Ratiometric detection of Cr3+ and Hg2+ by a naphthalimide-rhodamine based fluorescent probe

Newly synthesized rhodamine derivatives, L(1) and L(2), are found to bind specifically to Hg(2+) or Cr(3+) in presence of large excess of other competing ions with associated changes in their optical and fluorescence spectral behavior. These spectral changes are significant enough in the visible region of the spectrum and thus, allow the visual detection. For L(1), the detection limit is even lower than the permissible [Cr(3+)] or [Hg(2+)] in drinking water as per standard U.S. EPA norms; while the receptor, L2 could be used as a ratiometric sensor for detection of Cr(3+) and Hg(2+) based on the resonance energy transfer (RET) process involving the donor naphthalimide and the acceptor Cr(3+)/Hg(2+)-bound xanthene fragment. Studies reveal that these two reagents could be used for recognition and sensing of Hg(2+)/Cr(3+). Further, confocal laser microscopic studies confirmed that the reagent L(2) could also be used as an imaging probe for detection of uptake of these ions in A431 cells.     

Anion-controlled circular dichroism spectral changes in Hg2+ complexes with a chiral bidentate ligand

Anion-controlled circular dichroism (CD) spectral changes in Hg(2+) complexes with a chiral bidentate ligand are reported. Although the Hg(CF(3)SO(3))(2) and Hg(CF(3)CO(2))(2) complexes with (R)-(-)-1-(naphthalen-1-yl)-N,N-bis(pyridin-4-ylmethyl)ethanamine, (R)-(-)-1, show significant CD spectral changes, no CD spectral changes were observed in the HgCl(2), HgBr(2), Hg(CN)(2), or Hg(CH(3)CO(2))(2) complexes. X-ray analysis indicates that both the (R)-(-)-1-Hg(CF(3)SO(3))(2) and (R)-(-)-1-HgCl(2) complexes form a coordination polymer and a discrete 2:3 [=(R)-(-)-1/HgCl(2)] complex with a figure-eight structure. X-ray crystallography revealed that (i) the Hg-Hg distances bridged by anions vary depending on the anions used and (ii) a coordination polymer cannot be formed when the Hg-Hg distances are too short. Therefore, the formation of a coordination polymer is required to give the observed significant CD spectral changes.     

A chelation enhanced selective fluorescence sensing of Hg2+ by a simple quinoline substituted tripodal amide receptor

Two tris(2-aminoethyl)amine (tren) based tripodal amide fluoroionophores, 1 and 2, functionalized with quinoline (chelating fluorophore) and naphthalene (non-chelating fluorophore) respectively, are synthesized in good yields. Fluoroionophore 1 shows a selective UV-Vis spectral shift in the case of Hg(2+) in acetonitrile among different metal ions like Li(+), Na(+), Ca(2+), Mg(2+), Cr(2+), Mn(2+), Fe(2+), Co(2+), Ni(2+), Cu(2+), Zn(2+), Cd(2+), Hg(2+), Pb(2+), and Ag(+). On the other hand, fluoroionophore 2 shows no selectivity towards any of the above metal ions in the UV-Vis study. Furthermore, 1 shows a selective chelation induced fluorescence enhancement in the presence of Hg(2+) whereas 2 shows the enhancement of fluorescence with most of the metal ions via a photoinduced charge transfer mechanism. The naked eye detection of Hg(2+) in an acetonitrile solution of 1 shows a greenish fluorescence upon UV light irradiation. The isolated Hg(2+) complex of 1, 3, shows a similar UV-Vis and fluorescence spectral output as observed from in situ spectroscopic studies of 1 in the presence of Hg(2+). Infra-red (IR) and (1)H- NMR studies also reveal the interaction of Hg(2+) with the quinoline nitrogen atoms as well as with the amide functionality.     

Protein assisted fluorescence enhancement of a dansyl containing fluorescent reagent: detection of Hg+ ion in aqueous medium

Intramolecular charge transfer (ICT) based fluorescent reagents containing a dansyl fluorophore have been synthesized and characterized. The reagent 1 and its complex, 1+Hg(2+) in sodium acetate buffer (pH 6.7) revealed considerable fluorescence enhancement (switched-on) in the presence of bovine serum albumin (BSA) with 10 ppb detection sensitivity. (1)H NMR spectral analysis suggests complexation between 1 and Hg(2+) ion involving the N,N-dimethylamino and carboxylic functions.     

Azine-based receptor for recognition of Hg2+ ion: crystallographic evidence and imaging application in live cells

A newly synthesized azine-based receptor (L) is found to show remarkable specificity toward the Hg(2+) ion in aqueous media over other metal ions. Coordination of L to Hg(2+) induces a detectable change in color and a turn-on fluorescence response. Restricted C=N isomerization of the azine moieties in the excited state as well as the Photoinduced Electron Transfer (PET) involving the lone pair of electrons of N(1)/N(2) on coordination of L to the Hg(2+) ion account for the turn-on fluorescence response. This reagent could be used for imaging the accumulation of Hg(2+) ions in Epithelial cell line KB 31 cells.     

Recognition of Hg2+ ion through restricted imine isomerization: crystallographic evidence and imaging in live cells

A newly synthesized imine-based receptor (L) showed remarkable specificity toward the Hg(2+) ion in aqueous media over other metal ions. Coordination of L to Hg(2+) induces a turn-on fluorescence response. This was explained based on the restricted imine isomerization along with PET on coordination to Hg(2+). X-ray structural evidence tends to favor a C-C bond rotation rather than C═N isomerization for adopting a favorable conformation in L for coordination to Hg(2+). This reagent could be used for imaging the accumulation of Hg(2+) ions in HeLa cells.     

A naphthalene-based Al3+ selective fluorescent sensor for living cell imaging

An efficient fluorescent Al(3+) receptor, N-(2-hydroxy-1-naphthalene)-N'-(2-(2-hydroxy-1-naphthalene)amino-ethyl)-ethane-1,2-diamine (L) has been synthesized by the condensation reaction between 2-hydroxy naphthaldehyde and diethylenetriamine. High selectivity and affinity of L towards Al(3+) in ethanol (EtOH) as well as in HEPES buffer at pH 7.4, makes it suitable to detect intracellular Al(3+) with fluorescence microscopy. Metal ions, viz. Li(+), Na(+), K(+), Mg(2+), Ca(2+), Mn(2+), Co(2+), Ni(2+), Cu(2+), Zn(2+), Ag(+), Cd(2+), Hg(2+) and Pb(2+) do not interfere. The lowest detection limit for Al(3+) is 3.0 × 10(-7) M and 1.0 × 10(-7) M in EtOH and HEPES buffer respectively.     

Selective colorimetric and fluorometric sensing of Cu(II) by iminocoumarin derivative in aqueous buffer

A new iminocoumarin based receptor L (C(27)H(26)N(4)OS) is synthesized with pyridyl and benzothiazolyl functionality. Synthesis of L is easy and it is isolated in good yield. L shows a selective and distinct color change from yellow to orange with Cu(2+) over Li(+), Na(+), Ca(2+), Mg(2+), Cr(2+), Mn(2+), Fe(2+), Co(2+), Ni(2+), Cu(2+), Zn(2+), Cd(2+), Pb(2+), and Ag(+) whereas a slight change in color is also observed in the case of Hg(2+) but L shows selective fluorescent quenching only in the presence of Cu(2+) in aqueous HEPES buffer (pH 7.0). The naked eye detection limit of Cu(2+) is determined at 2 μM whereas an emission experiment shows a lower detection limit at 200 nM. Selectivity studies of L in presence of 50 equivalents of other ion(s) by emission experiment show no interference toward the detection of 1 equivalent of Cu(2+). Both UV-Vis and fluorescence studies in the presence of Cu(2+)-salts of different counter anions with various sizes and shapes (Cl(-), ClO(4)(-), NO(3)(-), CF(3)SO(3)(-), SO(4)(2-) and BF(4)(-)) show almost similar spectral output in buffer media irrespective of the nature of the counter anions. The detailed UV-Vis and fluorescence titration experiments suggest the existence of both 1:1 and 2:1 (L:Cu(2+)) complexation stoichiometry and EPR study shows d(x(2)-y(2)) ground state of the Cu(II) centre in the complex. Furthermore the formation of a mononuclear [Cu(L)(CH(3)CN)].2ClO(4) complex and the flexible conformation of L in the solid state are confirmed by the single-crystal X-ray structural study.     

Assembly of a new family of mercury(II) zwitterionic thiolate complexes from a preformed compound [Hg(Tab)2](PF6)2 [Tab = 4-(trimethylammonio)benzenethiolate

Reactions of Hg(OAc)2 with 2 equiv of TabHPF6 [TabH = 4-(trimethylammonio)benzenethiol] in MeCN/MeOH afforded a mononuclear linear complex [Hg(Tab)2](PF6)2 (1). By using 1 as a precursor, a new family of mercury(II) zwitterionic thiolate complexes, [Hg2(Tab)6](PF6)4.2MeCN (2.2MeCN), [Hg(Tab)2(SCN)](PF6) (3), [Hg(Tab)2(SCN)2] (4), [Hg(Tab)I2] (5), {[Hg(Tab)2]4[HgI2][Hg2I6]}(PF6)2(NO3)4 (6), [Hg(Tab)2][HgI4] (7), [Hg(Tab)2][HgCl2(SCN)2] (8), [Tab-Tab]2[Hg3Cl10] (9), and [Hg2(Tab)6]3(PF6)Cl11 (10), were prepared and characterized by elemental analysis, IR spectra, UV-vis spectra, 1H NMR, and single-crystal X-ray crystallography. The [Hg2(Tab)6]4+ tetracation of 2 or 10 contains an asymmetrical Hg2S2 rhomb with an inversion center lying on the midpoint of the Hg...Hg line. The Hg atom of the [Hg(Tab)2]2+ dication of 3 is coordinated to one SCN-, forming a rare T-shaped coordination geometry, while in 4, the Hg atom of [Hg(Tab)2]2+ is coordinated to two SCN-, forming a seesaw-shaped coordination geometry. Through weak secondary Hg...S coordinations, each cation in 3 is further linked to afford a one-dimensional zigzag chain. The trigonal [Hg(Tab)I2] molecules in 5 are held together by weak secondary Hg...I and Hg...S interactions, forming a one-dimensional chain structure. In 6, the four [Hg(Tab)2]2+ dications, one HgI2 molecule, one [Hg2I6]2- dianion, one PF6-, and four NO3- anions are interconnected by complicated secondary Hg...I and Hg...O interactions, forming a scolopendra-like chain structure. The secondary Hg...I interactions, [Hg(Tab)2]2+ and [HgI4]2- in 7, are combined to generate a one-dimensional chain structure, while [Hg(Tab)2]2+ and [HgCl2(SCN)2]2- in 8 are interconnected by secondary Hg...N interactions to form a one-dimensional zigzag chain structure. Compound 9 consists of two [Tab-Tab]2+ dications and one [Hg3Cl10]4- tetraanion. The facile approach to the construction of 2-8 and 10 from 1 may be applicable to the mimicking of a coordination sphere of the Hg sites of metallothioneins.     

Structure of solvated mercury(II) halides in liquid ammonia, triethyl phosphite and tri-n-butylphosphine solution

Liquid ammonia, trialkyl phosphites, and especially trialkylphosphines, are very powerful electron-pair donor solvents with soft bonding character. The solvent molecules act as strongly coordinating ligands towards mercury(ii), interacting strongly enough to displace halide ligands. In liquid ammonia mercury(ii) chloride solutions separate into two liquid phases; the upper contains tetraamminemercury(ii) complexes, [Hg(NH(3))(4)](2+), and chloride ions in low concentration, while the lower is a dense highly concentrated solution of [Hg(NH(3))(4)](2+) entities, ca. 1.4 mol dm(-3), probably ion-paired by hydrogen bonds to the chloride ions. Mercury(ii) bromide also dissociates to ionic complexes in liquid ammonia and forms a homogeneous solution for which (199)Hg NMR indicates weak bromide association with mercury(ii). When dissolving mercury(ii) iodide in liquid ammonia and triethyl phosphite solvated molecular complexes form in the solutions. The Raman nu(I-Hg-I) symmetric stretching frequency is 132 cm(-1) for the pseudo-tetrahedral [HgI(2)(NH(3))(2)] complex formed in liquid ammonia, corresponding to D(S) = 56 on the donor strength scale. For the Hg(ClO(4))(2)/NH(4)I system in liquid ammonia a (199)Hg NMR study showed [HgI(4)](2-) to be the dominating mercury(ii) complex for mole ratios n(I(-)) : n(Hg(2+)) > or = 6. A large angle X-ray scattering (LAXS) study of mercury(ii) iodide in triethyl phosphite solution showed a [HgI(2)(P(OC(4)H(9))(3))(2)] complex with the Hg-I and Hg-P bond distances 2.750(3) and 2.457(4) A, respectively, in near tetrahedral configuration. Trialkylphosphines generally form very strong bonds to mercury(ii), dissociating all mercury(ii) halides. Mercury(ii) chloride and bromide form solid solvated mercury(ii) halide salts when treated with tri-n-butylphosphine, because of the low permittivity of the solvent. A LAXS study of a melt of mercury(ii) iodide in tri-n-butylphosphine at 330 K resulted in the Hg-I and Hg-P distances 2.851(3) and 2.468(4) A, respectively. The absence of a distinct I-I distance indicates flexible coordination geometry with weak and non-directional mercury(ii) iodide association within the tri-n-butylphosphine solvated complex.     

Highly sensitive, selective, and rapid fluorescence Hg2+ sensor based on DNA duplexes of poly(dT) and graphene oxide

Coupling T base with Hg(2+) to form stable T-Hg(2+)-T complexes represents a new direction in detection of Hg(2+). Here a graphene oxide (GO)-based fluorescence Hg(2+) analysis using DNA duplexes of poly(dT) that allows rapid, sensitive, and selective detection is first reported. The Hg(2+)-induced T(15)-(Hg(2+))(n)-T(15) duplexes make T(15) unable to hybridize with its complementary A(15) labelled with 6'-carboxyfluorescein (FAM-A(15)), which has low fluorescence in the presence of GO. On the contrary, when T(15) hybridizes with FAM-A(15) to form double-stranded DNA because of the absence of Hg(2+), the fluorescence largely remains in the presence of GO. A linear range from 10 nM to 2.0 μM (R(2) = 0.9963) and a detection limit of 0.5 nM for Hg(2+) were obtained under optimal experimental conditions. Other metal ions, such as Al(3+), Ag(+), Ca(2+), Ba(2+), Mg(2+), Zn(2+), Mn(2+), Co(2+), Pb(2+), Ni(2+), Cu(2+), Cd(2+), Cr(3+), Fe(2+), and Fe(3+), had no significant effect on Hg(2+) detection. Moreover, the sensing system was used for the determination of Hg(2+) in river water samples with satisfactory results.     

A ratiometric fluorescent chemosensor for iron: discrimination of Fe2+ and Fe3+ and living cell application

A newly designed probe, 6-thiophen-2-yl-5,6-dihydrobenzo[4,5]imidazo-[1,2-c] quinazoline (HL(1)) behaves as a highly selective ratiometric fluorescent sensor for Fe(2+) at pH 4.0-5.0 and Fe(3+) at pH 6.5-8.0 in acetonitrile-HEPES buffer (1/4) (v/v) medium. A decrease in fluorescence at 412 nm and increase in fluorescence at 472 nm with an isoemissive point at 436 nm with the addition of Fe(2+) salt solution is due to the formation of mononuclear Fe(2+) complex [Fe(II)(HL)(ClO(4))(2)(CH(3)CN)(2)] (1) in acetonitrile-HEPES buffer (100 mM, 1/4, v/v) at pH 4.5 and a decrease in fluorescence at 412 nm and increase in fluorescence at 482 nm with an isoemissive point at 445 nm during titration by Fe(3+) salt due to the formation of binary Fe(3+) complex, [Fe(III)(L)(2)(ClO(4))(H(2)O)] (2) with co-solvent at biological pH 7.4 have been established. Binding constants (K(a)) in the solution state were calculated to be 3.88 × 10(5) M(-1) for Fe(2+) and 0.21 × 10(3) M(-1/2) for Fe(3+) and ratiometric detection limits for Fe(2+) and Fe(3+) were found to be 2.0 μM and 3.5 μM, respectively. The probe is a "naked eye" chemosensor for two states of iron. Theoretical calculations were studied to establish the configurations of probe-iron complexes. The sensor is efficient for detecting Fe(3+)in vitro by developing a good image of the biological organelles.     

A New Mixed Halide, Cs(2)HgI(2)Cl(2): Molecular Engineering for a New Nonlinear Optical Material in the Infrared Region

A new mixed halide, Cs(2)HgI(2)Cl(2), which contains the highly polar tetrahedron of anion (HgI(2)Cl(2))(2-), has been designed and synthesized by reaction in solution. In its single crystal, the isolated (HgCl(2)I(2))(2-) groups are arranged to form chains. The chains are then further connected into a three-dimensional framework through the Cs atoms that occupy the empty spaces surrounded by halide atoms. All the polar (HgCl(2)I(2))(2-) groups align in such a way that gives a net polarization, leading it to show a phase matchable second harmonic generation (SHG) effect as strong as that of KH(2)PO(4) (KDP) based on the powder SHG measurement. It also displays excellent transparency in the range of 0.4-41 μm with relatively high thermal stability. A preliminary measurement indicates that its laser-induced damage threshold is about 83 MW/cm(2), about twice that of AgGaS(2). This study demonstrates that Cs(2)HgI(2)Cl(2) is a promising nonlinear optical material in the infrared region.     

Acid-catalyzed oxidation of iodide ions by superoxo complexes of rhodium and chromium

Superoxometal complexes L(H(2)O)MOO(2+) (L = (H(2)O)(4), (NH(3))(4), or N(4)-macrocycle; M = Cr(III), Rh(III)) react with iodide ions according to the stoichiometry L(H(2)O)MOO(2+) + 3I(-) + 3H(+) --> L(H(2)O)MOH(2+) + 1.5I(2) + H(2)O. The rate law is -d[L(H(2)O)MOO(2+)]/dt = k [L(H(2)O)MOO(2+)][I(-)][H(+)], where k = 93.7 M(-2) s(-1) for Cr(aq)OO(2+), 402 for ([14]aneN(4))(H(2)O)CrOO(2+), and 888 for (NH(3))(4)(H(2)O)RhOO(2+) in acidic aqueous solutions at 25 degrees C and 0.50 M ionic strength. The Cr(aq)OO(2+)/I(-) reaction exhibits an inverse solvent kinetic isotope effect, k(H)()2(O)/k(D)2(O) = 0.5. In the proposed mechanism, the protonation of the superoxo complex precedes the reaction with iodide. The related Cr(aq)OOH(2+)/I(-) reaction has k(H)2(O)/k(D)2(O) = 0.6. The oxidation of (NH(3))(5)Rupy(2+) by Cr(aq)OO(2+) exhibits an [H(+)]-dependent pathway, rate = (7.0 x 10(4) + 1.78 x 10(5)[H(+)])[Ru(NH(3))(5)py(2+)][Cr(aq)OO(2+)]. Diiodine radical anions, I(2)(*)(-), reduce Cr(aq)OO(2+) with a rate constant k = 1.7 x 10(9) M(-1) s(-1).     

Micelle-induced versatile performance of amphiphilic intramolecular charge-transfer fluorescent molecular sensors

A series of amphiphilic intramolecular charge-transfer fluorescent molecular sensors AS1-3, equipped with a rod-shaped hydrophobic 2-phenylbenzoxazole fluorophore and a hydrophilic tetraamide Hg(2+)-ion receptor, have been prepared. These sensor molecules could be incorporated into the hydrophobic sodium dodecyl sulfate (SDS) micelle, which is confirmed by the clear spectral blue shift and emission enhancement observed at the critical micelle concentration of SDS. Systematic examination of the sensor-Hg(2+) complexation, by using both UV/visible and fluorescence spectroscopy, indicates that SDS significantly modulates both the binding event and signal transformation of these sensor molecules. The potential advantages are fourfold: 1) SDS substantially increases the Hg(2+)-ion association constant and results in an amplified sensitivity. 2) SDS initiates spectral features which facilitate Hg(2+)-ion analysis, for example, in addition to the strengthened fluorescence of the free sensors AS1-3, the original "on-off" response of AS2 toward the Hg(2+) ion is transformed into a self-calibrated two-wavelength ratiometric signal, while for AS3, Hg(2+)-ion complexation in the presence of SDS results in a 180 nm blue shift, which is preferred to the 51 nm spectral shift obtained without SDS. 3) Thermoreversible tuning of the dynamic detection range is realized. 4) Highly specific Hg(2+)-ion identification could be achieved by using the SDS-induced fingerprint emission (358 nm) of the AS2-Hg(2+) complex. Altogether, this work demonstrates a convenient and powerful strategy that remarkably elevates the performance of a given fluorescent molecular sensor. It also implies that for a specific utilization, much attention should be paid to the microenvironment in which the sensor resides, as the behavior of the sensor might be different from that in the bulk solution.     

A new Schiff base system bearing two naphthalene groups as fluorescent chemodosimeter for Zn2+ ion and its logic gate behavior

1-((E)-(2-((2-nitrobenzyl)(2-((E)-(2-hydroxynaphthalen-1-yl)methyleneamino)ethyl)amino)ethylimino)methyl)naphthalen-2-ol (H(2)L), The new compound featuring two naphthalene units was synthesized and characterized. We find that H(2)L has high selectivity and sensitivity to detect Zn(2+) ion over other metal ions such as Na(+), Ag(+), Cd(2+), Co(2+), Cr(3+), Cu(2+), Hg(2+), Mn(2+), Ni(2+), Fe(3+), and the sensitivity is about 10(-7)M. The fluorescent changes of H(2)L upon the addition of cations Zn(2+) and triethylamine is utilized as an AND logic gate at the molecular level, using Zn(2+) and triethylamine as chemical inputs and the fluorescence intensity signal as output.     

A water soluble Al(3+) selective colorimetric and fluorescent turn-on chemosensor and its application in living cell imaging

An efficient water soluble fluorescent Al(3+) receptor, 1-[[(2-furanylmethyl)imino]methyl]-2-naphthol (1-H) was synthesized and characterized by physico-chemical and spectroscopic tools along with single crystal X-ray crystallography. High selectivity and affinity of 1-H towards Al(3+) in HEPES buffer (DMSO/water: 1/100) of pH 7.4 at 25 °C showed it to be suitable for detection of intracellular Al(3+) by fluorescence microscopy. Metal ions, viz. alkali (Na(+), K(+)), alkaline earth (Mg(2+), Ca(2+)), and transition-metal ions (Ni(2+), Zn(2+), Cd(2+), Co(2+), Cu(2+), Fe(3+), Cr(3+/6+), Hg(2+)) and Pb(2+), Ag(+) did not interfere. The lowest detection limit for Al(3+) was calculated to be 6.03 × 10(-7) M in 100 mM HEPES buffer (DMSO/water: 1/100). Theoretical calculations have also been included in support of the configuration of the probe-aluminium complex.     

Ultra-sensitive fluorescent sensor for Hg2+ based on a donor-acceptor-donor framework

A new fluoroionophore [E-4,4'-di(N-(2-pyridyl)amino)stilbene, E1] with a donor-acceptor-donor framework, which features a central stilbene (acceptor) fluorophore and two terminal pyridylamino (donor) ionophores, is reported. The probe displays an ultrasensitive fluorescence quenching response toward Hg(2+) in H(2)O/THF. Coordination of Hg(2+) to E1 affords a 2:1 complex, enabling the detection of Hg(2+) at a concentration as low as 4.4 × 10(-14) M. The interactions between the two species have been thoroughly characterized with UV-vis absorption spectroscopy, fluorescence spectroscopy, and nuclear magnetic resonance spectroscopy. Density functional theory calculations provide further insights into the nature of the fluorescence quenching response. In contrast, a fluorescent molecule with the donor-acceptor architecture, E-4-(N-(2-pyridyl)amino)stilbene (E4), exhibits a greatly attenuated fluorescence quenching response toward Hg(2+).     

A highly selective redox, chromogenic, and fluorescent chemosensor for Hg2+ in aqueous solution based on ferrocene-glycine bioconjugates

The synthesis, electrochemical, optical, and metal-cation-sensing properties of ferrocene-glycine conjugates C(30)H(38)O(8)N(8)Fe (2) and C(20)H(24)O(4)N(4)Fe (3) have been documented. Both compounds 2 and 3 behave as very selective redox (ΔE(1/2) = 217 mV for 2 and ΔE(1/2) = 160 mV for 3), chromogenic, and fluorescent chemosensors for Hg(2+) cations in an aqueous environment. The considerable changes in their absorption spectra are accompanied by the appearance of a new low-energy peak at 630 nm (2, ε = 1600 M(-1) cm(-1); 3, ε = 822 M(-1) cm(-1)). This is also accompanied by a strong color change from yellow to purple, which allows a prospective for the "naked eye" detection of Hg(2+) cations. These chemosensors present immense brightness and fluorescence enhancement (chelation-enhanced fluorescence = 91 for 2 and 42 for 3) following Hg(2+) coordination within the limit of detection for Hg(2+) at 7.5 parts per billion.     

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.