A bisferrocene-benzobisimidazole triad as a multichannel ditopic receptor for selective sensing of hydrogen sulfate and mercury ions

The bisferrocene-benzobisimidazole triad behaves as a selective redox and fluorescent chemosensor for HSO(4)(-) and Hg(2+) ions, exhibiting an easily detectable signal change in both the redox potential of the ferrocene/ferrocinium redox couple and in the emission band which is red-shifted (Δλ = 10-13 nm) and enhanced in intensity (Chelation Enhanced Fluorescence, CHEF = 486-225) upon complexation with these ions, in EtOH solutions.     

Solvent dependent fluorescent properties of a 1,2,3-triazole linked 8-hydroxyquinoline chemosensor: tunable detection from zinc(II) to iron(III) in the CH3CN/H2O system

A triazole-containing 8-hydroxyquinoline (8-HQ) ether 2 was efficiently synthesized in two steps from the "click" strategy. Compound 2 gave a strong fluorescence (Φ = 0.21) in nonprotic solvent like CH(3)CN, and a weak fluorescence (Φ = 0.06) in protic solvent like water. In water, a more than 100 nm red shift of the fluorescence maximum was observed for compound 2 in comparison with that in CH(3)CN. This fluorescence difference may be attributed to the intermolecular photoinduced proton transfer (PPT) process involving the protic solvent water molecules. Similarly, this intermolecular PPT process was also observed in the high-water-content CH(3)CN aqueous solution (e.g., CH(3)CN/H(2)O = 5/95, v/v). The water content in the CH(3)CN/H(2)O binary solvent mixture greatly affected the fluorescence intensity (e.g., Φ = 0.06 and 0.25 when CH(3)CN/H(2)O = 5/95 and 95/5, v/v, respectively) and emission wavelength. Using this interesting property, by simple variation of the water content in the CH(3)CN aqueous solution, compound 2 was tuned from a selective "turn-on" fluorescent sensor for Zn(2+) (CH(3)CN/H(2)O = 5/95, v/v) to a ratiometric one for Zn(2+) and a selective "turn-off" one for Fe(3+) (CH(3)CN/H(2)O = 95/5, v/v) over a wide range of pH value. In high-water-content (CH(3)CN/H(2)O = 5/95, v/v) aqueous solution compound 2 shows a selective "turn-on" response toward Zn(2+), with a 10-fold enhancement in the fluorescence intensity at 428 nm and a 62 nm blue shift of the emission maximum (490 to 428 nm) due to the inhibition of intermolecular PPT process upon chelating with Zn(2+). However, in a less polar solvent (CH(3)CN/H(2)O = 95/5, v/v) in which compound 2 has high fluorescence (quantum yield =0.25), it shows a ratiometric response toward Zn(2+), with a continuous decrease of the fluorescence intensity at 399 nm and an increase at 423 nm. More interestingly, in this case, it also exhibits a very sensitive, selective, and ratiometric fluorescence quenching in the presence of Fe(3+), with an 81 nm red shift of the emission maximum (399 to 480 nm) in a wide range of pH through a metal ligand charge transfer (MLCT) effect.     

Fluorescence enhancement of di-p-tolyl viologen by complexation in cucurbit[7]uril

A viologen derivative, 1,1'-di-p-tolyl-(4,4'-bipyridine)-1,1'-diium dichloride (DTV(2+)), was studied in solution and encapsulated in cucurbit[7]uril (CB7), a macrocyclic host. Upon encapsulation, DTV(2+) exhibited dramatically enhanced fluorescence. Aqueous solutions of DTV(2+) were weakly fluorescent (Φ = 0.01, τ < 20 ps), whereas the emission of the DTV(2+)@2CB7 complex was enhanced by 1 order of magnitude (Φ = 0.12, τ = 0.7 ns) and blue-shifted by 35 nm. Similar properties were observed in the presence of NaCl. DTV(2+) in a poly(methyl methacrylate) matrix was fluorescent with a spectrum similar to that observed for the complex in solution. (1)H NMR and UV-vis titrations indicated that the DTV(2+)@2CB7 complex is formed in aqueous solutions with complexation constants K(1) = (1.2 ± 0.3) × 10(4) M(-1) and K(2)= (1.0 ± 0.4) × 10(4) M(-1) in water. Density functional theory and configuration interaction singles calculations suggested that the hindrance of the rotational relaxation of the S(1) state of DTV(2+) caused by encapsulation within the host or a polymer matrix plays a key role in the observed emission enhancement. The absorption and emission spectra of DTV(2+)@2CB7 in water exhibited a large Stokes shift (ΔSt ~ 9000 cm(-1)) and no fine structure. DTV(2+) is a good electron acceptor [E°(DTV(2+)/DTV(?+)) = -0.30 V vs Ag/AgCl] and a strong photooxidant [E°(DTV*(2+)/DTV(?+)) = 0.09 V vs NHE]).     

Ferrocene-based heteroditopic receptors displaying high selectivity toward lead and mercury metal cations through different channels

The synthesis and electrochemical, optical, and ion-sensing properties of ferrocene-imidazophenazine dyads are presented. Dyad 4 behaves as a highly selective chemosensor molecule for Pb(2+) cations in CH(3)-CN/H(2)O (9:1). The emission spectrum (λ(exc) = 317 nm) undergoes an important chelation-enhanced fluorescence effect (CHEF = 47) in the presence of Pb(2+) cations, a new low-energy band appeared at 502 nm, in its UV/vis spectrun, and the oxidation redox peak is anodically shifted (ΔE(1/2) = 230 mV). The presence of Hg(2+) cations also induced a perturbation of the redox potencial although in less extension than those found with Pb(2+) cations. Dyad 7, bearing two fused pyridine rings, has shown its ability for sensing Hg(2+) cations selectively through three channels: electrochemical, optical, and fluorescent; the oxidation redox peak is anodically shifted (ΔE(1/2) = 200 mV), a new low-energy band of the absorption spectrum appeared at 485 nm, and the emission spectrum (λ(exc) = 340 nm) is red-shifted by 32 nm accompanied by a remarkable chelation-enhanced fluorescent effect (CHEF = 165). Linear sweep voltammetry revealed that Cu(2+) cations induced oxidation of the ferrocene unit in both dyads. (1)H NMR studies have been carried out to obtain information about the molecular sites which are involved in the binding process.     

Mercaptothiadiazole capped gold nanoparticles as fluorophore for the determination of nanomolar mercury(II) in aqueous solution in the presence of 50,000-fold major interferents

The present work describes the determination of picogram Hg(II) using 2,5-dimercapto-1,3,4-thiadiazole stabilized gold nanoparticles (DMT-AuNPs) by a spectrofluorimetry method. DMT-AuNPs show emission maximum at 773 nm with excitation at 514 nm. They show a large stock shift (259 nm), narrow emission profile and good photostability. While adding 10 μM Hg(II) the red color solution of DMT-AuNPs changes to purple and the UV-visible spectrum of DMT-AuNPs band at 514 nm was decreased. This is due to aggregation of DMT-AuNPs and it was confirmed by high resolution transmission electron microscopy (HR-TEM). UV-visible spectra of DMT-AuNPs in the presence of nanomolar concentrations of Hg(II) do not show any significant changes at 514 nm. However, the emission intensity of DMT-AuNPs was enhanced during adding even at picomolar concentration of Hg(II) due to photoinduced electron transfer and metal binding-induced conformational restriction upon complexation. Based on the enhancement of emission intensity the concentration of Hg(II) was determined. The binding constant (K(A) = 2.6514 × 10(4) mol(-1) L) value suggested that there is a strong binding force between Hg(II) and DMT-AuNPs. The present fluorophore showed an extreme selectivity towards Hg(II). The emission intensity was increased linearly against a wide range of Hg(II) concentration from 1 × 10(-12) to 1 × 10(-7) M and a detection limit of 0.64 pg L(-1) Hg(II) (S/N = 3) was achieved for the first time using DMT-AuNPs by spectrofluorimetry method. The proposed method was successfully applied for the determination of Hg(II) in environmental samples. The obtained results were validated by ICP-AES.     

A highly selective and sensitive BODIPY-based colourimetric and turn-on fluorescent sensor for Hg2+ ions

A series of monostyryl boron dipyrromethenes appended with an NO(4), NO(2)S(2), N(3)O(4), or N(3)O(2)S(2)-type ligand have been prepared and characterised. While the UV-Vis spectra of the former three compounds in CH(3)CN/H(2)O (2?:?3 v/v) do not respond towards a wide range of metal ions, the derivative with an N(3)O(2)S(2)-ligand exhibits a highly selective and sensitive spectral response towards Hg(2+) ions. The absorption band is blue-shifted by 40 nm due to inhibition of the intramolecular charge transfer process upon metal complexation. The fluorescence is also turned on giving a strong emission band at 572 nm. The colour changes can be easily detected by the naked eye. The results suggest that this compound serves as a promising colourimetric and fluorescent sensor for Hg(2+) ions in this mixed aqueous medium.     

Strong near-infrared luminescence in BaSnO3

Powdered samples of the perovskite BaSnO(3) exhibit strong near-infrared (NIR) luminescence at room temperature, following band-gap excitation at 380 nm (3.26 eV). The emission spectrum is characterized by a broad band centered at 905 nm (1.4 eV), tailing on the high-energy side to approximately 760 nm. The Stokes shift is 1.9 eV, and measured lifetimes in the range 7-18 ms depend on preparative conditions. These extraordinary long values indicate that the luminescence involves a defect state(s). At low temperatures, both a sharp peak and a broad band appear in the visible portion of the luminescence spectrum at approximately 595 nm. Upon cooling, the intensity of the NIR emission decreases, while the integrated intensities of the visible emission features increase to approximately 40% of the NIR intensity at 77 K. Room-temperature photoluminescence (PL) is observed across the Ba(1-x)Sr(x)SnO(3) series. As the strontium content increases, the excitation maximum and band gap shift further into the UV, while the intensity of the NIR emission peak decreases and shifts further into the infrared. This combination leads to an unexpectedly large increase in the Stokes shift. The unusual NIR PL in BaSnO(3) may originate from recombination of a photogenerated valence-band hole and an occupied donor level, probably associated with a Sn(2+) ion situated roughly 1.4 eV above the valence-band edge.     

Synthesis, structural charaterization, and electrochemical and optical properties of ferrocene-triazole-pyridine triads

The synthesis and electrochemical, optical, and cation-sensing properties of the ferrocene-triazole-pyridine triads 3 and 5 are presented. Azidoferrocene 1 and 1,1'-diazidoferrocene 4 underwent the "click" reaction with 2-ethynylpyridine to give the triads 3 and 5 in 81% and 68% yield, respectively. Electrochemical studies carried out in CH(3)CN in the presence of increasing amounts of Zn(2+), Ni(2+), Cd(2+), Hg(2+), and Pb(2+) metal cations, showed that the wave corresponding to the ferrocene/ferrocenium redox couple is anodically shifted by 70-130 mV for triad 3 and 167-214 mV for triad 5. The maximum shift of the ferrocene oxidation wave was found for 5 in the presence of Zn(2+). In addition, the low-energy band of the absorption spectra of 3 and 5 are red-shifted (Δλ = 5-10 nm) upon complexation with these metal cations. The crystal structures of compounds 3 and 5 and the complex [3(2)·Zn](2+) have been determined by single-crystal X-ray methods. (1)H NMR studies as well as density functional theory calculations have been carried out to get information about the binding sites that are involved in the complexation process.     

Ratiometric fluorescent sensor based on inhibition of resonance for detection of cadmium in aqueous solution and living cells

Although cadmium has been recognized as a highly toxic heavy metal and poses many detrimental effects on human health, the Cd(2+)-uptake and nosogenesis mechanisms are still insufficiently understood, mainly because of the lack of facile analytical methods for monitoring changes in the environmental and intracellular Cd(2+) concentrations with high spatial and temporal reliability. To this end, we present the design, synthesis, and photophysical properties of a cadmium sensor, DQCd1 based on the fluorophore 4-isobutoxy-6-(dimethylamino)-8-methoxyquinaldine (model compound 1). Preliminary investigations indicate that 1 could be protonated under neutral media and yield a resonance process over the quinoline fluorophore. Upon excitation at 405 nm, 1 shows a strong fluorescence emission at 554 nm with a quantum yield of 0.17. Similarly, DQCd1 bears properties comparable to its precursor. It exhibits fluorescence emission at 558 nm (Φ(f) = 0.15) originating from the monocationic species under physiological conditions. Coordination with Cd(2+) causes quenching of the emission at 558 nm and simultaneously yields a significant hypsochromic shift of the emission maximum to 495 nm (Φ(f) = 0.11) due to inhibition of the resonance process. Thus, a single-excitation, dual-emission ratiometric measurement with a large blue shift in emission (Δλ = 63 nm) and remarkable changes in the ratio (F(495 nm)/F(558 nm)) of the emission intensity (R/R(0) up to 15-fold) is established. Moreover, the sensor DQCd1 exhibits very high sensitivity for Cd(2+) (K(d) = 41 pM) and excellent selectivity response for Cd(2+) over other heavy- and transition-metal ions and Na(+), K(+), Mg(2+), and Ca(2+) at the millimolar level. Therefore, DQCd1 can act as a ratiometric fluorescent sensor for Cd(2+) through inhibition of the resonance process. Confocal microscopy and cytotoxicity experiments indicate that DQCd1 is cell-permeable and noncytotoxic under our experimental conditions. It can indeed visualize the changes of intracellular Cd(2+) in living cells using dual-emission ratiometry.     

Lead(II) complex formation with glutathione

A structural investigation of complexes formed between the Pb(2+) ion and glutathione (GSH, denoted AH(3) in its triprotonated form), the most abundant nonprotein thiol in biological systems, was carried out for a series of aqueous solutions at pH 8.5 and C(Pb(2+)) = 10 mM and in the solid state. The Pb L(III)-edge extended X-ray absorption fine structure (EXAFS) oscillation for a solid compound with the empirical formula [Pb(AH(2))]ClO(4) was modeled with one Pb-S and two short Pb-O bond distances at 2.64 ± 0.04 and 2.28 ± 0.04 ?, respectively. In addition, Pb···Pb interactions at 4.15 ± 0.05 ? indicate dimeric species in a network where the thiolate group forms an asymmetrical bridge between two Pb(2+) ions. In aqueous solution at the mole ratio GSH/Pb(II) = 2.0 (C(Pb(2+)) = 10 mM, pH 8.5), lead(II) complexes with two thiolate ligands form, characterized by a ligand-to-metal charge-transfer band (LMCT) S(-) → Pb(2+) at 317 nm in the UV-vis spectrum and mean Pb-S and Pb-(N/O) bond distances of 2.65 ± 0.04 and 2.51 ± 0.04 ?, respectively, from a Pb L(III)-edge EXAFS spectrum. For solutions with higher mole ratios, GSH/Pb(II) ≥ 3.0, electrospray ionization mass spectroscopy spectra identified a triglutathionyllead(II) complex, for which Pb L(III)-edge EXAFS spectroscopy shows a mean Pb-S distance of 2.65 ± 0.04 ? in PbS(3) coordination, (207)Pb NMR spectroscopy displays a chemical shift of 2793 ppm, and in the UV-vis spectrum, an S(-) → Pb(2+) LMCT band appears at 335 nm. The complex persists at high excess of GSH and also at ～25 K in frozen glycerol (33%)/water glasses for GSH/Pb(II) mole ratios from 4.0 to 10 (C(Pb(2+)) = 10 mM) measured by Pb L(III)-edge EXAFS spectroscopy.     

FLUORESCENCE SPECTROSCOPY OF BENZO[a]PYRENE DIOL EPOXIDE-DNA ADDUCTS. CONFORMATION-SPECIFIC EMISSION SPECTRA

The fluorescence characteristics of adducts derived from the covalent binding of the highly tumorigenic (+) and the non-tumorigenic (-) enantiomers of trans-7,8-dihydroxy-anti-9,10-epoxy-7,8,9,10-tetrahydrobenzo[a]pyrene (BPDE) to native calf thymus DNA are significantly different from one another both at room temperature and at 77 K. The ratio R of fluorescence intensities of the (0,0) band I (situated near 380 nm) and vibronic band V (near 400 nm) of the pyrene ring system in the BPDE-DNA adducts and of the tetraol (BPT) hydrolysis product of BPDE is very sensitive to the polarity of the solvent, thus mimicking the well known behavior of pyrene itself (A. Nakajima, 1971, Bull. Chem. Soc. Jpn. 44, 3272). The fluorescence excitation and emission spectra of the (+)-BPDE-DNA adducts are relatively sharp and only slightly red-shifted (2-3 nm) with respect to those of BPT in aqueous buffer solution, and R = 1.07 when the fluorescence is excited at the maximum of the absorption spectrum; this compares with R = 1.17 for BPT in water, R = 0.75 in ether, and R = 0.84 for noncovalently intercalated BPT. These results suggest that the pyrene ring system in the covalent (+)-BPDE-DNA adducts is located in an environment which is relatively exposed to the aqueous environment, while physically intercalated BPT molecules are located at hydrophobic binding sites. The fluorescence characteristics of the (-)-BPDE-DNA adducts are more heterogeneous and thus more complex than those of the (+)-adducts. The R ratio depends rather strongly on the wavelength of excitation; a minor, more highly fluorescent and relatively solvent-accessible form of adducts exhibits an R ratio of 1.01. The major, less solvent accessible form is characterized by a larger red shift in the absorption spectrum (approximately 10 nm) and emission spectrum (approximately 6 nm for the (0,0) band) relative to BPT, and an R ratio of 1.07. These characteristics suggest that the local environments of the pyrenyl residues in the (-)-BPDE-DNA adducts are significantly different from those of BPT bound noncovalently to DNA by the intercalation mechanism. Fluorescence methods, particularly at low temperatures where the bands are better resolved and the fluorescence yields are significantly greater than at room temperature, can also be used to distinguish covalent DNA adducts derived from the binding of (+)-BPDE and (-)-BPDE to native double-stranded DNA.     

Determination of lead in phosphate ore and phosphogypsum

Laser induced breakdown spectroscopy (LIBS) is applied to analyze aqueous solutions of Li(+), Na(+), Ca(2+), Ba(2+), Pb(2+), Cd(2+), Hg(2+) and Er(3+) and suspensions of ErBa(2)Cu(3)O(x) particles (d=0.2 microm). An excimer (308 nm) pumped dye laser with laser pulse at 500 nm and pulse energy at 22+/-2 mJ is used to produce plasma in aqueous solution. Plasma emission lines of the elements are detected by a photodiode array detector. Detection limits of the metal ions are 500 mg/l for Cd(2+), 12.5 mg/l for Pb(2+), 6.8 mg/l for Ba(2+), 0.13 mg/l for Ca(2+), 13 microg/l for Li(+) and 7.5 microg/l for Na(+). No mercury and erbium emission can be detected, even at Hg(2+) and Er(3+) concentrations of up to the g/l range. On the other side, for Er in suspensions of ErBa(2)Cu(3)O(x) particles a more than 10(3) times higher sensitivity is found than for dissolved Er(3+). This result gives a possibility to analyze colloid-borne metal ions with an increased sensitivity.     

Ferrocene-based small molecules for dual-channel sensing of heavy- and transition-metal cations

The synthesis, electrochemical, optical, and cation-sensing properties of ferrocene-pentakis(phenylthio)benzene dyads, linked through a putative cation-binding 2-azadiene bridge, are presented. Dyad 5 behaves as a highly selective dual-redox and chromogenic chemosensor molecule for Pb(2+) cations; the oxidation redox peak is anodically shifted (DeltaE(1/2) = 125 mV), and the low energy band of the absorption spectrum is red-shifted (Delta lambda = 119 nm) upon complexation with this metal cation. Linear sweep voltammetry and spectroelectrochemical studies revealed that Cu(2+) and Hg(2+) metal cations induced oxidation of the ferrocene unit. The isomeric dyad 7, in which the nitrogen atom and the ferrocene unit are in closer proximity, has shown its ability for sensing both Pb(2+) and Hg(2+) ions; the oxidation redox peak is anodically higher shifted (DeltaE(1/2) = 340 mV), and the low energy band of the absorption spectrum is lower red-shifted (Delta lambda = 61 nm) that those found for dyad 5. The changes in the absorption spectra are accompanied by dramatic color changes which allow the potential for "naked eye" detection. A further exciting property of dyad 7 is that it behaves as an electrochemically induced switchable chemosensor for Pb(2+) and Hg(2+) because of the low metal-ion affinity of the oxidized 7(*+) species for these metal cations. The experimental data and conclusions about the ion-sensing properties are supported by DFT calculations.     

Mononuclear and dinuclear complexes of dibenzoeilatin: synthesis, structure, and electrochemical and photophysical properties

This work describes a study of Ru(II) and Os(II) polypyridyl complexes of the symmetrical, fused-aromatic bridging ligand dibenzoeilatin (1). The synthesis, purification, and structural characterization by NMR of the mononuclear complexes [Ru(bpy)(2)(dbneil)](2+) (2), [Ru(tmbpy)(2)(dbneil)](2+) (3), and [Os(bpy)(2)(dbneil)](2+) (4), the homodinuclear complexes [[Ru(bpy)(2)](2)[micro-dbneil]](4+) (5), [[Ru(tmbpy)(2)](2)[micro-dbneil]](4+) (6), and [[Os(bpy)(2)](2)[micro-dbneil]](4+) (7), and the heterodinuclear complex [[Ru(bpy)(2)][micro-dbneil][Os(bpy)(2)]](4+) (8) are described, along with the crystal structures of 4, 6, and 7. Absorption spectra of the mononuclear complexes feature a low-lying MLCT band around 600 nm. The coordination of a second metal fragment results in a dramatic red shift of the MLCT band to beyond 700 nm. Cyclic and square wave voltammograms of the mononuclear complexes exhibit one reversible metal-based oxidation, as well as several ligand-based reduction waves. The first two reductions, attributed to reduction of the dibenzoeilatin ligand, are substantially anodically shifted compared to [M(bpy)(3)](2+) (M = Ru, Os), consistent with the low-lying pi orbital of dibenzoeilatin. The dinuclear complexes exhibit two reversible, well-resolved, metal-centered oxidation waves, despite the chemical equivalence of the two metal centers, indicating a significant metal-metal interaction mediated by the conjugated dibenzoeilatin ligand. Luminescence spectra, quantum yield, and lifetime measurements at room temperature in argon-purged acetonitrile have shown that the complexes exhibit (3)MLCT emission, which occurs in the IR-region between 950 and 1300 nm. The heterodinuclear complex 8 exhibits luminescence only from the Ru-based fragment, the intensity of which is less than 1% of that observed in the corresponding homodinuclear complex 5; no emission from the Os-based unit is observed, and an intramolecular quenching constant of k(q) > or = 3 x10(9) s(-)(1) is evaluated. The nature of the quenching process is briefly discussed.     

Photoluminescence and Raman studies of Sm3+ and Nd3+ ions in zirconia matrices: example of energy transfer and host-guest interactions

Photoluminescence and Raman studies on Sm(3+)- and Nd(3+)-doped zirconia are reported. The Raman studies indicate that the monoclinic (m) phase dominates up to a 10 at.% lanthanide level, while stabilization of the cubic phase is attained at approximately 20 and approximately 25 at.% of Sm(3+) and Nd(3+), respectively. Both systems are strongly luminescent under photo-excitation. The emission spectrum at 77 K of the ZrO(2):Sm(3+) system consists of a broad band at 505 nm, that corresponds to the zirconia matrix. At room temperature the band maximum blue-shifts to 490 nm. Sharper bands corresponding to f-f transitions within the Sm(3+)ion are also exhibited in the longer wavelength region of the spectrum. Exclusive excitation of the zirconia matrix provides sensitized emission from the acceptor Sm(3+) ion. The excitation profile is dominated by a broad band at 325 nm when monitored either at the zirconia or at one of the Sm(3+) emissions. A spectral overlap between the 6H(5/2)-->(4)G(7/2) absorption of the Sm(3+) ion with the zirconia emission leads to an efficient energy transfer process in the systems. Multiple facets of the spectral behavior of the Sm(3+) or Nd(3+) in the zirconia matrices, as well as the effects of compositions on the emission and Raman properties of the materials, and the role of defect centers in photoluminescence and the energy transfer processes are discussed.     

Silica-coated Ln3+-Doped LaF3 nanoparticles as robust down- and upconverting biolabels

The preparation of nearly monodisperse (40 nm), silica-coated LaF(3):Ln(3+) nanoparticles and their bioconjugation to FITC-avidin (FITC=fluorescein isothiocyanate) is described in this report. Doping of the LaF(3) core with selected luminescent Ln(3+) ions allows the particles to display a range of emission lines from the visible to the near-infrared region (lambda=450-1650 nm). First, the use of Tb(3+) and Eu(3+) ions resulted in green (lambda=541 nm) and red (lambda=591 and 612 nm) emissions, respectively, by energy downconversion processes. Second, the use of Nd(3+) gave emission lines at lambda=870, 1070 and 1350 nm and Er(3+) gave an emission line at lambda=1540 nm by energy downconversion processes. Additionally, the Er(3+) ions gave green and red emissions and Tm(3+) ions gave an emission at lambda=800 nm by upconversion processes when codoped with Yb(3+) (lambda(ex)=980 nm). Bioconjugation of avidin, which has a bound fluorophore (FITC) as the reporter, was carried out by means of surface modification of the silica particles with 3-aminopropyltrimethoxysilane, followed by reaction with the biotin-N-hydroxysuccinimide activated ester to form an amide bond, imparting biological activity to the particles. A 25-fold or better increase in the FITC signal relative to the non-biotinylated silica particles indicated that there is minimal nonspecific binding of FITC-avidin to the silica particles.     

A BODIPY-based colorimetric and fluorometric chemosensor for Hg(II) ions and its application to living cell imaging

A new monostyryl boron dipyrromethene derivative (MS1) appended with two triazole units indicates the presence of Hg(2+) among other metal ions with high selectivity by color change and red emission. Upon Hg(2+) binding, the absorption band of MS1 is blue-shifted by 29 nm due to the inhibition of the intramolecular charge transfer from the nitrogen to the BODIPY, resulting in a color change from blue to purple. Significant fluorescence enhancement is observed with MS1 in the presence of Hg(2+); the metal ions Ag(+), Ca(2+), Cd(2+), Co(2+), Cu(2+), Fe(2+), Fe(3+), K(+), Mg(2+), Mn(2+), Ni(2+), Pb(2+), and Zn(2+) cause only minor changes in the fluorescence of the system. The apparent association constant (K(a)) of Hg(2+) binding in MS1 is found to be 1.864 × 10(5) M(-1). In addition, fluorescence microscopy experiments show that MS1 can be used as a fluorescent probe for detecting Hg(2+) in living cells.     

Bright and compact alloyed quantum dots with broadly tunable near-infrared absorption and fluorescence spectra through mercury cation exchange

We report a new strategy based on mercury cation exchange in nonpolar solvents to prepare bright and compact alloyed quantum dots (QDs) (Hg(x)Cd(1-x)E, where E = Te, Se, or S) with equalized particle size and broadly tunable absorption and fluorescence emission in the near-infrared. The main rationale is that cubic CdE and HgE have nearly identical lattice constants but very different band gap energies and electron/hole masses. Thus, replacement of Cd(2+) by Hg(2+) in CdTe nanocrystals does not change the particle size, but it greatly alters the band gap energy. After capping with a multilayer shell and solubilization with a multidentate ligand, this class of cation-exchanged QDs are compact (6.5 nm nanocrystal size and 10 nm hydrodynamic diameter) and very bright (60-80% quantum yield), with narrow and symmetric fluorescence spectra tunable across the wavelength range from 700 to 1150 nm.     

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.     

用水溶液中合成的量子点作为生物荧光标记物的研究

以巯基丙酸(HS-CH₂CH₂COOH)为稳定剂,在水溶液中合成了具有窄而对称(FWHM=40nm)的荧光发射带且尺寸为3nm的CdTe半导体纳米粒子,并用此纳米粒子成功地标记了生物分子胰蛋白酶.与单独的CdTe纳米粒子的溶液相比较,CdTe-胰蛋白酶溶液的吸收光谱在400～600nm范围内较为平坦,其发射光谱蓝移8nm,但发射峰的半峰宽不变.实验证明,CdTe-胰蛋白酶溶液吸收和发射光谱的变化是由CdTe纳米粒子与胰蛋白酶之间的结合反应引起的,而不是由空气中的O₂所引起的,加热可促进CdTe纳米粒子与胰蛋白酶之间的结合反应.