Elucidation of Selectivity for Silver Ion Based on Metal-Induced H-Type Aggregation of Fluorescent Receptor.

In present work, a new substituted phthalonitrile derivative was prepared by the nucleophilic displacement reaction and then highly soluble zinc phthalocyanine (ZnPc) with four peripheral 1-hydroxyhexan-3-ylthio groups was synthesized by cyclotetramerization and characterized by FTIR, 1H and 13C NMRs spectroscopies, fluorescence and UV-vis measurements. The optical property and quantum yield of ZnPc were elucidated in mixed solvent of ethanol/water with varying compositions. The pH-dependent fluorescence and absorbance spectra of ZnPc in the absence and presence of Ag+ ions were obtained to elucidate the optimum pH value that is convenient for stable complex formation in predetermined mixture. A comparative study for recognition of Ag+ ion has been carried out to evaluate the effect of the solution parameters on selective sensing ability of ZnPc as a fluorescent receptor. Interference effect was investigated by spectrofluorometric titration based on fluorescence quenching of ZnPc upon addition of Ag+ ion in the presence of foreign metal ions. Stepwise complexation/decomplexation cycles with Na2S-titration by fluorescence quenching/enhancement were investigated to establish the reversible response rate and reusability of ZnPc toward Ag+ ions. Graphical Abstract Selective determination of silver ion based on H-type aggregation of zinc phthalocyanine.

Ratiometric sensor based on imprinted quantum dots-cationic dye nanohybrids for selective sensing of dsDNA.

A ratiometrically responsive sensor for dsDNA is reported, based on molecularly imprinted polymer coated quantum dots (MIP-QDs). A new platform is described for probing dsDNA by tracing the "turn on" fluorescence signal of malachite green (MG) as a cationic dye and "turn off-on" room temperature phosphorescence (RTP) signal of MIP-QDs/MG nanohybrids. The interaction between MIP-QDs surface and MG discloses an intense quenching in RTP (turning off) by a phosphorescence resonance energy transfer (PRET) process. After the addition of dsDNA, MG molecules escape from the MIP-QDs surface and intercalate into the dsDNA, resulting in the restoration of RTP intensity of MIP-QDs (turning on) and also enhancing in fluorescence of MG. This outcome hereby can be employed for the selective sensing of dsDNA via optical response. The ratio of fluorescence enhancement of MG to RTP intensity of MIP-QDs is proportional to the concentration of dsDNA in the range of 0.089-1.79 µg/mL with a detection limit (3σ/K) of 19.48 ng/mL under the optimized experimental conditions.

Monitoring the Instant Creation of a New Fluorescent Signal for Evaluation of DNA Conformation Based on Intercalation Complex.

Here we report the monitoring the instant creation of a new fluorescent signal (FS) aroused from a positively charged water-soluble fluorogenic probe, ethidium bromide (EtBr) in the presence of a radical initiator, ammonium persulfate (APS) and an accelerator, tetraethylmetilendiamine (TEMED) for evaluation of deoxyribonucleic acid (DNA) conformation. The results revealed that the occurred FS (λex = 430 nm; λmax = 525 nm) is a reduced form of EtBr (λex = 480 nm; λmax = 617 nm) and it is completely distinct from hydroethidine (λex = 350 nm; λmax = 430 nm), which is two-electron reduced form of EtBr. It was noticed that EtBr was reduced to a new FS during the polymerization of N, N dimethyacrylamide (DMAA) too, at 25 °C in the presence of APS and TEMED or at 55 °C with only APS, and the rate of formation of FS was increased upon treatment time. The effect of nanoclays such as Laponite XLG® and Laponite XLS®, which provide a protective environment for DNA in nature, were also investigated through the reduction process of EtBr in the absence and presence of a water soluble monomer DMAA. We demonstrated that DNA conformation might be evaluated by monitoring FS effectuated during the reduction of EtBr in the presence of nanoclays having positively and negatively charged surfaces. Protective property of DNA against the formation of reduced product was elucidated by carrying out the polymerization at 55 °C. The results revealed that the monitoring of formation of FS in the presence of radical initiator could lead to elucidate the conformation of DNA upon formation of intercalator complex.

Highly Stretchable DNA/Clay Hydrogels with Self-Healing Ability.

We present mechanically strong and self-healable clay hydrogels containing 2-8 w/v % ds-DNA together with a synthetic biocompatible polymer, poly( N, N-dimethylacrylamide). Clay nanoparticles in the hydrogels act like a chemical cross-linker and promote their elastic behavior, whereas DNA contributes to their viscoelastic energy dissipation. The extent of mechanical hysteresis during cyclic tensile tests reveals that the strength of intermolecular bonds in DNA/clay hydrogels is in the range of the strength of hydrogen bonds. The hydrogels exhibit a high stretchability (up to 1500%) and a tensile strength between 20 and 150 kPa. They have the ability to self-heal, which is induced by heating the damaged gel samples above the melting temperature of ds-DNA. When comparing the mechanical properties of the hydrogels before and after healing, the healing efficiency is greater than 100%. We also demonstrate that ds-DNA molecules entrapped in the gel network undergoes thermal denaturation/renaturation cycles, leading to a further improvement in the mechanical properties of the hydrogels.

Elucidation of selectivity for uranyl ions with an ICT organosilane-modified fluorescent receptor.

A fluorescent receptor, isocyanatopropyl trimethoxysilane grafted 9-amino acridine (AcI), was synthesized and characterized by elemental analysis, FTIR and NMR spectroscopy. Photophysical properties and pH-dependent fluorescence behavior of AcI were investigated and its complex stoichiometry with uranyl ion was elucidated. Change in fluorescence emission of AcI with pH of the solution was observed and pKa value was determined by using integrated emission intensity versus pH. It was found that AcI exhibited fluorescence enhancement, which can be attributed to an internal charge transfer (ICT) mechanism, upon titration with uranyl ions in mixture of ethanol-buffer solution while the fluorescence emission of AcI was not affected by addition of other divalent transition metal ions except mercury (II) ions. On the other hand, the both fluorescence and UV-vis titration measurements revealed unique selectivity for uranyl ions over the interfering mercury (II) ions. The spectrofluorometric titration clarified that uranyl interacted with AcI to form AcI 2(UO2(2 +))3 (2:3) complex structure with an apparent association constant of K = 7.41 × 10(6) M(-2/3). The interference effect of some cations on fluorescence enhancement exhibited by complex was also tested.

Synthesis and photophysical properties of metallophthalocyanines substituted with a benzofuran based fluoroprobe.

The synthesis, characterization and photophysical properties of the tetra- {6-(-benzofuran-2-carboxylate)-hexylthio} substituted copper(II), cobalt(II), manganese(III) and zinc (II) phthalocyanines, {M[Pc(ß-S(CH(2))(6)OCOBz-Furan)(4)], which were derived from 6-(3,4-dicyanophenylthio)-hexyl-2-benzofuranate (BzF) (1-4) are reported for the first time. The new compounds have been synthesized and fully characterized by elemental analysis, FTIR, UV-vis, (1)H- and (13)C NMR, MS (Maldi-TOF). In this work, we also report the effects of peripherally bound BzF substituent on the photophysical properties of metallo phthalocyanine derivatives. The effects of changing the central metal ions on quantum yield are discussed. It was found that the substitution of BzF groups on the framework of phthalocyanines diminished the fluorescence quantum yield of these complexes depending on paramagnetic behavior of central metal atoms. In addition, central metal atoms like Co and Cu also caused to decrease in quantum yield of phthalocyanine backbone.

Elucidation of multiple-point interactions of pyranine fluoroprobe during the gelation.

We have studied the multiple-point interactions of the pyranine (8-hydroxypyrene-1,3,6-trisulfonic acid, trisodium salt; 3sPyOH) fluoroprobe with polymer chains during the free-radical polymerization of acrylamide (AAm) by using the steady state fluorescence measurements. We observed a considerable blue shift from 515nm to 406nm in the emission spectra due to a C-O ether bond formation between the hydroxylic oxygen of 3sPyOH and a terminal C-atom of the growing AAm chain. Furthermore ionic (electrostatic) interactions occur between the three ionized sulfonic acid groups (SO(3)(-)) of 3sPyOH and protonated amide groups on the AAm chains. These electrostatic interactions also cause a gradual red shift in the maximum of the short-wavelength-peak, from 406nm to 430nm. The results showed that the pyranine can be used as a probe for real time monitoring of the polymerization process of AAm system since it monitors both the progression of the polymerization via chemical binding over OH group and the change in the local density of the polymerizing sample by means of the gradual red shift in the short-wavelength-peak via ionic interactions over SO(3)(-) groups.

Multiple-point adsorption of terbium ions by lead ion templated thermosensitive gel: elucidating recognition of conformation in gel by terbium probe.

Lead ion templated thermosensitive heteropolymer gel which has recognition ability of methacrylate pairs has been synthesized and characterized. The gel consists of a main monomer component, N-isopropylacrylamide (NIPA), responsible for volume phase transition, methacrylic acid (MAA) moieties imprinted as pairs to adsorb terbium ions and cross-links. An imprinting technique was applied using lead ion complex with methacrylate ligands in dioxane media. After gel was obtained, lead ions were removed by washing and the imprinted gel showed strong binding ability to terbium ions, comparable with that of the non-imprinted gel prepared without lead ions. It was found that the Tb(3+) fluorescence intensity was considerably increased upon binding this ion to both imprinted and non-imprinted gels, but the largest enhancement of fluorescence intensity was observed when Tb(3+) was bound to imprinted gel in shrunken state. This is because of the decrease of coordinated water molecules on Tb(3+) and the strong binding of this ion to methacrylate pairs which are encoded within the weakly cross-linked network of imprinted gel.