seed-derived polyphenols such as tannic acid and catechin in an effort to find novel NOCs showing stable anionic forms for removal of cationic organic pollutants. The target substances tested were malachite green (MG) and crystal violet (CV), both mutagenic cationic dyes. Polyphenol treatment induced fast decolorization followed by gradual floc formation concomitant with red or blue shifts in maximum absorbance wavelengths of the cationic dyes. Liquid chromatography analysis of flocs formed by polyphenols directly showed that initial supramolecular complexes attributed mainly to electrostatic attraction between polyphenol hydroxyphenyl groups and cationic dyes further progressed into stronger aggregates, leading to precipitation of dye-polyphenol complexes. Consistent with the results obtained using catechin and tannic acid, use of GSE also resulted in effective decolorization and coagulation of soluble MG and CV in aqueous solutions. Screening of several organic GSE components for NOC activity strongly suggested that natural polyphenols are the main organic ingredients causing MG and CV removal via gradual floc formation. The treatment by natural polyphenols and GSE decreased toxicity of MG- or CV-contaminated water. PMID:19786292

  3. Ground and Excited-Electronic-State Dissociations of Hydrogen-Rich and Hydrogen-Deficient Tyrosine Peptide Cation Radicals

    NASA Astrophysics Data System (ADS)

    Viglino, Emilie; Lai, Cheuk Kuen; Mu, Xiaoyan; Chu, Ivan K.; Tureček, František

    2016-09-01

    We report a comprehensive study of collision-induced dissociation (CID) and near-UV photodissociation (UVPD) of a series of tyrosine-containing peptide cation radicals of the hydrogen-rich and hydrogen-deficient types. Stable, long-lived, hydrogen-rich peptide cation radicals, such as [AAAYR + 2H]+● and several of its sequence and homology variants, were generated by electron transfer dissociation (ETD) of peptide-crown-ether complexes, and their CID-MS3 dissociations were found to be dramatically different from those upon ETD of the respective peptide dications. All of the hydrogen-rich peptide cation radicals contained major (77%-94%) fractions of species having radical chromophores created by ETD that underwent photodissociation at 355 nm. Analysis of the CID and UVPD spectra pointed to arginine guanidinium radicals as the major components of the hydrogen-rich peptide cation radical population. Hydrogen-deficient peptide cation radicals were generated by intramolecular electron transfer in CuII(2,2 ':6 ',2 ″-terpyridine) complexes and shown to contain chromophores absorbing at 355 nm and undergoing photodissociation. The CID and UVPD spectra showed major differences in fragmentation for [AAAYR]+● that diminished as the Tyr residue was moved along the peptide chain. UVPD was found to be superior to CID in localizing Cα-radical positions in peptide cation radical intermediates.

  4. Ground and Excited-Electronic-State Dissociations of Hydrogen-Rich and Hydrogen-Deficient Tyrosine Peptide Cation Radicals.

    PubMed

    Viglino, Emilie; Lai, Cheuk Kuen; Mu, Xiaoyan; Chu, Ivan K; Tureček, František

    2016-09-01

    We report a comprehensive study of collision-induced dissociation (CID) and near-UV photodissociation (UVPD) of a series of tyrosine-containing peptide cation radicals of the hydrogen-rich and hydrogen-deficient types. Stable, long-lived, hydrogen-rich peptide cation radicals, such as [AAAYR + 2H](+●) and several of its sequence and homology variants, were generated by electron transfer dissociation (ETD) of peptide-crown-ether complexes, and their CID-MS(3) dissociations were found to be dramatically different from those upon ETD of the respective peptide dications. All of the hydrogen-rich peptide cation radicals contained major (77%-94%) fractions of species having radical chromophores created by ETD that underwent photodissociation at 355 nm. Analysis of the CID and UVPD spectra pointed to arginine guanidinium radicals as the major components of the hydrogen-rich peptide cation radical population. Hydrogen-deficient peptide cation radicals were generated by intramolecular electron transfer in Cu(II)(2,2':6',2″-terpyridine) complexes and shown to contain chromophores absorbing at 355 nm and undergoing photodissociation. The CID and UVPD spectra showed major differences in fragmentation for [AAAYR](+●) that diminished as the Tyr residue was moved along the peptide chain. UVPD was found to be superior to CID in localizing Cα-radical positions in peptide cation radical intermediates. Graphical Abstract ᅟ. PMID:27278824

  5. Ground and Excited-Electronic-State Dissociations of Hydrogen-Rich and Hydrogen-Deficient Tyrosine Peptide Cation Radicals

    NASA Astrophysics Data System (ADS)

    Viglino, Emilie; Lai, Cheuk Kuen; Mu, Xiaoyan; Chu, Ivan K.; Tureček, František

    2016-06-01

    We report a comprehensive study of collision-induced dissociation (CID) and near-UV photodissociation (UVPD) of a series of tyrosine-containing peptide cation radicals of the hydrogen-rich and hydrogen-deficient types. Stable, long-lived, hydrogen-rich peptide cation radicals, such as [AAAYR + 2H]+● and several of its sequence and homology variants, were generated by electron transfer dissociation (ETD) of peptide-crown-ether complexes, and their CID-MS3 dissociations were found to be dramatically different from those upon ETD of the respective peptide dications. All of the hydrogen-rich peptide cation radicals contained major (77%-94%) fractions of species having radical chromophores created by ETD that underwent photodissociation at 355 nm. Analysis of the CID and UVPD spectra pointed to arginine guanidinium radicals as the major components of the hydrogen-rich peptide cation radical population. Hydrogen-deficient peptide cation radicals were generated by intramolecular electron transfer in CuII(2,2':6',2″-terpyridine) complexes and shown to contain chromophores absorbing at 355 nm and undergoing photodissociation. The CID and UVPD spectra showed major differences in fragmentation for [AAAYR]+● that diminished as the Tyr residue was moved along the peptide chain. UVPD was found to be superior to CID in localizing Cα-radical positions in peptide cation radical intermediates.

  6. Monovalent cation transport in irreversibly sickled cells.

    PubMed Central

    Clark, M R; Morrison, C E; Shohet, S B

    1978-01-01

    Using discontinuous density gradients of Stractan II, we have separated sickle cell blood into discrete subpopulations of reticulocytes, mature discoid cells, and irreversibly sickled cells (ISCs). We have measured active and passive fluxes of monovalent cations in mature discoid cells, ISCs, and normal control cells, also separated upon density gradients. These measurements revealed a decreased active cation transport in ISC-rich populations. However, parallel measurements of Na, K-ATPase activity showed normal ouabain-sensitive ATPase activity in ISCs. Passive permeability to external Rb was also normal in ISCs. The observation of depressed pump activity in intact ISCs, contrasted with normal ATPase activity in ISC membranes, suggests the presence of factors in the intact cell which inhibit the active transport of Na and K in ISCs. PMID:149799

  7. Structurally Distinct Cation Channelrhodopsins from Cryptophyte Algae.

    PubMed

    Govorunova, Elena G; Sineshchekov, Oleg A; Spudich, John L

    2016-06-01

    Microbial rhodopsins are remarkable for the diversity of their functional mechanisms based on the same protein scaffold. A class of rhodopsins from cryptophyte algae show close sequence homology with haloarchaeal rhodopsin proton pumps rather than with previously known channelrhodopsins from chlorophyte (green) algae. In particular, both aspartate residues that occupy the positions of the chromophore Schiff base proton acceptor and donor, a hallmark of rhodopsin proton pumps, are conserved in these cryptophyte proteins. We expressed the corresponding polynucleotides in human embryonic kidney (HEK293) cells and studied electrogenic properties of the encoded proteins with whole-cell patch-clamp recording. Despite their lack of residues characteristic of the chlorophyte cation channels, these proteins are cation-conducting channelrhodopsins that carry out light-gated passive transport of Na(+) and H(+). These findings show that channel function in rhodopsins has evolved via multiple routes. PMID:27233115

  8. Cation specific binding with protein surface charges.

    PubMed

    Hess, Berk; van der Vegt, Nico F A

    2009-08-11

    Biological organization depends on a sensitive balance of noncovalent interactions, in particular also those involving interactions between ions. Ion-pairing is qualitatively described by the law of "matching water affinities." This law predicts that cations and anions (with equal valence) form stable contact ion pairs if their sizes match. We show that this simple physical model fails to describe the interaction of cations with (molecular) anions of weak carboxylic acids, which are present on the surfaces of many intra- and extracellular proteins. We performed molecular simulations with quantitatively accurate models and observed that the order K(+) < Na(+) < Li(+) of increasing binding affinity with carboxylate ions is caused by a stronger preference for forming weak solvent-shared ion pairs. The relative insignificance of contact pair interactions with protein surfaces indicates that thermodynamic stability and interactions between proteins in alkali salt solutions is governed by interactions mediated through hydration water molecules. PMID:19666545

  9. Electronic spectrum of 9-methylanthracenium radical cation

    NASA Astrophysics Data System (ADS)

    O'Connor, Gerard D.; Sanelli, Julian A.; Dryza, Vik; Bieske, Evan J.; Schmidt, Timothy W.

    2016-04-01

    The predissociation spectrum of the cold, argon-tagged, 9-methylanthracenium radical cation is reported from 8000 cm-1 to 44 500 cm-1. The reported spectrum contains bands corresponding to at least eight electronic transitions ranging from the near infrared to the ultraviolet. These electronic transitions are assigned through comparison with ab initio energies and intensities. The infrared D1←D0 transitions exhibit significant vibronic activity, which is assigned through comparison with TD-B3LYP excited state frequencies and intensities, as well as modelled vibronic interactions. Dissociation of 9-methylanthracenium is also observed at high visible-photon energies, resulting in the loss of either CH2 or CH3. The relevance of these spectra, and the spectra of other polycyclic aromatic hydrocarbon radical cations, to the largely unassigned diffuse interstellar bands, is discussed.

  10. [PAH Cations as Viable Carriers of DIBs

    NASA Technical Reports Server (NTRS)

    Snow, Ted

    1998-01-01

    This report is intended to fill in the blanks in NASA's file system for our lab astro study of molecular ions of astrophysical interest. In order to give NASA what it needs for its files, I attach below the text of the section from our recent proposal to continue this work, in which we describe progress to date, including a large number of publications. Our initial studies were focused on PAH cations, which appear to be viable candidates as the carriers of the DIBs, an idea that has been supported by laboratory spectroscopy of PAH cations in inert matrices. Beginning with the simplest aromatic (benzene; C6H6) and moving progressively to larger species (naphthalene, C10OH8; pyrene, C16H10; and most recently chrysene, C18H12), we have been able to derive rate coefficients for reactions with neutral spices that are abundant in the diffuse interstellar medium.

  11. Ultrafast dynamics of water in cationic micelles

    NASA Astrophysics Data System (ADS)

    Dokter, Adriaan M.; Woutersen, Sander; Bakker, Huib J.

    2007-03-01

    The effect of confinement on the dynamical properties of liquid water is investigated for water enclosed in cationic reverse micelles. The authors performed mid-infrared ultrafast pump-probe spectroscopy on the OH-stretch vibration of isotopically diluted HDO in D2O in cetyltrimethylammonium bromide (CTAB) reverse micelles of various sizes. The authors observe that the surfactant counterions are inhomogeneously distributed throughout the reverse micelle, and that regions of extreme salinity occur near the interfacial Stern layer. The authors find that the water molecules in the core of the micelles show similar orientational dynamics as bulk water, and that water molecules in the counterion-rich interfacial region are much less mobile. An explicit comparison is made with the dynamics of water confined in anionic sodium bis(2-ethythexyl) sulfosuccinate (AOT) reverse micelles. The authors find that interfacial water in cationic CTAB reverse micelles has a higher orientational mobility than water in anionic AOT reverse micelles.

  12. Plant NHX cation/proton antiporters

    PubMed Central

    Rodríguez-Rosales, M Pilar; Gálvez, Francisco J; Huertas, Raúl; Aranda, M Nieves; Baghour, Mourad; Cagnac, Olivier

    2009-01-01

    Although physiological and biochemical data since long suggested that Na+/H+ and K+/H+ antiporters are involved in intracellular ion and pH regulation in plants, it has taken a long time to identify genes encoding antiporters that could fulfil these roles. Genome sequencing projects have now shown that plants contain a very large number of putative Cation/Proton antiporters, the function of which is only beginning to be studied. The intracellular NHX transporters constitute the first Cation/Proton exchanger family studied in plants. The founding member, AtNHX1, was identified as an important salt tolerance determinant and suggested to catalyze Na+ accumulation in vacuoles. It is, however, becoming increasingly clear, that this gene and other members of the family also play crucial roles in pH regulation and K+ homeostasis, regulating processes from vesicle trafficking and cell expansion to plant development. PMID:19794841

  13. Alkaline earth cation extraction from acid solution

    DOEpatents

    Dietz, Mark; Horwitz, E. Philip

    2003-01-01

    An extractant medium for extracting alkaline earth cations from an aqueous acidic sample solution is described as are a method and apparatus for using the same. The separation medium is free of diluent, free-flowing and particulate, and comprises a Crown ether that is a 4,4'(5')[C.sub.4 -C.sub.8 -alkylcyclohexano]18-Crown-6 dispersed on an inert substrate material.

  14. Novel penetrating cations for targeting mitochondria.

    PubMed

    Chernyak, Boris V; Antonenko, Yuri N; Domnina, Lidia V; Ivanova, Olga Yu; Lyamzaev, Konstantin G; Pustovidko, Antonina V; Rokitskaya, Tatiana I; Severina, Inna I; Simonyan, Ruben A; Trendeleva, Tatiana A; Zvyagilskaya, Renata A

    2013-01-01

    Novel penetrating cations were used for the design of mitochondria-targeted compounds and tested in model lipid membranes, in isolated mitochondria and in living human cells in culture. Rhodamine-19, berberine and palmatine were conjugated by aliphatic linkers with plastoquinone possessing antioxidant activity. These conjugates (SkQR1,SkQBerb, SkQPalm) and their analogs lacking plastoquinol moiety (C12R1,C10Berb and C10Palm) penetrated bilayer phospholipid membrane in their cationic forms and accumulated in isolated mitochondria or in mitochondria of living cells due to membrane potential negative inside. Reduced forms of SkQR1, SkQBerb and SkQPalm inhibited lipid peroxidation in isolated mitochondria at nanomolar concentrations. In human fibroblasts SkQR1, SkQBerb and SkQPalm prevented fragmentation of mitochondria and apoptosis induced by hydrogen peroxide. SkQR1 was effective at subnanomolar concentrations while SkQberb, SkQPalm and SkQ1 (prototypic conjugate of plastoquinone with dodecyltriphenylphosphonium) were effective at 10-times higher concentrations. The aliphatic conjugates of berberine and palmatine (as well as the conjugates of triphenylphosphonium) induced proton transport mediated by free fatty acids (FA) both in the model and mitochondrial membrane. In mitochondria this process was facilitated by the adenine nucleotide carrier. In contrast to the other cationic conjugates, SkQR1 and C12R1 induced FA-independent proton conductivity due to protonation/deprotonation of the rhodamine residue. This property in combination with the antioxidant activity probably makes rhodamine conjugates highly effective in protection against oxidative stress. The novel cationic conjugates described here are promising candidates for drugs against various pathologies and aging as mitochondria-targeted antioxidants and selective mild uncouplers. PMID:23092317

  15. Regulation of Cation Balance in Saccharomyces cerevisiae

    PubMed Central

    Cyert, Martha S.; Philpott, Caroline C.

    2013-01-01

    All living organisms require nutrient minerals for growth and have developed mechanisms to acquire, utilize, and store nutrient minerals effectively. In the aqueous cellular environment, these elements exist as charged ions that, together with protons and hydroxide ions, facilitate biochemical reactions and establish the electrochemical gradients across membranes that drive cellular processes such as transport and ATP synthesis. Metal ions serve as essential enzyme cofactors and perform both structural and signaling roles within cells. However, because these ions can also be toxic, cells have developed sophisticated homeostatic mechanisms to regulate their levels and avoid toxicity. Studies in Saccharomyces cerevisiae have characterized many of the gene products and processes responsible for acquiring, utilizing, storing, and regulating levels of these ions. Findings in this model organism have often allowed the corresponding machinery in humans to be identified and have provided insights into diseases that result from defects in ion homeostasis. This review summarizes our current understanding of how cation balance is achieved and modulated in baker’s yeast. Control of intracellular pH is discussed, as well as uptake, storage, and efflux mechanisms for the alkali metal cations, Na+ and K+, the divalent cations, Ca2+ and Mg2+, and the trace metal ions, Fe2+, Zn2+, Cu2+, and Mn2+. Signal transduction pathways that are regulated by pH and Ca2+ are reviewed, as well as the mechanisms that allow cells to maintain appropriate intracellular cation concentrations when challenged by extreme conditions, i.e., either limited availability or toxic levels in the environment. PMID:23463800

  16. Cationic carbosilane dendrimers and oligonucleotide binding: an energetic affair

    NASA Astrophysics Data System (ADS)

    Marson, D.; Laurini, E.; Posocco, P.; Fermeglia, M.; Pricl, S.

    2015-02-01

    Generation 2 cationic carbosilane dendrimers hold great promise as internalizing agents for gene therapy as they present low toxicity and retain and internalize the genetic material as an oligonucleotide or siRNA. In this work we carried out complete in silico structural and energetical characterization of the interactions of a set of G2 carbosilane dendrimers, showing different affinity towards two single strand oligonucleotide (ODN) sequences in vitro. Our simulations predict that these four dendrimers and the relevant ODN complexes are characterized by similar size and shape, and that the molecule-specific ODN binding ability can be rationalized only by considering a critical molecular design parameter: the normalized effective binding energy ΔGbind,eff/Neff, i.e. the performance of each active individual dendrimer branch directly involved in a binding interaction.Generation 2 cationic carbosilane dendrimers hold great promise as internalizing agents for gene therapy as they present low toxicity and retain and internalize the genetic material as an oligonucleotide or siRNA. In this work we carried out complete in silico structural and energetical characterization of the interactions of a set of G2 carbosilane dendrimers, showing different affinity towards two single strand oligonucleotide (ODN) sequences in vitro. Our simulations predict that these four dendrimers and the relevant ODN complexes are characterized by similar size and shape, and that the molecule-specific ODN binding ability can be rationalized only by considering a critical molecular design parameter: the normalized effective binding energy ΔGbind,eff/Neff, i.e. the performance of each active individual dendrimer branch directly involved in a binding interaction. Electronic supplementary information (ESI) available: Additional figures and tables. See DOI: 10.1039/c4nr04510f

  17. Use of MgO doped with a divalent or trivalent metal cation for removing arsenic from water

    DOEpatents

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

    2013-08-13

    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.

  18. Effects of divalent cations on the formation of 4(5)-methylimidazole in fructose/ammonium hydroxide caramel model reaction.

    PubMed

    Wu, Xinlan; Yu, Di; Kong, Fansheng; Yu, Shujuan

    2016-06-15

    The objective of the present study was to detail the changes of 4(5)-methylimidazole (4-MI) and its precursors in the presence of divalent cations (Ca(2+), Mg(2+)) in a fructose/ammonium hydroxide caramel model system. The content of 4-MI and its precursor methylglyoxal (MGO) was inhibited by divalent cations (Ca(2+), Mg(2+)). The possible explanation might be that fructose and its Heyns product glucosamine interact with divalent cations to form complexes and inhibit the degradation of glucosamine into MGO. Moreover, the changes of fructose, NH4(+) and brown intensity in the presence of divalent cations indicated that fructose and glucosamine underwent intra-intermolecular polymerisation into melanoidins rather than the degradation reaction into aldehydes and ketones. PMID:26868573

  19. Sn Cation Valency Dependence in Cation Exchange Reactions Involving Cu2-xSe Nanocrystals

    PubMed Central

    2014-01-01

    We studied cation exchange reactions in colloidal Cu2-xSe nanocrystals (NCs) involving the replacement of Cu+ cations with either Sn2+ or Sn4+ cations. This is a model system in several aspects: first, the +2 and +4 oxidation states for tin are relatively stable; in addition, the phase of the Cu2-xSe NCs remains cubic regardless of the degree of copper deficiency (that is, “x”) in the NC lattice. Also, Sn4+ ions are comparable in size to the Cu+ ions, while Sn2+ ones are much larger. We show here that the valency of the entering Sn ions dictates the structure and composition not only of the final products but also of the intermediate steps of the exchange. When Sn4+ cations are used, alloyed Cu2–4ySnySe NCs (with y ≤ 0.33) are formed as intermediates, with almost no distortion of the anion framework, apart from a small contraction. In this exchange reaction the final stoichiometry of the NCs cannot go beyond Cu0.66Sn0.33Se (that is Cu2SnSe3), as any further replacement of Cu+ cations with Sn4+ cations would require a drastic reorganization of the anion framework, which is not possible at the reaction conditions of the experiments. When instead Sn2+ cations are employed, SnSe NCs are formed, mostly in the orthorhombic phase, with significant, albeit not drastic, distortion of the anion framework. Intermediate steps in this exchange reaction are represented by Janus-type Cu2-xSe/SnSe heterostructures, with no Cu–Sn–Se alloys. PMID:25340627

  20. Low cation coordination in oxide melts

    SciTech Connect

    Skinner, Lawrie; Benmore, Chris J; Du, Jincheng; Weber, Richard; Neuefeind, Joerg C; Tumber, Sonia; Parise, John B

    2014-01-01

    The complete set of Faber-Ziman partial pair distribution functions for a rare earth oxide liquid were measured for the first time by combining aerodynamic levitation, neutron diffraction, high energy x-ray diffraction and isomorphic substitution using Y2 O3 and Ho2 O3 melts. The average Y- O coordination is measured to be 5.5(2), which is significantly less than the octahedral coordination of crystalline Y2 O3 (or Ho2 O3 ). Investigation of high temperature La2 O3 , ZrO2 , SiO2 , and Al2 O3 melts by x-ray diffraction and molecular dynamics simulations also show lower-than-crystal cation- oxygen coordination. These measurements suggest a general trend towards lower M-O coordination compared to their crystalline counterparts. It is found that this coordination number drop is larger for lower field strength, larger radius cations and is negligible for high field strength (network forming) cations. These findings have broad implications for predicting the local structure and related physical properties of metal-oxide melts and oxide glasses.

  1. Study of the fluoro- and chlorodimethylbutyl cations

    PubMed Central

    Olah, George A.; Prakash, G. K. Surya; Rasul, Golam

    2013-01-01

    A comparative study of the 2,3-dimethyl-3-fluoro-2-butyl cation and its chloro analog was carried out by the ab initio/GIAO-CCSD(T) (gauge invariant atomic orbital-coupled cluster with single, double, and perturbative triple excitation) method. The structures and 13C NMR chemical shifts of the cations were calculated at the GIAO-CCSD(T)/tzp/dz//MP2/cc-pVTZ level. Bridged fluoronium ion 1, carbenium ion 2, and fluorocarbenium ion 3 were found to be minima on the potential energy surface. Bridged fluoronium ion 1, although a minimum on the potential energy surface, is 12.8 kcal/mol less stable than the open chain fluorobutyl cation 3. In contrast to the fluorinated ion, bridged chloronium ion 5 was found to be the lowest energy minimum being 10.6 kcal/mol more stable than ion 6 and 7.4 kcal/mol more stable than ion 7. PMID:23650369

  2. Cationic nanoemulsion as a delivery system for oligonucleotides targeting malarial topoisomerase II.

    PubMed

    Bruxel, F; Cojean, S; Bochot, A; Teixeira, H; Bories, C; Loiseau, P-M; Fattal, E

    2011-09-20

    A promising strategy based on the antisense oligonucleotides against the Plasmodium falciparum topoisomerase II has been considered using cationic nanoemulsion as oligonucleotide delivery system. Phosphodiester and chemically modified phosphorothioate oligonucleotides bearing negative charges were adsorbed on positively charged emulsion composed of medium chain triglycerides, egg lecithin, 1,2-dioleoyl-3-trimethylammonium-propane (DOTAP), and water, at different +/- charge ratios (positive charges from cationic lipid/negative charges from oligonucleotide): +0.5/-, +2/-, +4/- and +6/-. The physicochemical properties of the complexes were determined, as well as their stability in culture medium. Their interaction with erythrocytes through hemolysis, binding experiments and confocal microscopy were also evaluated. Finally, the in vitro evaluation of parasite growth and reinfection capacity was performed. The overall results showed that antisense oligonucleotides against P. falciparum topoisomerase II gene can be efficiently adsorbed onto a cationic nanoemulsion forming complexes. Whereas unloaded nanoemulsion displayed an hemolytic effect due to the presence of the cationic lipid, this was not the case of loaded nanoemulsion at low +/- ratios. Oligonucleotide-loaded nanoemulsions were found to be located inside the infected erythrocytes, inhibiting efficiently parasite growth (until 80%) and causing a delay in P. falciparum life cycle. PMID:21291974

  3. A self-assembled polymeric micellar immunomodulator for cancer treatment based on cationic amphiphilic polymers.

    PubMed

    Yim, Hyeona; Park, Wooram; Kim, Dongin; Fahmy, Tarek M; Na, Kun

    2014-12-01

    Here, we report a self-assembled polymeric micellar immunomodulator (SPI) for enhanced cancer treatment based on cationic amphiphilic polymers. To obtain the cationic amphiphilic polymer, the hydrophobic all-trans-retinoic acid (ATRA) was conjugated with a hydrophilic low-molecular-weight PEI (LowPEI, Mn = 1.8 kDa). The ATRA-LowPEI conjugates could self-assemble in aqueous media, forming micelles with a strong positive charge (∼+40 mV) and particle sizes of ~70 nm. Compared to conventional therapeutic agents (e.g., cisplatin), the SPI exhibited enhanced anti-cancer activity regardless of drug resistance. After mechanistic in vitro cell death studies, we revealed that the mechanical disruptive force generated by the cationic charge of SPI primarily induced necrotic cell death. Furthermore, the organelle fragments induced by the necrotic cell death triggered antitumoral immune responses. Therefore, SPI induced synergistic effects of the cationic charge-induced necrosis and antitumoral immune responses could produce an effective cancer treatment. In addition, the SPI was shielded by hyaluronic acid (HA/SPI complex) to enhance its tumor selectivity in vivo. Finally, the HA/SPI complex accumulated selectively into tumor sites after systemic administration into tumor-bearing mice, exhibiting effective antitumoral effects without systemic toxicity. Therefore, this technology holds great potential for translation into a clinical cancer treatment. PMID:25239044

  4. Cation uptake and allocation by red pine seedlings under cation-nutrient stress in a column growth experiment

    Technology Transfer Automated Retrieval System (TEKTRAN)

    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 stress on cation uptake in an experimental plant-mineral system. Methods: Column experim...

  5. Infrared photodissociation spectroscopy of vanadium oxide-carbonyl cations.

    PubMed

    Brathwaite, A D; Ricks, A M; Duncan, M A

    2013-12-19

    Mass selected vanadium oxide-carbonyl cations of the form VO(m)(CO)(n)(+) (m = 0-3 and n = 3-6) are studied via infrared laser photodissociation spectroscopy in the 600-2300 cm(-1) region. Insight into the structure and bonding of these complexes is obtained from the number of infrared active bands, their relative intensities and their frequency positions. Density functional theory calculations are carried out in support of the experimental data. The effect of oxidation on the carbonyl stretching frequencies of VO(CO)(n)(+), VO2(CO)(n)(+), and VO3(CO)(n)(+) complexes is investigated. All of these oxide-carbonyl species have C-O stretch vibrations blue-shifted from those of the pure vanadium ion carbonyls. The V-O stretches of these complexes are also investigated, revealing the effects of CO coordination on these vibrations. The oxide-carbonyls all have a hexacoordinate core analogous to that of V(CO)6(+). The fully coordinated vanadium monoxide-carbonyl species is VO(CO)5(+), and those of the dioxide and trioxide are VO2(CO)4(+) and VO3(CO)3(+), respectively. PMID:23927497

  6. Experimental and theoretical study on interaction of the silver cation with nonactin

    NASA Astrophysics Data System (ADS)

    Makrlík, Emanuel; Vaňura, Petr

    2015-12-01

    From extraction experiments and γ-activity measurements, the extraction constant corresponding to the equilibrium ? occurring in the two-phase water-nitrobenzene system (1 = nonactin, aq = aqueous phase, nb = nitrobenzene phase) was evaluated as log Kex (Ag+, 1 ṡ Na+) = 0.6 ± 0.1. Furthermore, the stability constant of the 1 ṡ Ag+ complex in nitrobenzene saturated with water was calculated for a temperature of 25 °C: log βnb(1 ṡ Ag+) = 6.6 ± 0.2. Finally, employing quantum mechanical calculations, the most probable structure of the cationic complex species 1 ṡ Ag+ was derived. In the resulting complex, having a tennis-ball-seam conformation with the C2 symmetry, the 'central' cation Ag+ is bound by eight relatively strong bonding interactions to eight oxygen atoms of the parent nonactin ligand. The interaction energy of the considered 1 ṡ Ag+ complex was found to be -468.5 kJ/mol, confirming also the formation of this cationic species.

  7. Potential-energy surface and van der Waals motions of p-difluorobenzene-argon cation

    NASA Astrophysics Data System (ADS)

    Makarewicz, Jan

    2005-07-01

    The structure and dynamics of the van der Waals complex of argon with the p-difluorobenzene cation are investigated using the ab initio theory. The restricted open-shell Møller-Plesset second-order perturbation method combined with the augmented correlation-consistent polarized valence double-ζ basis set is employed to determine the electronic ground-state potential-energy surface of the cationic complex. This surface is extremely flat in a wide region of the configuration space of the Ar atom which moves almost freely over the monomer ring. However, it is bound to the monomer stronger in the cationic than in the neutral complex. Its binding energy is calculated to be 621cm-1 at a distance of 3.445Å from the monomer center. The calculated dissociation energy of 572cm-1 agrees perfectly with the experimental value of 572±6cm-1 [S. M. Belm, R. J. Moulds, and D. Lawrence, J. Chem. Phys. 115, 10709 (2001)]. The effect of a strong coupling of large-amplitude intermolecular motions on the character of van der Waals vibrational states is investigated. The vibrational structure of the spectrum of the complex is explained and its earlier assignment is partly corrected.

  8. Comparative analysis of cation/proton antiporter superfamily in plants

    SciTech Connect

    Ye, Chuyu; Yang, Xiaohan; Xia, Xinli; Yin, Weilun

    2013-01-01

    The cation/proton antiporter superfamily is associated with the transport of monovalent cations across membranes. This superfamily was annotated in the Arabidopsis genome and some members were functionally characterized. In the present study, a systematic analysis of the cation/proton antiporter genes in diverse plant specieswas reported.We identified 240 cation/proton antiporters in alga, moss, and angiosperm. A phylogenetic tree was constructed showing these 240members are separated into three families, i.e., Na+/H+ exchangers, K+ efflux antiporters, and cation/H+ exchangers. Our analysis revealed that tandem and/or segmental duplications contribute to the expansion of cation/H+ exchangers in the examined angiospermspecies. Sliding windowanalysis of the nonsynonymous/synonymous substitution ratios showed some differences in the evolutionary fate of cation/proton antiporter paralogs. Furthermore, we identified over-represented motifs among these 240 proteins and foundmostmotifs are family specific, demonstrating diverse evolution of the cation/proton antiporters among three families. In addition, we investigated the co-expressed genes of the cation/proton antiporters in Arabidopsis thaliana. The results showed some biological processes are enriched in the co-expressed genes, suggesting the cation/proton antiporters may be involved in these biological processes. Taken together, this study furthers our knowledge on cation/proton antiporters in plants.

  9. Cation Exchange Reactions for Improved Quality and Diversity of Semiconductor Nanocrystals

    NASA Astrophysics Data System (ADS)

    Beberwyck, Brandon James

    Observing the size and shape dependent physical properties of semiconductor nanocrystals requires synthetic methods capable of not only composition and crystalline phase control but also molecular scale uniformity for a particle consisting of tens to hundreds of thousands of atoms. The desire for synthetic methods that produce uniform nanocrystals of complex morphologies continues to increase as nanocrystals find roles in commercial applications, such as biolabeling and display technologies, that are simultaneously restricting material compositions. With these constraints, new synthetic strategies that decouple the nanocrystal's chemical composition from its morphology are necessary. This dissertation explores the cation exchange reaction of colloidal semiconductor nanocrystals, a template-based chemical transformation that enables the interconversion of nanocrystals between a variety of compositions while maintaining their size dispersity and morphology. Chapter 1 provides an introduction to the versatility of this replacement reaction as a synthetic method for semiconductor nanocrystals. An overview of the fundamentals of the cation exchange reaction and the diversity of products that are achievable is presented. Chapter 2 examines the optical properties of nanocrystal heterostructures produced through cation exchange reactions. The deleterious impact of exchange on the photoluminescence is correlated to residual impurities and a simple annealing protocol is demonstrated to achieve photoluminescence yields comparable to samples produced by conventional methods. Chapter 3 investigates the extension of the cation exchange reaction beyond ionic nanocrystals. Covalent III-V nanocrystal of high crystallinity and low size dispersity are synthesized by the cation exchange of cadmium pnictide nanocrystals with group 13 ions. Lastly, Chapter 4 highlights future studies to probe cation exchange reactions in colloidal semiconductor nanocrystals and progress that needs to be

  10. Influence of Divalent Cations on Deformation and Rupture of Adsorbed Lipid Vesicles.

    PubMed

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

    2016-06-28

    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. PMID:27182843

  11. Radiolytic generation of radical cations in xenon matrices. Tetramethylcyclopropane radical cation and its transformations

    SciTech Connect

    Qin, X.Z.; Trifunac, A.D. )

    1990-04-05

    Radiolytic generation of radical cations in xenon matrices containing electron scavengers is illustrated by studying the 1,1,2,2-tetramethylcyclopropane radical cation. Dilute and concentrated solutions of tetramethylcyclopropane in xenon without electron scavengers and neat tetramethylcyclopropane yielded neutral radicals upon {gamma}-irradiation. Speculation on the mechanisms of radical formation is presented. The radical species observed in the {gamma}-irradiation of neat tetramethylcyclopropane appears to be identical with the paramagnetic species observed in CF{sub 2}ClCFCl{sub 2} above 120 K, suggesting that a neutral radical rather than the ring-opened distonic radical cation is observed in the CF{sub 2}ClCFCl{sub 2} matrix.

  12. Ultrafast dynamics of pyrrolidinium cation ionic liquids.

    PubMed

    Shirota, Hideaki; Funston, Alison M; Wishart, James F; Castner, Edward W

    2005-05-01

    We have investigated the ultrafast molecular dynamics of five pyrrolidinium cation room temperature ionic liquids using femtosecond optical heterodyne-detected Raman-induced Kerr effect spectroscopy. The ionic liquids studied are N-butyl-N-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide P14+/NTf2-), N-methoxyethyl-N-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide P1EOE+/NTf2-), N-ethoxyethyl-N-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide P1EOE+/NTf2-), N-ethoxyethyl-N-methylpyrrolidinium bromide P1EOE+, and N-ethoxyethyl-N-methylpyrrolidinium dicyanoamide P1EOE+/DCA-). For comparing dynamics among the five ionic liquids, we categorize the ionic liquids into two groups. One group of liquids comprises the three pyrrolidinium cations P14+, P1EOM+, and P1EOE+ paired with the NTf2- anion. The other group of liquids consists of the P1EOE+ cation paired with each of the three anions NTf2-, Br-, and DCA-. The overdamped relaxation for time scales longer than 2 ps has been fit by a triexponential function for each of the five pyrrolidinium ionic liquids. The fast ( approximately 2 ps) and intermediate (approximately 20 ps) relaxation time constants vary little among these five ionic liquids. However, the slow relaxation time constant correlates with the viscosity. Thus, the Kerr spectra in the range from 0 to 750 cm(-1) are quite similar for the group of three pyrrolidinium ionic liquids paired with the NTf2- anion. The intermolecular vibrational line shapes between 0 and 150 cm(-1) are fit to a multimode Brownian oscillator model; adequate fits required at least three modes to be included in the line shape. PMID:15918734

  13. Ultrafast dynamics of pyrrolidinium cation ionic liquids

    NASA Astrophysics Data System (ADS)

    Shirota, Hideaki; Funston, Alison M.; Wishart, James F.; Castner, Edward W.

    2005-05-01

    We have investigated the ultrafast molecular dynamics of five pyrrolidinium cation room temperature ionic liquids using femtosecond optical heterodyne-detected Raman-induced Kerr effect spectroscopy. The ionic liquids studied are N-butyl-N-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide P14+/NTf2-), N-methoxyethyl-N-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide P1EOE+/NTf2-), N-ethoxyethyl-N-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide P1EOE+/NTf2-), N-ethoxyethyl-N-methylpyrrolidinium bromideP1EOE+, and N-ethoxyethyl-N-methylpyrrolidinium dicyanoamide P1EOE+/DCA-). For comparing dynamics among the five ionic liquids, we categorize the ionic liquids into two groups. One group of liquids comprises the three pyrrolidinium cations P14+, P1EOM+, and P1EOE+ paired with the NTf2- anion. The other group of liquids consists of the P1EOE+ cation paired with each of the three anions NTf2-,Br-, and DCA-. The overdamped relaxation for time scales longer than 2 ps has been fit by a triexponential function for each of the five pyrrolidinium ionic liquids. The fast (˜2ps) and intermediate (˜20ps) relaxation time constants vary little among these five ionic liquids. However, the slow relaxation time constant correlates with the viscosity. Thus, the Kerr spectra in the range from 0 to 750cm-1 are quite similar for the group of three pyrrolidinium ionic liquids paired with the NTf2- anion. The intermolecular vibrational line shapes between 0 and 150cm-1 are fit to a multimode Brownian oscillator model; adequate fits required at least three modes to be included in the line shape.

  14. Cationic bituminous emulsions and emulsion aggregate slurries

    SciTech Connect

    Schilling, P.

    1986-07-01

    A cationic bituminous emulsion is described which consists of from about 30% to about 80% by weight of bitumen, from about 0.1% to about 10% by weight of an emulsifier selected from the group consisting of reaction products of a polyamine reacted with a member of the group consisting of epoxidized unsaturated fatty acids of chain lengths between C/sub 8/ and C/sub 22/ and the esters thereof and adding water to make up 100% by weight, the emulsion having a pH in the range of from 2-7.

  15. Nonclassical 21-Homododecahedryl Cation Rearrangement Revisited.

    PubMed

    Jalife, Said; Mondal, Sukanta; Osorio, Edison; Cabellos, José Luis; Martínez-Guajardo, Gerardo; Fernández-Herrera, María A; Merino, Gabriel

    2016-03-01

    The degenerate rearrangement in the 21-homododecahedryl cation (1) has been studied via density functional theory computations and Born-Oppenheimer Molecular Dynamics simulations. Compound 1 can be described as a highly fluxional hyperconjugated carbocation. Complete scrambling of 1 can be achieved by the combination of two unveiled barrierless processes. The first one is a "rotation" of one of the six-membered rings via a 0.8 kcal·mol(-1) barrier, and the second one is a slower interconvertion between two hyperconjomers via an out-of-plane methine bending (ΔG(⧧) = 4.0 kcal·mol(-1)). PMID:26862680

  16. Mobility of cations in magnesium aluminate spinel

    NASA Astrophysics Data System (ADS)

    Martinelli, J. R.; Sonder, E.; Weeks, R. A.; Zuhr, R. A.

    1986-04-01

    Transport of cations in magnesium aluminate spinel due to an applied electric field at approximately 1000 °C has been measured by observing changes in elemental concentrations near the cathode and anode surfaces using ion backscattering techniques. The results indicate that magnesium ions are the mobile species at 1000 °C and that these ions combine with ambient oxygen at the cathode surface to form a MgO layer. Quantitative interpretation of the data leads to the conclusion that the ionic transference number of spinel becomes approximately 0.5 after treatment in an electric field.

  17. Fragmentation Pathways in the Uracil Radical Cation

    SciTech Connect

    Zhou, Congyi; Matsika, Spiridoula; Kotur, Marija; Weinacht, Thomas C.

    2012-08-24

    We investigate pathways for fragmentation in the uracil radical cation using ab initio electronic structure calculations. We focus on the main fragments produced in pump–probe dissociative ionization experiments. These are fragments with mass to charge ratios (m/z) of 69, 28, 41, and 42. Barriers to dissociation along the ground ionic surface are reported, which provide an estimate of the energetic requirements for the production of the main fragments. Finally, direct and sequential fragmentation mechanisms have been analyzed, and it is concluded that sequential fragmentation after production of fragment with m/z 69 is the dominant mechanism for the production of the smaller fragments.

  18. ESI MS, spectroscopic and PM5 semiempirical studies of Colchicine complexes with lithium, sodium and potassium salts

    NASA Astrophysics Data System (ADS)

    Kurek, Joanna; Boczoń, Władysław; Przybylski, Piotr; Brzezinski, Bogumił

    2007-11-01

    The colchicine complexes with Li +, Na + and K + cations have been synthesized and studied by ESI MS, 1H and 13C NMR, FT-IR and PM5 semiempirical methods. It has been shown that colchicine forms stable complexes of 1:1 stoichiometry with monovalent metal cations. For Li + cations also formation of the 2:1 stoichiometry complexes has been detected. The most stable structures of the complexes are those in which the acetamide groups are involved in the coordination process. The structures of the colchicine complexes with Li +, Na + and K + cations are visualized and discussed in details.

  19. Interactions of cationic trimeric, gemini and monomeric surfactants with trianionic curcumin in aqueous solution.

    PubMed

    Wang, Meina; Wu, Chunxian; Tang, Yongqiang; Fan, Yaxun; Han, Yuchun; Wang, Yilin

    2014-05-21

    Interactions of trianionic curcumin (Cur(3-)) with a series of cationic surfactants, monomeric surfactant dodecyl trimethylammonium bromide (DTAB), dimeric surfactant hexamethylene-1,6-bis(dodecyldimethylammonium bromide) (12-6-12) and trimeric surfactant tri(dodecyldimethylammonioacetoxy)diethyltriamine trichloride (DTAD), have been investigated in aqueous solution of pH 13.0. Surface tension and spectral measurements indicate that the cationic surfactants display a similar surfactant concentration dependent interaction process with Cur(3-), involving three interaction stages. At first the three cationic surfactants electrostatically bind on Cur(3-) to form the surfactant-Cur(3-) complex. Then the bound and unbound cationic surfactants with Cur(3-) aggregate into surfactant-Cur(3-) mixed micelles through hydrophobic interactions above the critical micelle concentration of the surfactants (CMCC) in the presence of Cur(3-). Finally excess unbound surfactants self-assemble into micelles like those without Cur(3-). For all the three surfactants, the addition of Cur(3-) only decreases the critical micelle concentration of 12-6-12 but does not affect the critical micelle concentration of DTAB and DTAD. As the oligomeric degree of surfactants increases, the intermolecular interaction of the cationic surfactants with Cur(3-) increases and the surfactant amount needed for Cur(3-) encapsulation decreases. Compared with 12-6-12, either the weaker interaction of DTAB with Cur(3-) or stronger interaction of DTAD with Cur(3-) limits the stability or solubility of Cur(3-) in surfactant micelles. Therefore, gemini surfactant 12-6-12 is the best choice to effectively suppress Cur(3-) degradation at very low concentrations. Isothermal titration microcalorimetry, surface tension and (1)H NMR results reveal that 12-6-12 and Cur(3-) form a (12-6-12)2-Cur(3-) complex and start to form micelles at extremely decreased concentrations, where either 12-6-12 or Cur(3-) works as a bridge

  20. Laser Spectroscopy and Density Functional Study on Niobium Dimer Cation

    NASA Astrophysics Data System (ADS)

    Aydin, Metin; Lombardi, John R.

    2009-06-01

    Resonant multiphoton fragmentation spectra of niobium dimer cation (Nb2+) have been obtained by utilizing laser vaporization of a Nb metal target. Ions are mass-selected with a time-of-flight mass spectrometer followed by a mass gate, then fragmented with a pulsed dye laser, and the resulting fragment ions are detected with a second time-of-flight reflectron mass spectrometer and multichannel plate. Photon resonances are detected by monitoring ion current as a function of fragmentation laser wavelength. A rich, but complex spectrum of the cation is obtained. The bands display a characteristic multiplet structure that may be interpreted as due to transitions from the ground state X^{4}{Σ}^{-}({Ω}g) to several excited states, X^{4}{Π}({Ω}u) and X^{4}{Σ}(^{-}{Ω}u). The ground state X^{4}{Σ}^{-}({Ω}g) is derived from the electron configuration ({π}{_u})^{4} (1{σ}{_g})^{2}(2{σ}{_g})^{1} ({δ}{_g})^{2}. The two spin-orbit components are split by 145 cm^{-1} due to a strong second-order isoconfigurational spin-orbit interaction with the low-lying ^{2}{Σ}^{+}({Ω}g) state. The vibrational frequencies of the ground sate and the excited state of Nb2+ are identified as well as molecular spin-orbit constants (A{_S}{_O}) in the excited state. The electronic structure of niobium dimer cation was investigated using density functional theory. For the electronic ground state, the predicted spectroscopic properties were in good agreement with experiment. Calculations on excited states reveal congested manifolds of quartet and doublet electronic states in the range 0-30,000 cm^{-1}, reflecting the multitude of possible electronic promotions among the 4d- and 5s-based molecular orbitals. Comparisons are drawn between Nb^{+}{_2} and the prevalent isoelectronic molecules V^{+}{_2}/NbV^{+}/Nb{_2}/V{_2}/NbV. M. Aydin and John R. Lombardi J. Phys. Chem. A. xx XXXX 2009.

  1. Calixarenes and cations: a time-lapse photography of the big-bang.

    PubMed

    Casnati, Alessandro

    2013-08-01

    The outstanding cation complexation properties emerging from the pioneering studies on calixarene ligands during a five-year period in the early 1980s triggered a big-bang burst of publications on such macrocycles that is still lasting at a distance of more than 30 years. A time-lapse photography of this timeframe is proposed which allows the readers to pinpoint the contributions of the different research groups. PMID:23792898

  2. Soil Cation Status in Southern California: Interactions of Vehicular Emissions

    NASA Astrophysics Data System (ADS)

    Rossi, R.; Bain, D. J.; Jenerette, D.; Clarke, L. W.

    2012-12-01

    Roadside soils are often enriched in trace metals due to vehicular deposition. However, less attention is given to base cation pools in roadside soils. Relatively high loadings of nitrate from vehicular exhaust should acidify roadside soils, potentially mobilizing cationic species by displacing them from soil exchange sites. In contrast, weathering of road materials can contribute substantial amounts of these cations to the same soils, potentially replenishing cation pools. Base cations are essential nutrients and these dynamics may alter ecosystem processes in near-road environments. Metal concentrations in park and garden soils collected from Southern California (Los Angeles and Riverside Counties) were examined across gradients of road network intensity, climate and geology. In these samples, base cation concentrations decrease in areas of denser road networks. Base cation concentrations also decrease with distance from the road, with near-road samples relatively depleted in base cation concentrations. In addition, base cation concentrations are associated with traffic flux density, with exchange pools decreasing near heavily trafficked areas. These relationships suggest road activity is mobilizing cations, depleting near-road soils of essential nutrient pools, despite road material weathering. This depletion of soil nutrients from exchange pools in roadside soils likely influences local ecological function in unpredictable ways. This observation lays the groundwork for continued characterization of soil metal processes in the increasingly common roadside environment.

  3. Evaluation of cation-anion interaction strength in ionic liquids.

    PubMed

    Fernandes, Ana M; Rocha, Marisa A A; Freire, Mara G; Marrucho, Isabel M; Coutinho, João A P; Santos, Luís M N B F

    2011-04-14

    Electrospray ionization mass spectrometry with variable collision induced dissociation of the isolated [(cation)(2)anion](+) and/or [(anion)(2)cation](-) ions of imidazolium-, pyridinium-, pyrrolidinium-, and piperidinium-based ionic liquids (ILs) combined with a large set of anions, such as chloride, tetrafluoroborate, hexafluorophosphate, trifluoromethanesulfonate, and bis[(trifluoromethyl)sulfonyl]imide, was used to carry out a systematic and comprehensive study on the ionic liquids relative interaction energies. The results are interpreted in terms of main influences derived from the structural characteristics of both anion and cation. On the basis of quantum chemical calculations, the effect of the anion upon the dissociation energies of the ionic liquid pair, and isolated [(cation)(2)anion](+) and/or [(anion)(2)cation](-) aggregates, were estimated and are in good agreement with the experimental data. Both experimental and computational results indicate an energetic differentiation between the cation and the anion to the ionic pair. Moreover, it was found that the quantum chemical calculations can describe the trend obtained for the electrostatic cation-anion attraction potential. The impact of the cation-anion interaction strengths in the surface tension of ionic liquids is further discussed. The surface tensions dependence on the cation alkyl chain length, and on the anion nature, follows an analogous pattern to that of the relative cation-anion interaction energies determined by mass spectrometry. PMID:21425809

  4. Lithium ionophore VIII as an extraordinarily strong receptor for the trivalent europium cation

    NASA Astrophysics Data System (ADS)

    Makrlík, Emanuel; Novák, Vít; Vaňura, Petr

    2015-01-01

    On the basis of extraction experiments and γ-activity measurements, the extraction constant corresponding to the equilibrium Eu3+(aq) + 3A-(aq) + 1(nb) ⇆ 1.Eu3+(nb) + 3A‑(nb) occurring in the two-phase water-nitrobenzene system (A- = CF3SO-3; 1 = lithium ionophore VIII; aq = aqueous phase, nb = nitrobenzene phase) was determined as log Kex (1.Eu3+, 3A‑) = 2.5 ± 0.1. Furthermore, the extremely high stability constant of the 1.Eu3+ complex in nitrobenzene saturated with water was calculated: log βnb (1.Eu3+) = 15.6 ± 0.1. Finally, by using DFT calculations, the most probable structure of the cationic complex species 1.Eu3+ was derived. In the resulting complex, the 'central' cation Eu3+ is bound by six very strong bond interactions to the corresponding six oxygen atoms of the parent ligand 1. It is evident that this exceptionally effective receptor 1 for the Eu3+ cation could be considered as a potential extraction agent for nuclear waste treatment.

  5. Zero kinetic energy photoelectron spectroscopy of tryptamine and the dissociation pathway of the singly hydrated cation cluster

    NASA Astrophysics Data System (ADS)

    Gu, Quanli; Knee, J. L.

    2012-09-01

    The relative ionization energies of tryptamine conformations are determined by zero kinetic energy photoelectron spectroscopy and photoionization efficiency measurements. The relative cationic conformational stabilities are compared to the published results for the neutral molecule. In the cation, the interaction strength changes significantly between amino group and either the phenyl or the pyrrole moiety of the indole chromophore where most of the positive charge is located, leading to different conformational structures and relative conformer energies in the cation. In particular, the measured adiabatic ionization potential of isomer B is 60 928 ± 5 cm-1, at least 400 cm-1 higher than any of the 6 other tryptamine isomers which all have ionization potentials within 200 cm-1 of each other. In addition to the monomer, measurements were made on the A conformer of the tryptamine+-H2O complex including the ionization threshold and cation dissociation energy measured using a threshold photoionization fragmentation method. The water cluster exhibits an unexpectedly high ionization potential of 60 307 ± 100 cm-1, close to the conformer A monomer of 60 320 ± 100 cm-1. It also exhibits surprisingly low dissociation energy of 1750 ± 150 cm-1 compared to other H-bonding involved cation-H2O complexes which are typically several thousands of wavenumbers higher. Quantum chemical calculations indicate that upon ionization the structure of the parent molecule in the water complex remains mostly unchanged due to the rigid intermolecular double hydrogen bonded water molecule bridging the monomer backbone and its side chain thus leading to the high ionization potential in the water cluster. The surprisingly low dissociation energy measured in the cationic water complex is attributed to the formation of a much more stable structural isomer H+ in the exit channel.

  6. Nanomolar cationic dendrimeric sulfadiazine as potential antitoxoplasmic agent.

    PubMed

    Prieto, M J; Bacigalupe, D; Pardini, O; Amalvy, J I; Venturini, C; Morilla, M J; Romero, E L

    2006-12-01

    The high doses of sulfadiazine (SDZ), used in synergistic combination with pyrimethamine, are mainly responsible for severe side effects and discontinuation of toxoplasmosis treatments. In the search for new strategies that improve the efficacy of treatments with reduced doses of SDZ, we have determined the performance of cationic G4 (DG4) and anionic G4.5 (DG4.5) poly(amidoamine) (PAMAM) dendrimers to act as SDZ nanocarriers. Both dendrimers could efficiently load SDZ (SDZ-DG4 and SDZ-DG4.5) up to a ratio of 30 molecules SDZ per dendrimer molecule. The MTT assay on Vero and J774 cells showed no cytotoxicity for DG4.5 and its SDZ complex incubated between 0.03 and 33 microM of dendrimer concentration. On the other hand, DG4 and its SDZ complex resulted cytotoxic when incubated at dendrimer concentrations higher than 3.3 microM. Finally, complexes and empty dendrimers were in vitro tested against Vero cells infected with RH strain of Toxoplasma gondii along 4h of treatment. For SDZ-DG4.5 and DG4.5 to cause an infection decrease between 25 and 40%, respectively, a dendrimer concentration of 33 microM was required; however, SDZ-DG4 produced the highest infection decrease of 60% at 0.03 microM. These preliminary results, achieved with nanomolar doses of SDZ-DG4 as unique active principle, point to this complex as a suitable potential candidate for antitoxoplasmic therapy. PMID:16920292

  7. Photodissociation of Cerium Oxide Nanocluster Cations.

    PubMed

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

    2016-04-21

    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(-)). PMID:27035210

  8. Antibacterial Activity of Geminized Amphiphilic Cationic Homopolymers.

    PubMed

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

    2015-12-22

    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. PMID:26606647

  9. Divalent cation affinity sites in Paramecium aurelia.

    PubMed

    Fisher, G; Kaneshiro, E S; Peters, P D

    1976-05-01

    Sites with high calcium affinity in Paramecium aurelia were identified by high calcium (5 mM) fixation and electron microscope methods. Electron-opaque deposits were observed on the cytoplasmic side of surface membranes, particularly at the basal regions of cilia and trichocyst-pellicle fusion sites. Deposits were also observed on some smooth cytomembranes, within the axoneme of cilia, and on basal bodies. The divalent cations, Mg2+, Mn2+, Sr2+, Ni2+, Ba2+, and Zn2+, could be substituted for Ca2+ in the procedure. Deposits were larger with 5 mM Sr2+. Ba2+, and Mn2+ at ciliary transverse plates and the terminal plate of basal bodies. Microprobe analysis showed that Ca and C1 were concentrated within deposits. In some analyses, S and P were detected in deposits. Also, microprobe analysis of 5 mM Mn2+-fixed P. aurelia showed that those deposits were enriched in Mn and C1 and sometimes enriched in P. Deposits were seen only when the ciliates were actively swimming at the time of fixation. Locomotory mutants having defective membrane Ca-gating mechanisms and ciliates fixed while exhibiting ciliary reversal showed no obvious differences in deposition pattern and intensity. Possible correlations between electron-opaque deposits and the locations of intramembranous particles seen by freeze-fracture studied, as well as sites where fibrillar material associate with membranes are considered. The possibility that the action sites of calcium and other divalent cations were identified is discussed. PMID:1262398

  10. Cationic Antimicrobial Polymers and Their Assemblies

    PubMed Central

    Carmona-Ribeiro, Ana Maria; de Melo Carrasco, Letícia Dias

    2013-01-01

    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. PMID:23665898

  11. Ceramic Spheres From Cation Exchange Beads

    NASA Technical Reports Server (NTRS)

    Dynys, F. W.

    2003-01-01

    Porous ZrO2 and hollow TiO2 spheres were synthesized from a strong acid cation exchange resin. Spherical cation exchange beads, polystyrene based polymer, were used as a morphological-directing template. Aqueous ion exchange reaction was used to chemically bind (ZrO)(2+) ions to the polystyrene structure. The pyrolysis of the polystyrene at 600 C produces porous ZrO2 spheres with a surface area of 24 sq m/g with a mean sphere size of 42 microns. Hollow TiO2 spheres were synthesized by using the beads as a micro-reactor. A direct surface reaction - between titanium isopropoxide and the resin beads forms a hydrous TiO2 shell around the polystyrene core. The pyrolysis of the polystyrene core at 600 C produces hollow anatase spheres with a surface area of 42 sq m/g with a mean sphere size of 38 microns. The fo