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Query: UNIPROT:Q86TM3 (cage)
 29,987 document(s) hit in 31,850,051 MEDLINE articles (0.00 seconds)

Electrospray ionization (ESI)/quadrupole ion trap mass spectrometry is used to evaluate the heavy metal binding selectivities of five caged crown ethers and two polyether reference compounds in methanol solution. The binding preferences for Hg2+, Pb2+, Cd2+, and Cu2+ were analyzed by comparison of ESI mass spectral intensities with the aim of developing this method for the rapid screening of binding selectivities of new synthetic ligands. The cage compounds preferentially bind Hg2+, except for the cage cryptand derivative, which favors Pb2+. The preference for Hg2+ stems from the favorable positioning of the nitrogen or sulfur atoms for linear coordination of Hg2+, whereas the cryptand derivative favors Pb2+ because of its larger cavity size. The counterions of the metal salts influence the type of complexes observed in the ESI mass spectra because the strengths of the metal-anion bonds affect retention of the anion in the complexes.
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PMID:Evaluation of binding selectivities of caged crown ligands toward heavy metals by electrospray ionization/quadrupole ion trap mass spectrometry 1085 18

This case study demonstrates that the normal human body frequency, which can be disturbed by electromagnetic influences of the environment, can be modulated by 0.9% sodium chloride solutions (physiological saline) and that occurrence of allergic reactions have subsequently been suppressed as a result of this modulation. The use of distilled water as control showed no effect on occurrence of allergic reactions. Further observations on the growth of various plants in a greenhouse exposed to various geomagnetic fields support the previous observations on humans. The neutralization of electromagnetic influences on humans using 0.9% sodium chloride solution or by enclosure of plants within a copper wire Faraday cage resulting in a normal and uniform growth of plants as compared with disturbed and irregular growth in unenclosed controls, is demonstrated. These original observations propose a new strategy to suppress or prevent allergic reactions and possibly other effects observed in various human pathologies in relation to a disturbance of human body frequencies. It is hypothesized that the double helix structure of desoxyribonucleic acid (DNA) could be modified by environmental electromagnetic fields and that disresonance between the two chains of DNA could lead to the expression of specific pathology.
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PMID:Human body frequency modulation by 0.9% sodium chloride solutions: a new paradigm and perspective for human health. 1090 34

Free radicals can induce lipid peroxidation, leading to the formation of atherosclerosis. A new class of water-soluble C60 derivative, hexasulfobutyl [60] fullerene [C60-(CH2CH2CH2CH2SO3Na)6; (FC4S)], comprising six sulfobutyl functional groups covalently bound on a C60 cage, is a potent free radical scavenger. This study sought to define the effect of FC4S in protecting plasma from peroxidation. At concentrations of 10-100 microM, FC4S efficiently protected plasma against Cu2+-induced oxidation, as shown by maintenance of apoprotein B integrity and decrease in oxidative products levels, conjugated diene, and thiobarbituric acid-reactive substances. Addition of FC4S to both plasma and isolated lipoproteins, including very low density, low-density, and high-density lipoproteins, resulted in an increased mobility of the lipoprotein on agarose gel electrophoresis. This was attributed to FC4S associating with the lipoproteins because of the negative charge of the sulfonate groups after hydrolysis in the electrophoretic buffer. When lipoprotein was oxidized by 2,2-azobis (2,4-dimethyl-valeronitrile), which produces peroxyl radicals within lipoprotein, but not in the aqueous phase, the FC4S still efficiently inhibited lipoprotein oxidation. These data substantiate that FC4S acts efficiently in protecting plasma lipid from oxidation by associating with lipoprotein to scavenge free radicals in both the aqueous and lipophilic phases.
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PMID:Water-soluble hexasulfobutyl [60] fullerene inhibits plasma lipid peroxidation by direct association with lipoproteins. 1102 41

Reactions between chloroacetate and both "free" and coordinated forms of the cage amine diaminosarcophagine (1,8-diamino-3,6,10,13,16,19-hexaazabicyclo[6.6.6]icosane) result in the introduction of between one and four pendent carboxymethyl substituents on the nitrogen atoms of the cage. While at least the first two steps in the reaction of the free ligand have been found to involve only the secondary nitrogen centers, in both the Cu(II) and Co(III) complexes alkylation occurs only at the primary (1,8) centers, the greater ease of achieving a higher degree of alkylation of the Cu(II) complex being attributed to the lower charge of this species causing a lesser reduction of the nucleophilicity of the uncoordinated primary nitrogen atoms. All the new ligands have been characterized by X-ray structure determinations of their Cu(II) or Co(III) complexes. In some cases, this has shown that the methods used to isolate the crystalline complexes result in lactamization of the ligand.
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PMID:Carboxymethylation of cage amines: control of alkylation by metal ion coordination. 1115 85

The new heteronuclear iminodiacetic acid (H2L) complexes [LnCu6(mu 3-OH)3(HL)2(L)4](ClO4)(2).25H2O with Ln = La (1) and Tb (2) have been prepared in aqueous solution and characterized by single-crystal X-ray diffraction to be isomorphous (crystallographic data for 1 and 2: hexagonal, P63/m; a = b = 12.6425(14) A, c = 24.541(5) A, Z = 2 (1); a = b = 12.5802(9) A, c = 24.285(4) A, Z = 2 (2)). Ln3+ was found to be located in the center of the trigonal prismatic cage formed by six Cu2+ ions, with a tricapped trigonal prismatic coordination environment of nine O atoms. The magnetic properties of complexes 1 and 2 have been studied. The results indicate the presence of ferromagnetic couplings between Tb3+ and Cu2+ in compound 2.
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PMID:Structures and magnetism of two novel heptanuclear lanthanide-centered trigonal prismatic clusters: [LnCu6(mu 3-OH)3(HL)2(L)4](ClO4)2.25H2O (Ln = La, Tb; H2L = iminodiacetic acid). 1119 99

Copper K-edge X-ray absorption spectroscopic (XAS) measurements were recorded for the veterinary antiinflammatory Cu(II) complexes of indomethacin (1-(4-chlorobenzoyl)-5-methoxy-2-methyl-1H-indole-3-acetic acid = IndoH), of the general formula [Cu(2)(Indo)(4)L(2)] (L = N,N-dimethylformamide (DMF), N,N-dimethylacetamide (DMA), N-methylpyrrolidone (NMP), and water), and [Cu(2)(OAc)(4)(OH(2))(2)] at room temperature and 10 K. The bond lengths and bridging O-C-O angles of the dimeric Cu(II) cage (Cu(2)O(10)C(8)) obtained from the multiple-scattering (MS) fitting of the X-ray absorption fine structure (XAFS) using a centrosymmetric model of [Cu(2)(Indo)(4)(DMF)(2)] gave Cu.Cu = 2.62(2) A, mean Cu-O(Ac) = 1.95(2) A, Cu-O(L) = 2.15(2) A, bridging O-C-O = 125(1) degrees, Cu displacement from plane 0.19 A compared with the XRD data Cu.Cu = 2.630(1) A, mean Cu-O(Ac) = 1.959 A, Cu-O(L) = 2.143(5) A, bridging O-C-O angles = 123.2(5) degrees, Cu displacement from plane 0.20 A. The excellent agreement between the XAFS- and XRD-derived data allowed the structures of related [Cu(2)(Indo)(4)L(2)] (L = DMA, NMP) complexes to be determined. All display a similar Cu(2)O(10)C(8) coordination geometry, which is independent of the nature of the axial ligand. While XAFS analysis of [Cu(2)(Indo)(4)(OH(2))(2)] and [Cu(2)(OAc)(4)(OH(2))(2)] indicates a coordination geometry similar to that of [Cu(2)(Indo)(4)L(2)] (L = DMF, DMA, NMP), removal of symmetry restraints in the MS model is required to obtain axial bond lengths comparable to those derived in the XRD structures of the acetate complex. For the Indo complex, the fitted bond lengths with the lower symmetry model give a mean Cu-L(OH2) bond distance within experimental errors of the value for [Cu(2)(Indo)(4)(DMSO)(2)] (2.16(2) A) (XRD). The difficulty in refining the Cu-O(OH2) distance of [Cu(2)(OAc)(4)(OH(2))(2)] and [Cu(2)(Indo)(4)(OH(2))(2)] using a centrosymmetric MS model is attributed to a symmetry reduction due to hydrogen-bonding effects characteristic of the aqua adducts, as is observed in the XRD structure of the acetate complex.
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PMID:Determination of the structures of antiinflammatory copper(II) dimers of indomethacin by multiple-scattering analyses of X-ray absorption fine structure data. 1130 Aug 32

The interaction of Cu(II) with the ligand tdci (1,3,5-trideoxy-1,3,5-tris(dimethylamino)-cis-inositol) was studied both in the solid state and in solution. The complexes that were formed were also tested for phosphoesterase activity. The pentanuclear complex [Cu(5)(tdciH(-2))(tdci)(2)(OH)(2)(NO(3))(2)](NO(3))(4).6H(2)O consists of two dinuclear units and one trinuclear unit, having two shared copper(II) ions. The metal centers within the pentanuclear structure have three distinct coordination environments. All five copper(II) ions are linked by hydroxo/alkoxo bridges forming a Cu(5)O(6) cage. The Cu-Cu separations of the bridged centers are between 2.916 and 3.782 A, while those of the nonbridged metal ions are 5.455-5.712 A. The solution equilibria in the Cu(II)-tdci system proved to be extremely complicated. Depending on the pH and metal-to-ligand ratio, several differently deprotonated mono-, di-, and trinuclear complexes are formed. Their presence in solution was supported by mass, CW, and pulse EPR spectroscopic study, too. In these complexes, the metal ions are presumed to occupy tridentate [O(ax),N(eq),O(ax)] coordination sites and the O-donors of tdci may serve as bridging units between two metal ions. Additionally, deprotonation of the metal-bound water molecules may occur. The dinuclear Cu(2)LH(-3) species, formed around pH 8.5, provides outstanding rate acceleration for the hydrolysis of the activated phosphodiester bis(4-nitrophenyl)phosphate (BNPP). The second-order rate constant of BNPP hydrolysis promoted by the dinuclear complex (T = 298 K) is 0.95 M(-1) s(-1), which is ca. 47600-fold higher than that of the hydroxide ion catalyzed hydrolysis (k(OH)). Its activity is selective for the phosphodiester, and the hydrolysis was proved to be catalytic. The proposed bifunctional mechanism of the hydrolysis includes double Lewis acid activation and intramolecular nucleophilic catalysis.
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PMID:Highly efficient phosphodiester hydrolysis promoted by a dinuclear copper(II) complex. 1153 40

Depending upon the position and degree of substitution, carboxymethyl derivatives of cage amines of the "sarcophagine" (3,6,10,13,16,19-hexaazabicyclo[6.6.6]icosane) type vary considerably in the stability of their lactamized forms. For 1,8-diamino-3-carboxymethylsarcophagine, L(1), only indirect evidence for some involvement of a lactamized form of its Ni(II) complex has been obtained. Crystal structure determinations for [Cu(H(2)L(1))](NO(3))(3.5)Cl(0.5) x 2.5H(2)O and [Ni(HL(1))]Cl(3) x 3H(2)O show distorted octahedral coordination of all six endocyclic N-donor atoms in both cases. For related diaminosarcophagine derivatives with either two (1,8; L(2)) or three (1,1,8; L(3)) carboxymethyl substituents on the exocyclic N atoms, crystallographic studies have shown a dilactam form for the ligands in their Ni(II) and Cu(II) complexes which is of almost identical conformation to that of the diprotonated "free" ligand in [H(2)L(3)][ZnCl(4)] x 6H(2)O. The lactamized ligands appear to strongly favor square planar four-coordination, and the Co(II) complex of L(2) shows a remarkable lack of reactivity toward oxygen. Kinetic studies indicate that the hydrolytic stability of the lactam rings is comparable to that of uncoordinated analogues.
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PMID:Carboxymethylated cage amines: coordination and lactamization. 1159 65

Two hexaphenylhexaazatriphenylene L(1)()and three quaterpyridine L(2)() ligands are well-known to associate around six copper(I) ions to form a cylindrical inorganic cage 1. Spectrophotometric and electrospray mass spectrometry (ESMS) titrations have been conducted to gain information on the thermodynamics and the formation pathway of the assembly 1. From these data, the nature of intermediates present in solution was determined and the association constants of these species were calculated. It was also found that this assembling process occurs with positive cooperativity.
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PMID:Self-Assembly of an 11-Component Cylindrical Inorganic Architecture: Electrospray Mass Spectrometry and Thermodynamic Studies. 1166 29

Electron and energy transfer from copper 1,10-phenanthroline excited states is observed at room temperature in organic solvents. The copper phenanthroline excited states are metal-to-ligand charge-transfer in nature and have lifetimes of approximately 70-250 ns in dichloromethane solution if methyl or phenyl substituents are placed in the 2- and 9-positions of the phenanthroline ligand. The unsubstituted cuprous compound Cu(phen)(2)(PF(6)) is nonemissive under these conditions, and the excited state lifetime is <20 ns. The rate and efficiency of energy transfer to anthracene or electron transfer to viologens is reported. The cage escape efficiency of [Cu(dpp)(2)(2+), MV(+)(*)], where dpp is 2,9-diphenyl-1,10-phenanthroline, is close to unity within experimental error. Back electron transfer to ground state products occurs at the diffusion limit, 2 x 10(10) M(-)(1) s(-)(1).
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PMID:Photodriven Electron and Energy Transfer from Copper Phenanthroline Excited States. 1166 87


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