Chun-Ying Duan

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.

Crystal Structures and Properties of Large Protonated Water Clusters Encapsulated by Metal−Organic Frameworks

A large ionic water cluster H(H(2)O)(28)(+), consisting of a water shell (H(2)O)(26) and an encaged species H(H(2)O)(2)(+) as a center core, was trapped in the well-modulated cavity of a porous metal-organic framework (MOF) {[Co(4)(dpdo)(12)(PMo(12)O(40))(3)](-)}(infinity) and structurally characterized. Degeneration of the protonated water cluster H(H(2)O)(28)(+) into a smaller cluster H(H(2)O)(21)(+) and recovery of H(H(2)O)(28)(+) from the resulting H(H(2)O)(21)(+) cluster in a reversible way demonstrated the unusual stability of the protonated water clusters H(H(2)O)(28)(+) and H(H(2)O)(21)(+) in the robust crystal host. Proton transport and proton/potassium ion exchange through the channels of the crystal host have been investigated by a well-established fluorometry method. X-ray fluorescence experiments and X-ray structural analyses of the exchanged crystals confirmed the occurrence of the proton/potassium ion-exchange reaction and the transformation of the protonated water cluster H(H(2)O)(28)(+) to an ionic cluster K(H(2)O)(27)(+). Comparison of the H(+)/K(+) exchange of H(H(2)O)(28)(+) with that of its neighboring protonated water cluster H(H(2)O)(27)(+) suggested that the abundance of hydrogen bonds associated with the hydronium/water cluster in the H(H(2)O)(28)(+) cluster was essential for proton transport through the Grotthuss mechanism. On the basis of the results, our porous network could be described as a synthetic non-peptide ion channel, in terms of not only structural features but also the functions addressed. Direct observation of the structures of various large ionic water clusters trapped by porous MOFs, coupled with the proton/ion-exchange processes and the reversible dehydration/rehydration, provided valuable insights into the aqueous proton transfer and its mobility pertaining to the large protonated water clusters in the condensed phase.

Coexistence of chiral hydrophilic and achiral hydrophobic channels in one multi-helical-array metal–organic framework incorporating helical water cluster chains

A novel host-guest metal-organic compound with both chiral hydrophilic and achiral hydrophobic channels has been obtained through the reaction of Cd(II) ion and a versatile asymmetrical ligand of H(4)bptc (H(4)bptc = 1,1-biphenyl-2,2,3,3-tetracarboxylic acid) based on hydro(solvo)thermal reactions.

Conformational switching fluorescent chemosensor for chloride anion

A new fluorescent “off–on” signaling chemical sensor with high selectivity for chloride anion through a guest-induced conformational switching process was achieved by using a positively charged tripodal receptor with naphthyl groups attached to the benzoimidazolium arms.

A highly selective fluorescent sensor for fluoride through ESPT signaling transduction

A highly selective fluorescent sensor for fluoride, bis(2-hydroxy-1-naphthaldehyde)-2,6-pyridinedicarboxylic acid hydrazone (H-NP1) was synthesized and structurally characterized. UV-Vis and luminescent titrations of H-NP1 with F− demonstrated the presence of an H-NP1⋯F− interaction species with association constant logu2006K# = 5.26 ± 0.01. The sensor responded to fluoride ion through an excited-state intermolecular proton transfer (ESPT) mechanism with the emission band red-shifted and enhanced. For further studying the potential mechanism, binding-signaling transduction of related compound H-NP2, bis(2-hydroxy-1-naphthaldehyde)-1,3-benzenedicarboxylic acid hydrazone and two control compounds (H-NP3) and (H-NP4) derived from 1-naphthaldehyde was also investigated for comparison.

Lanthanide heterometallic molecular squares Ru2–Ln2 exhibiting sensitized near-infrared emission

New lanthanide heterometallic molecular squares functionalized with Ru-bipy antenna chromophore Ru2-Ln2 exhibit sensitized near-infrared emission upon photo-excitation of the Ru-centered antenna at 420 nm.

A ferromagnetically coupled Fe 42 cyanide-bridged nanocage

Self-assembly of artificial nanoscale units into superstructures is a prevalent topic in science. In biomimicry, scientists attempt to develop artificial self-assembled nanoarchitectures. However, despite extensive efforts, the preparation of nanoarchitectures with superior physical properties remains a challenge. For example, one of the major topics in the field of molecular magnetism is the development of high-spin (HS) molecules. Here, we report a cyanide-bridged magnetic nanocage composed of 18 HS iron(III) ions and 24 low-spin iron(II) ions. The magnetic iron(III) centres are ferromagnetically coupled, yielding the highest ground-state spin number (S=45) of any molecule reported to date.

Ligand-to-metal ratio controlled assembly of nanoporous metal–organic frameworks

Two bilayered metal-organic frameworks with nanoporous channels were synthesized at different ligand-to-metal ratios, which demonstrated an interesting crystal-to-crystal transformation property and a special fluorescent response to the different guest molecules included.

A sugar-quinoline fluorescent chemosensor for selective detection of Hg2+ ion in natural water

A selective and sensitive fluorescent sensor for detection of Hg2+ in natural water was achieved by incorporating the well-known fluorophore quinoline group and a water-soluble D-glucosamine group within one molecule.

Host–guest complexation of a fluorescent and electrochemical chemsensor for fluoride anion

Host-guest complexation of a ferrocenenylphalene dyad 1, 1,1-diaceylferrocenyl-3-hydroxyl-2-naphthoylhydrazone, as a fluorescent and electrochemical chemosensor for fluoride anion, was investigated. Crystal structure analysis revealed that the two naphthyl arms of compound 1 positioned in the same side about the ferrocene moiety and interacted through pi-pi stacking interactions. The intermolecular pi-pi stacking interactions and the C-H...pi interactions between the ferrocene moieties and the naphthalene rings linked the molecules together featuring a two-dimensional layered structure. Fluorescence titrations of compound 1 indicated that in the presence of F- and H2PO4-, the emission intensities enhanced significantly. Electrochemical titrations revealed that compound 1 sensed the F- anion in high selectivity with a cathodic shift of 120 mV, and had no sense in recognizing H2PO4- anion. 1H NMR titrations demonstrated that while compound 1 hydrogen-bonded to H2PO4- forming simple 1 : 1 host-guest complex, further addition of F- induced the deprotonation of compound 1.