Divalent First-row Transition Research Articles

Imperfect coordination chemistry facilitates metal ion release in the Psa permease

The relative stability of divalent first-row transition metal ion complexes, as defined by the Irving-Williams series, poses a fundamental chemical challenge for selectivity in bacterial metal ion acquisition. Here we show that although the substrate-binding protein of Streptococcus pneumoniae, PsaA, is finely attuned to bind its physiological substrate manganese, it can also bind a broad range of other divalent transition metal cations. By combining high-resolution structural data, metal-binding assays and mutational analyses, we show that the inability of open-state PsaA to satisfy the preferred coordination chemistry of manganese enables the protein to undergo the conformational changes required for cargo release to the Psa permease. This is specific for manganese ions, whereas zinc ions remain bound to PsaA. Collectively, these findings suggest a new ligand binding and release mechanism for PsaA and related substrate-binding proteins that facilitate specificity for divalent cations during competition from zinc ions, which are more abundant in biological systems.

Role of the Metal in the Bonding and Properties of Bimetallic Complexes Involving Manganese, Iron, and Cobalt

A multidentate ligand platform is introduced that enables the isolation of both homo- and heterobimetallic complexes of divalent first-row transition metal ions such as Mn(II), Fe(II), and Co(II). By means of a two-step metalation strategy, five bimetallic coordination complexes were synthesized with the general formula M1M2Cl(py3tren), where py3tren is the triply deprotonated form of N,N,N-tris(2-(2-pyridylamino)ethyl)amine. The metal-metal pairings include dicobalt (1), cobalt-iron (2), cobalt-manganese (3), diiron (4), and iron-manganese (5). The bimetallic complexes have been investigated by X-ray diffraction and X-ray anomalous scattering studies, cyclic voltammetry, magnetometry, Mössbauer spectroscopy, UV-vis-NIR spectroscopy, NMR spectroscopy, combustion analyses, inductively coupled plasma optical emission spectrometry, and ab initio quantum chemical methods. Only the diiron chloride complex in this series contains a metal-metal single bond (2.29 Å). The others show weak metal-metal interactions (2.49 to 2.53 Å). The diiron complex is also distinct with a septet ground state, while the other bimetallic species have much lower spin states from S = 0 to S = 1. We propose that the diiron system has delocalized metal-metal bonding electrons, which seems to correlate with a short metal-metal bond and a higher spin state. Multiconfigurational wave function calculations revealed that, indeed, the metal-metal bonding orbitals in the diiron complex are much more delocalized than those of the dicobalt analogue.

Syntheses and Ion Selectivities of Dimeric Rhodamine 6G Chemosensors

Novel rhodamine 6G fluorescent chemosensors 1 and 2 for the detection of transition metal cations were synthesized through the condensation of rhodamine 6G ethylenediamine with each of 2-hydroxy-1-naphthaldehyde and 2,6-pyridinedicarbaldehyde, respectively. 1 and 2 were characterized using NMR, NMR and mass spectroscopy. Fluorometric and colorimetric measurements involving various metal ions revealed the ring opening of the rhodamine 6G spirocycle framework. In the absence of metal cations, 2 was colorless and non-fluorescent, whereas the addition of metal cations ( and others) changed the color to pink, accompanied by the appearance of an orange fluorescence. The chemosensors exhibited high selectivity for over other divalent first-row transition metals. The complexes of with 1 and 2 were successfully isolated. A huge enhancement in the fluorescence for both one- and two-photon excitations makes these compounds suitable candidates to be used for fluorescent labeling of biological systems.

Energy-Resolved Collision-Induced Dissociation Studies of 1,10-Phenanthroline Complexes of the Late First-Row Divalent Transition Metal Cations: Determination of the Third Sequential Binding Energies

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

The Mg member of the isotypic seriesMTe6O13

MgTe6O13, magnesium hexa­tellurate(IV), is isotypic with the structures of divalent first-row transition metal analogues MTe6O13 (M = Mn, Fe, Co, Ni and Zn). The asymmetric unit contains one Mg, two Te and five O atoms of which the Mg and one O atom lie on a threefold rotation axis. The structure is made up from slightly distorted [MgO6] octa­hedra (isolated from each other), distorted [TeO4] bis­phenoids and [TeO4 + 1] tetra­gonal pyramids sharing corners and edges. This arrangement leads to the formation of a dense three-dimensional structure.

Comparative computational analysis of binding energies between several divalent first-row transition metals (Cr2+, Mn2+, Fe2+, Co2+, Ni2+, and Cu2+) and ligands (porphine, corrin, and TMC)

B3LYP density functional theory calculations were performed to quantify the binding affinities of six divalent first-row transition metals (Cr2+, Mn2+, Fe2+, Co2+, Ni2+, and Cu2+) for three well-known macrocyclic ligands (porphine, corrin, and 1,4,8,11-tetramethyl-1,4,8,11-tetraazacyclotetradecane [TMC]). Our calculations show that, as expected from the neutral, monoanionic, and dianionic characters of the TMC, corrin, and porphine ligands, respectively, the binding energy increases in the order TMC<corrin<porphine. This is because a more anionic ligand gives rise to greater electrostatic stabilization upon interaction with the metal cations. For all ligands, the binding energy increases in the order Mn2+<Cr2+∼Fe2+<Co2+<Ni2+<Cu2+. Single occupation of all five d orbitals in the high-spin Mn2+ complexes does not afford large stabilization due to either ligand-to-metal or metal-to-ligand charge transfer, thereby resulting in the minimum binding energies observed for Mn2+ among the six different metal ions considered.

Fluorinated Heterometallic β-Diketonates as Volatile Single-Source Precursors for the Synthesis of Low-Valent Mixed-Metal Fluorides

Hexafluoroacetylacetonates that contain lead and divalent first-row transition metals, PbM(hfac)(4) (M = Ni (1), Co (2), Mn (3), Fe (4), and Zn (5)), have been synthesized. Their heterometallic structures are held together by strong Lewis acid-base interactions between metal atoms and diketonate ligands acting in chelating-bridging fashion. Compounds 1-5 are highly volatile and decompose below 350 °C. Fluorinated heterometallic β-diketonates have been used for the first time as volatile single-source precursors for the preparation of mixed-metal fluorides. Complex fluorides of composition Pb(2)MF(6) have been obtained by decomposition of 1-5 in a two-zone furnace under low-pressure nitrogen flow. Lead-transition metal fluorides conform to orthorhombically distorted Aurivillius-type structure with layers of corner-sharing [MF(6)] octahedra separated by α-PbO-type (Pb(2)F(2)) blocks. Pb(2)NiF(6) and Pb(2)CoF(6) were found to exhibit magnetic ordering below 80 and 43 K, respectively. The ordering is antiferromagnetic, with a weak, uncompensated moment due to the canting of spins. The Pb(2)MF(6) fluorides represent a new class of prospective magnetoelectric materials combining transition metals and lone-pair main-group cations.

Indenyl Complexes of Manganese(II). Conformational Flexibility of the Manganese(II)−(RnC9H7−n) Bond

Bis(cyclopentadienyl) complexes (Cp2M) of the divalent first-row transition metals V−Ni have been known and used for over 50 years. For almost as long, an analogous series of compounds has been known with the indenyl ligand (i.e., Ind2M), with the conspicuous exception of M = Mn. Bis(indenyl) complexes of manganese(II), Ind′2MnLn, have now been synthesized by halide metathesis from MnCl2 and an appropriate potassium indenide. Depending on the indenyl ligand substituents and the presence of coordinated bases, a variety of structural motifs and bonding modes of the indenyl ligand are found in the resulting complexes. Single-crystal X-ray structures obtained for [2-(SiMe3)C9H6]2Mn, [1,3-(SiMe3)2C9H5]2Mn, and [1,3-(i-Pr)2C9H5]2Mn confirm that they possess classic η5-bound sandwich structures. In contrast, the unsubstituted parent complex recrystallizes from THF as a disolvate with two differently bonded indenyl ligands: i.e., (η3-C9H7)(η1-C9H7)Mn(thf)2. Without the coordinated solvent, density functional theory calculations suggest that the complex would have two slipped η5-bound ligands. When methyl groups are present on the benzo portion of the indenyl ligand, specifically in the 4,7-positions, the corresponding manganese complex is isolated as a cyclic octomer, {(4,7-Me2C9H5)2Mn}8, containing both bridging and terminal indenyl ligands. In the presence of 1,4-dioxane, however, attempted synthesis of (4,7-Me2C9H5)2Mn results in the isolation of the [K(dioxane)1.5][Mn(4,7-Me2C9H5)3] salt, in which each manganese atom is surrounded by a paddlewheel of three η2-bound 4,7-dimethylindenyl ligands. Cation−π bonding to the potassium and the presence of coordinated dioxane molecules generates a layered structure for the salt. Magnetic susceptibility measurements on the compounds indicate the presence of high-spin Mn(II) centers in all cases. These compounds demonstrate the high degree of conformational flexibility in the Mn(II)−indenyl bond.

Influence of the crystal field effect on chemical transport in Earth's mantle: Cr 3+ and Ga 3+ diffusion in periclase

Experiments were performed to determine concentration-dependent diffusion coefficients of Cr 3+ and Ga 3+ in periclase at temperatures of 1563–2273 K. Diffusion profiles measured in the quenched samples are consistent with a theoretical model in which the mobile species is a bound M 3+-vacancy pair, and each profile was fitted to determine the binding energy and diffusion coefficient of the pair. Trivalent chromium-vacancy pairs diffuse more slowly than Ga 3+-vacancy pairs, and with higher migration energy, 237 kJ/mol vs. 190 kJ/mol. Cation vacancies also bind less tightly to Cr 3+ than to Ga 3+, with average binding free energies of −22 and −83 kJ/mol, respectively. At all concentrations and temperatures, Cr 3+ diffuses much more slowly than Ga 3+, by up to two orders of magnitude. The differences between Cr 3+ and Ga 3+ cannot be explained by differences in ionic radius or dipole polarizability, but are consistent with the influence of the crystal field on the partially occupied 3d orbitals of Cr 3+. The crystal field splitting stabilizes Cr 3+ on the octahedral cation site, increasing the energy required for Cr 3+ to exchange positions with an adjacent vacancy. It also makes Cr 3+-vacancy pairs less favorable, with the presence of a nearest-neighbor vacancy disrupting the symmetry of the octahedral site, thus diminishing the crystal field stabilization. Trends in the diffusion of first-row divalent transition metals in periclase can also be explained by the crystal field effect. High-spin to low-spin transitions in Fe 2+, Co 2+ or Mn 2+ would significantly enhance their crystal field stabilization in periclase, and if such spin transitions occur in the deep mantle, they would be expected to slow the diffusivity of these ions significantly, perhaps by several orders of magnitude.

Recognition Preference of Rhodamine-Thiospirolactams for Mercury(II) in Aqueous Solution

This work presents the design, syntheses, photophysical properties and Hg(2+)-binding of the red-emitting rhodamine derivatives RS1, RS2, and RS3 with different coordination ability and different spatial effects that derived from rhodamine thiohydrazone chromophores and respective carboxaldehydes (benzaldehyde, pyridine-2-carboxaldehyde, ferrocenecarboxaldehyde). Chemosensors RS2 and RS3 afford turn-on fluorescence enhancement and display high brightness in water with the EC(50) for Hg(2+) of 0.5 ppb. The fluorescence intensities are nearly proportional to the amount of Hg(2+) at ppb level, when employing 100 nM probes in water. The fluorescence responses of these two chemosensors are Hg(II) specific, and the probes are selective for Hg(II) over alkali, alkaline earth metals, divalent first-row transition metal ions, and Group 12 congeners Zn(II) and Cd(II), as well as heavy metals Pb(II) and Ag(I). X-ray crystal structure analyses exhibit the thioether derivative of the spirolactone in these compounds. Hg(II)-specific binding in water would make the opening of the spirolactam ring and consequently causes the appearance of strong absorption at visible range, and the obvious and characteristic color change from colorless to pink. Compared to the thioamides, the improved selectivity for Hg(2+) is attributed to the poorer coordination affinity of the thioether over other interference metal ions.

Structural modification of rhodamine-based sensors toward highly selective mercury detection in mixed organic/aqueous media

In virtue of the sulfurphilic nature of Hg(2+), three new sensors RN1, RN2 and RST1 that combine a thiophene group and one or two rhodamine choromophores, or a thiospirolactam rhodamine chromophore, were designed and prepared for the selective detection of Hg(2+) in aqueous media, respectively. These sensors all displayed good brightness and fluorescence enhancement following Hg(2+) coordination with limits of detection for Hg(2+) at the ppb level. Thus, they have the potential for distinguishing between safe and toxic levels of inorganic mercury in drinking water. RN1 exhibited chromogenic and fluorogenic selectivity over alkali, alkaline earth metals, divalent first-row transition metal ions as well as heavy metals, but the presence of Cu(2+) had a small but significant influence on the absorption detection of Hg(2+). Compared to RN1, the introduction of sufficient sulfur atoms could increase the binding capability of RST1 towards Hg(2+) relative to the sensor RN1, but decrease its Hg specific ability. The existence of some heavy and transition metal ions, such as Pb(2+), Ag(+), Cu(2+) enhance the silent absorption spectra of RST1. Spectral evidence and X-ray structural investigations of the mercury complex revealed a possible 1:2 complexation behaviour between the Hg(2+) ion and the sensor RN1 or RST1. Sensor RN2 which contains two rhodamine carboxhydrazone arms exhibited better selectivity, compared to those of RN1 and RST1. The addition of Cu(2+) only caused a small interference for the absorption detection of Hg(2+) under the same conditions, demonstrating the efficiency of the robust bis-chelating mode with regard to the selectivity for Hg(2+).

BaCo2(AsO4)2

Suitable single crystals of the title compound, barium dicobalt(II) bis­[orthoarsenate(V)], were prepared under hydro­thermal conditions. This phase belongs to a series of compounds with general formula AM 2(XO4)2, where A = alkaline earth metal, M = Mg or a divalent first-row transition element, and X = P, As or V. BaCo2(AsO4)2 is isotypic with BaNi2(XO4)2 (X = P, V or As) and is characterized by brucite-like sheets of edge-sharing CoO6 octa­hedra (3 symmetry) parallel to (001), with one-third of the octa­hedral positions being vacant. The sheets are capped above and below by AsO4 tetra­hedra (3 symmetry) and are inter­connected by distorted BaO12 cubocta­hedra ( symmetry).

First-Row Transition-Metal Complexes of a New Pentadentate Ligand, α,α,α′,α′-Tetra(pyrazolyl)lutidine

A new pentadentate ligand, alpha,alpha,alpha',alpha'-tetra(pyrazolyl)lutidine, pz 4lut, has been prepared by a CoCl 2-catalyzed rearrangement reaction between 2,6-pyridinedicarboxaldehyde and dipyrazolylthione. The coordination chemistry with some divalent first-row transition metal (Mn, Fe, Co, Ni, Cu, and Zn) chlorides has been explored. The electronic properties indicate that the new kappa (5)N ligand is a slightly stronger-field donor to Ni (2+) and Co (2+) than a related pentadentate ligand with five pyridyl donors presumably because of greater interaction between the metal and axial pyridyl.

Highly Sensitive Multiresponsive Chemosensor for Selective Detection of Hg2+ in Natural Water and Different Monitoring Environments

A new chemosensor RF1 that combines a ferrocene unit and a rhodamine block via the linkage of a carbohydrazone binding unit was designed and prepared for the highly selective detection of Hg (2+) in natural water. This chemosensor displays great brightness and fluorescence enhancement following Hg (2+) coordination within the limit of detection for Hg (2+) at 1 parts per billion (ppb). The fluorescence intensities are nearly proportional to the amount of Hg (2+) at the ppb level. It is capable of distinguishing between the safe and the toxic levels of inorganic mercury in drinking water. Hg (2+)-binding also arouses the absorption of the rhodamine moiety in RF1 significantly with the chromogenic detection limit for Hg (2+) at 50 ppb. The conventional UV-vis spectroscopic method thus has the potential to provide the critical information about the mercury hazard assessment for industrial wastewater discharging. The obvious and characteristic color change of the titration solution from colorless to pink upon the addition of Hg (2+) demonstrates that RF1 can be used for "naked-eye" detection of Hg (2+) in water. The Hg (2+) complexation also causes a significant shift of the redox potential about the ferrocene/ferrocenium couple. The electrochemical responses provide the possibility to quantitative analysis of Hg (2+) at the parts per million (ppm) level. Preliminary investigations in natural water samples including seawater and freshwater indicate that RF1 offers a direct and immediate Hg (2+) detection in complex media, pointing out its potential utility in environment monitoring and assessment. The responses of RF1 are Hg (2+) specific, and the chemosensor exhibits high selectivity toward Hg (2+) over other Group 12 metals, alkali, alkaline earth metals, and most of the divalent first-row transition metals. The RF1-Hg (2+) complex is successfully isolated and the Hg (2+)-binding is reversible. The crystal structure and spectral properties of its congener RF2 that contains one ferrocene group and two rhodamine 6G moieties were also investigated for a comparison.

Helicates, Boxes, and Polymers from Simple Pyridine-Alcohol Ligands: the Impact of the Identity of the Transition Metal Ion

The coordination chemistry of 6-methylpyridine-2-methanol (1) and enantiopure (R)-1-(6-methylpyridin-2-yl)ethanol (2) with a range of divalent first-row transition metal salts has been investigated in an effort to determine whether hydrogen-bonded helicates will form, as observed for cobalt(II) salts. Hydrogen-bonded helicates, [Cu2(1)2(1-H)2X2] (X = Cl, Br), were only observed upon combining 1 with CuCl2 and CuBr2 in MeOH solution. Other metal salts led to alternative products, viz. Cu(ClO4)2 in the presence of base gives [Cu2(1)2(1-H)2](ClO4)2, ZnCl2 and ZnBr2 give the 1-D helical coordination polymers [Zn(1-H)Cl]infinity and [Zn(1-H)Br]infinity, a mixture of NiCl2 and Ni(OAc)2 produces the [Ni4(1-H)4Cl2(OAc)2(MeOH)2] cubane, NiCl2 leads to the [Ni4(1-H)4Cl4(MeOH)4] cubane, while MnCl2 gives the known cubane [Mn4(1-H)6Cl4]. The reaction of 2 with CuCl2 produces the mononuclear complex Lambda-[Cu(2)2Cl]Cl, while reaction with CuBr2 leads to a dimer, Lambda,Lambda-[Cu2(2)3(2-H)Br2]Br, which is held together by a single hydrogen bond between the monomeric subunits. The solid-state CD spectra of these latter complexes were recorded and found to be very similar. The temperature-dependent magnetic behavior of [Cu2(1)2(1-H)2X2] (X = Cl, Br), [Cu2(1)2(1-H)2](ClO4)2, [Cu2(2)3(2-H)Br2]Br, and [Ni4(1-H)4Cl2(OAc)2(MeOH)2] was investigated. Weak antiferromagnetic coupling between the copper(II) centers is mediated by the hydrogen bonds in the [Cu2(1)2(1-H)2X2] (X = Cl, Br) complexes.

Turn-on and ratiometric mercury sensing in water with a red-emitting probe.

The synthesis, photophysical properties, and Hg(II) binding of a red-emitting sensor for mercuric ion are presented. 2-[11-[(2-[[Bis-(2-ethylsulfanylethyl)amino]methyl]phenylamino)methyl]-3-hydroxy-10-oxo-10H-benzo[c]xanthen-7-yl]benzoic acid (MS5) is based on the seminaphthofluorescein chromophore and employs a thioether-rich metal-binding unit. This sensor affords both turn-on and single-excitation dual-emission ratiometric Hg(II) detection in aqueous solution. The fluorescence response of MS5 is Hg(II)-specific, and the probe is selective for Hg(II) over alkali and alkaline earth metals, most divalent first-row transition metal ions, and the Group 12 congeners Zn(II) and Cd(II). MS5 binds Hg(II) reversibly and can be recycled. The EC50 for 1 microM MS5 is 910 nM, and a lower detection limit of 50 nM is obtained when employing 500 nM probe. X-ray crystallographic studies using a salicylaldehyde-based model of MS5 are also presented. 2-[(2-[[Bis-(2-ethylsulfanylethyl)amine]methyl]phenylamine)methyl]phenol coordinates Hg(II) with two thioether sulfur atoms, two amino nitrogen atoms, and a phenol oxygen atom arranged in a distorted trigonal bipyramidal geometry. Studies of natural water samples spiked with mercuric salts indicate that MS5 can rapidly detect Hg(II) in such complex solutions and demonstrate its potential utility in the field.

Properties of a new 4-imidazolyl derivative of a 14-membered tetraazamacrocyclic chelating agent

A new bis-N,N'-(5-methylimidazol-4-ylmethyl) derivative of a 14-membered tetraazamacrocycle, L1, has been synthesized. The protonation constants of this compound and the stability constants of its complexes with divalent first-row transition metal ions and Fe3+ were determined at 298.2 K in aqueous 0.10 mol dm(-3) KNO3. Compound L1 exhibits high overall basicity, which is mainly conferred by the imidazolyl groups. The complexes of the divalent first row-transition metal ions of L1 follow the Irving-Williams order of stability with the maximum for Cu2+ as expected, but a steep fall of constants is verified for the Mn2+, Fe2+ and Co2+, in one side, and for the Zn2+ complexes, in the other side. Additionally, L1 shows a large affinity for Fe3+, and the relative stability constants for its Cd2+ and Pb2+ complexes indicate that L1 may be useful for the complexometric determination of these two toxic metal ions in solutions containing both metal ions. These studies together with NMR, UV-vis and EPR spectroscopic data indicated the presence of mononuclear complexes, which adopt distorted pyramidal or octahedral geometries depending on the metal centre. The X-ray crystal structure of [Cu(HL1)](PF6)2(NO3).H2O showed that the coordination sphere of the copper centre can be described as a distorted square pyramid with the basal plane defined by three nitrogen donors of the macrocycle backbone and one nitrogen atom from one imidazolyl pendant arm. The apical position is occupied by the nitrogen atom of the macrocycle trans to the pyridine ring. To achieve this coordination environment, the macrocycle is folded along the axis defined by the two N atoms contiguous to the pyridine ring. The free methylimidazolyl arm points away from the metal centre leading to an intramolecular Cu[dot dot dot]N distance of 5.155(1) A.

A novel pseudo-2D structural motif in an anionic copper(II) dicyanamide coordination polymer

Abstract Anionic coordination polymers of divalent first-row transition elements are promising components of multifunctional molecular materials in which electronic conduction and magnetism can coexist. We report that a tetraphenylphosphonium salt containing a copper(II) dicyanamide anion has a novel pseudo-two-dimensional anionic structure and may provide a suitable electrolyte for the electrocrystallization of charge transfer salts. This (PPh4)3Cu4(dca)11 salt crystallizes in the monoclinic space group P21 with lattice parameters, a = 7.1911(4) A, = 55.050(3) A, c = 11.7964(7) A, β = 99.166(3)° and V = 4610.2(7) A3 at T = 298 K.

EXAFS signature of structural Zn at trace levels in natural and synthetic trioctahedral 2:1 phyllosilicates

EXAFS spectroscopy has been used to determine the medium-range structural environment (within a radius of 7 A) of trace levels of Zn2+ ions within the octahedral sheets of trioctahedral 2:1 phyllosilicates. EXAFS signatures of trace quantities (800–4000 ppm) of Zn in natural and synthetic trioctahedral 2:1 phyllosilicates (talcs and biotite) were analyzed using ab initio FEFF calculations (FEFF 8.10 code) in which various second-neighbor atomic configurations around a Zn-containing octahedral site were examined. Comparison of the results of these model calculations with observed Zn K -edge EXAFS spectra provides constraints on the distribution of Zn within the octahedral sheet. Zn was found to be randomly distributed within the octahedral sheets of the synthetic talc containing 4000 ppm Zn. In the natural biotite containing 800 ppm Zn, the distribution of Zn could not be determined because of significant Fe content, which precluded unambiguous FEFF analysis. Finally, FEFF analysis of single-scattering and multiple-scattering contributions to the EXAFS data of the Zn-dilute talc sample, followed by comparison with EXAFS data from a natural dioctahedral illite sample containing 140 ppm Zn, allowed unambiguous identification of spectral features characteristic of Zn2+ ions incorporated within the octahedral sheets of trioctahedral phyllosilicates. These results indicate that EXAFS spectroscopy can be used to distinguish between incorporation of trace levels of Zn2+ ions within the octahedral sheet of di- or trioctahedral phyllosilicates. They also provide a strong basis for determining the speciation of Zn at trace concentration levels in natural phyllosilicates from Zn-contaminated soils and sediments using Zn K -edge EXAFS spectroscopy. Because the crystal chemistry of other potentially toxic first-row divalent transition elements (i.e., Co2+, Ni2+, and Cu2+) is similar to that of Zn2+, this FEFF-based EXAFS approach could be used to (1) complement existing FTIR and polarized-EXAFS approaches in assessing the distribution of these elements within the octahedral sheets of di- and trioctahedral plyllosilicates and (2) better determine the speciation of these elements in contaminated soils and sediments.

Selective Hg(II) Detection in Aqueous Solution with Thiol Derivatized Fluoresceins

The syntheses and photophysical properties of mercury sensors 2 and 3 (MS2 and MS3), two asymmetrically derivatized fluorescein-based dyes designed for Hg(II) detection, are described. These sensors each contain a single pyridyl-amine-thiol metal-binding moiety, form 1:1 complexes with Hg(II), and exhibit selectivity for Hg(II) over other Group 12 metals, alkali and alkaline earth metals, and most divalent first-row transition metals. Both dyes display superior brightness (Phi x epsilon) and fluorescence enhancement following Hg(II) coordination in aqueous solution. At neutral pH, the fluorescence turn-on derives from greater brightness due to increased molar absorptivity. At higher pH, photoinduced electron transfer quenching of the free dye is enhanced, and the Hg(II)-induced turn-on also benefits from alleviation of this pathway. MS2 can detect ppb levels of Hg(II) in aqueous solution, demonstrating its ability to identify environmentally relevant concentrations of Hg(II).