RESUMEN
The lanthanide binding ability of a macrocyclic ligand H6L2 comprising two bis(iminomethyl)phenol and two calix[4]arene units has been studied. H6L2 is a ditopic ligand which provides dinuclear neutral complexes of composition [Ln2(L2)(MeOH)2] (Ln = La (1), Eu (2), Tb (3), and Yb (4)) in very good yield. X-ray crystal structure analyses for 2 and 3 show that (L2)6- accommodates two seven coordinated lanthanide ions in a distorted monocapped trigonal prismatic/octahedral coordination environment. UV-vis spectroscopic titrations performed with La3+, Eu3+, Tb3+ and Yb3+ ions in mixed MeOH/CH2Cl2 solution (I = 0.01 M NBu4PF6) reveal that a 2 : 1 (metal : ligand) stoichiometry is present in solution, with log K11 and K21 values ranging from 5.25 to 6.64. The ratio α = K11/K21 of the stepwise formation constants for the mononuclear (L2 + M = ML2, log K11) and the dinuclear complexes (ML2 + M = M2L2, log K21) was found to be invariably smaller than unity indicating that the binding of the first Ln3+ ion augments the binding of the second Ln3+ ion. The present complexes are less luminescent than other seven-coordinated Eu and Tb complexes, which can be traced to vibrational relaxation of excited EuIII and TbIII states by the coligated MeOH and H2O molecules and/or low-lying ligand-to-metal charge-transfer (LMCT) states.
RESUMEN
The synthesis of the new lanthanide complexes [HNEt3][Dy2(HL1)(L1)] (5), and [Ln2(L2)2] (Ln = TbIII (7), DyIII (8)) supported by the hybrid Schiff-base/calix[4]arene ligands H4L1 (25-[2-((2-methylphenol)imino)ethoxy]-26,27,28-trihydroxy-calix[4]arene) and H3L2 (25-[2-((2-methylpyridine)imino)ethoxy]-26,27,28-trihydroxy-calix[4]arene) are reported. Spectroscopic data (for 5) and X-ray crystallographic analysis (for 7·4MeCN, 8·4MeCN) reveal the presence of dimeric structures, featuring doubly-bridged NO4Ln(µ-O)2LnO4N (5) or N2O3Ln(µ-O)2LnO3N2 cores (7, 8) with seven-coordinated Ln3+ ions. The magnetic properties of polycrystalline samples of 5, 7 and 8 were studied by variable temperature dc and ac magnetic susceptibility measurements. The χ''(T) vs. T plots show no maxima in zero field, but the maxima can be detected under a 3 kOe dc field. The relaxation times τ obey the Arrhenius law above 5 K. Anisotropy barriers of â¼18 cm-1 (26 K) for 5 and â¼23 cm-1 (33 K) for 8 were determined.
RESUMEN
The synthesis, structures, and properties of a new calix[4]arene ligand with an appended salicylaldimine unit (H4L = 25-[2-((2-methylphenol)imino)ethoxy]-26,27,28-trihydroxy-calix[4]arene) and four lanthanide complexes (HNEt3)[Ln2(HL)(L)] (Ln = SmIII (4), EuIII (5), GdIII (6), and TbIII (7)) are reported. X-ray crystallographic analysis (for 4 and 6) reveals an isostructural series of dimeric complexes with a triply-bridged NO3Ln(µ-O)2(OHO)LnO3N core and two seven coordinated lanthanide ions. According to UV-vis spectrometric titrations in MeCN and ESI-MS the dimeric nature is maintained in solution. The apparent stability constants range between log K = 5.8 and 6.3. The appended salicylaldimines sensitize EuIII and TbIII emission (λexc 311 nm) in the solid state or immersed in a polycarbonate glass at 77 K (for 5, 7) and at 295 K (for 7).
RESUMEN
The synthesis and photophysical properties of four new hybrid salicylaldiminato-calix[4]arene ligands and their corresponding zinc(ii) complexes are described. The Schiff bases were obtained from condensation reactions between cone-25,27-di(aminoethoxy)-26,28-dihydroxy-calix[4]arene and salicylaldehyde (H2L1) or o-vanillin (H2L2) and 1,3-alt-25,27-di(aminoethoxy)-26,28-di(n-propyloxy)-calix[4]arene and 3,5-di-tert-butyl-salicylaldehyde (H2L3) or o-vanillin (H2L4). Complexation reactions were investigated by ESI-MS, IR, NMR, UV-vis absorption and steady-state and time resolved fluorescence spectroscopy, and X-ray crystallography. All ligands support 1 : 1 complexes (ZnL1-ZnL4), with equilibrium constants derived from absorption spectrophotometry in the range log K11 = 5.5-8.2 (MeCN or MeOH/CH2Cl2, I = 0.01 M). The zinc complexes show blue fluorescence, both in solution as well as in the solid state, with λem, Φf, and τ ranging from 472-504 nm, 0.11-0.60, and 2-9 ns, respectively. The nature of the substituents on the salicylaldiminato fragments was found to be the main parameter that influences the photophysical properties of the zinc complexes. Insights into the electronic nature of the UV-vis transitions were obtained with time dependent density functional theory (TD-DFT) calculations.
RESUMEN
A macrocyclic ligand (H2 L) containing two o,o'-bis(iminomethyl)phenol and two calix[4]arene head units has been synthesized and its coordination chemistry towards divalent Ni and Zn investigated. The new macrocycle forms complexes of composition [ML] (M=Zn, M=Ni) and [ZnL(py)2 ], which were characterized by elemental analysis; IR, UV/Vis, and NMR spectroscopy; electrospray ionization mass spectrometry (ESI-MS); and X-ray crystallography (for [ZnL(py)2 ] and [NiL]). H2 L allows the sensitive optical detection of Zn2+ among a series of biologically relevant metal ions by a dual fluorescence enhancement/quenching effect in solution. The fluorescence intensity of the macrocycle increases by a factor of ten in the presence of Zn2+ with a detection limit in the lower nanomolar region.
RESUMEN
Human respiratory and digestive illnesses can be caused by exposures to brevetoxins from blooms of the marine alga Karenia brevis, also known as Florida red tide (FRT). K. brevis requires macro-nutrients to grow; although the sources of these nutrients have not been resolved completely, they are thought to originate both naturally and anthropogenically. The latter sources comprise atmospheric depositions, industrial effluents, land runoffs, or submerged groundwater discharges. To date, there has been only limited research on the extent of human health risks and economic impacts due to FRT. We hypothesized that FRT blooms were associated with increases in the numbers of emergency room visits and hospital inpatient admissions for both respiratory and digestive illnesses. We sought to estimate these relationships and to calculate the costs of associated adverse health impacts. We developed environmental exposure-response models to test the effects of FRT blooms on human health, using data from diverse sources. We estimated the FRT bloom-associated illness costs, using extant data and parameters from the literature. When controlling for resident population, a proxy for tourism, and seasonal and annual effects, we found that increases in respiratory and digestive illnesses can be explained by FRT blooms. Specifically, FRT blooms were associated with human health and economic effects in older cohorts (≥55 years of age) in six southwest Florida counties. Annual costs of illness ranged from $60,000 to $700,000 annually, but these costs could exceed $1.0 million per year for severe, long-lasting FRT blooms, such as the one that occurred during 2005. Assuming that the average annual illness costs of FRT blooms persist into the future, using a discount rate of 3%, the capitalized costs of future illnesses would range between $2 and 24 million.
