A strategy for synthesis of ion-bonded amphiphilic miktoarm star copolymers via supramolecular macro-RAFT agent

Amphiphilic supramolecular miktoarm star copolymers linked by ionic bonds with controlled molecular weight and low polydispersity have been successfully synthesized via reversible addition-fragmentation chain transfer (RAFT) polymerization using an ion-bonded macromolecular RAFT agent (macro-RAFT agent). Firstly, a new tetrafunctional initiator, dimethyl 4,6-bis(bromomethyl)-isophthalate, was synthesized and used as an initiator for atom transfer radical polymerization (ATRP) of styrene to form polystyrene (PSt) containing two ester groups at the middle of polymer chain. Then, the ester groups were converted into tertiary amino groups and the ion-bonded supramolecular macro-RAFT agent was obtained through the interaction between the tertiary amino group and 2-dodecylsulfanylthiocarbonylsulfanyl-2-methyl propionic acid (DMP). Finally, ion-bonded amphiphilic miktoarm star copolymer, (PSt)(2)-poly(N-isopropyl-acrylamide)(2), was prepared by RAFT polymerization of N-isopropylacrylamide (NIPAM) in the presence of the supramolecular macro-RAFT agent. The polymerization kinetics was investigated and the molecular weight and the architecture of the resulting star polymers were characterized by means of H-1-NMR, FTIR, and GPC techniques. (c) 2008 Wiley Periodicals, Inc.

Structural characterization and identification of dibenzocyclooctadiene lignans in Fructus Schisandrae using electrospray ionization ion trap multiple-stage tandem mass spectrometry and electrospray ionization Fourier transform ion cyclotron resonance multiple-stage tandem mass spectrometry

The electrospray ionization ion trap multiple-stage tandem mass spectrometry (ESI-MSn) and electrospray ionization Fourier transform ion cyclotron resonance multiple-stage tandem mass spectrometry (ESI-FT-ICR-MSn) have been applied successfully to the direct investigation of a number of dibenzocyclooctadiene lignan constituents from the methanol extracts of the Fructus Schisandrae in the positive ion mode. The detailed structural characterization of the same skeleton and different peripheral substituents had been studied and the precise elemental compositions of ions at high mass resolution had been obtained. So the fragmentation mechanisms could be clarified.

Studies on alkaloids binding to GC-rich human survivin promoter DNA using positive and negative ion electrospray ionization mass spectrometry

Electrospray ionization mass spectrometry (ESI-MS) was used to investigate the binding of 13 alkaloids to two GC-rich DNA duplexes which are critical sequences in human survivin promoter. Negative ion ESI-MS was first applied to screen the binding of the alkaloids to the duplexes. Six alkaloids (including berberine, jatrorrhizine, palmatine, reserpine, berbamine, and tetrandrine) show complexation with the target DNA sequences. Relative binding affinities were estimated from the negative ion ESI data, and the alkaloids show a binding preference to the duplex with higher GC content. Positive ion ESI mass spectra of the complexes were also recorded and compared with those obtained in negative ion mode.

Studies of the intermolecular DNA triplexes of C+center dot GC and T center dot AT triplets by electrospray ionization Fourier-transform ion cyclotron resonance mass spectrometry

Formation and stabilities of four 14-mer intermolecular DNA triplexes, consisting of third strands with repeating sequence CTCT, CCTT, CTT, or TTT, were studied by electrospray ionization Fourier-transform ion cyclotron resonance mass spectrometry (ESI-FTICR-MS) in the gas phase. The gas-phase stabilities of the triplexes were compared with their CD spectra and melting behaviors in solution, and parallel correlation between two phases were obtained. In the presence of 20 mm NH4+ (pH 5.5), the formation of the TTT triplex was not detected in both solution and the gas phase.

Ion-Responsive Behavior of Ionic-Liquid Surfactant Aggregates with Applications in Controlled Release and Emulsification

We propose a simple but efficient, rapid, and quantitative ion-responsive micelle system based on counter-anion exchange of a surfactant with an imidazolium unit. The ion-exchange reaction results in the amphiphilic-to-hydrophobic transition of the imidazolium salt, leading to the destruction of the micelles, which has been successfully applied to control led release and emulsification.

Colorimetric detection of mercury ion (Hg2+) based on DNA oligonucleotides and unmodified gold nanoparticles sensing system with a tunable detection range

Here, we report a simple and Sensitive colorimetric detection method for Hg2+ ions With a tunable detection range based on DNA oligonucleotides and unmodified gold nanoparticles (DNA/AuNPs) sensing system. Complementary DNA strands with T-T mismatches could effectively protect AuNPs from salt-induced aggregation. While in the presence of Hg2+ ions T-Hg2+-T coordination chemistry leads to the formation of DNA duplexes, and AuNPs are less well protected thus aggregate at the same salt concentration, accompanying by color change from red to blue. By rationally varying the number of T-T mismatches in DNA oligonucleotides, the detection range could be tuned.

Electrochemiluminescence detection based on Ruthenium(II) tris(bipyridine) immobilised in sulfonic-functionalised titania nanoparticles by ion exchange strategy

A novel Ruthenium(II) tris(bipyridine)-based solid-state electrochemiluminescence (ECL) sensor was developed in this paper. The sensor was fabricated by immobilising tris(2,2'-bipyridyl) ruthenium(II) (Ru(bpy)(3)(2+)) in sulfonic-functionalised porous titania (TiO2-SO3H) nanoparticles via an ion exchange strategy, followed by employing environment friendly and stable biopolymer chitosan (CHIT) to entrap Ru(bpy)(3)(2+)/TiO2-SO3H onto the ITO electrode.

A one-dimensional network from the self-assembly of gold nanoparticles by a necklace-like polyelectrolyte template mediated by metallic ion coordination

A new approach to one-dimensional organization of gold nanoparticles (2-4 nm) is described, using poly(4-vinylpyridine) (P4VP) molecular chain as a template with the mediation of free Cu2+ ion coordination. The assembly was conducted on freshly prepared mica surfaces and in aqueous solution, respectively. The surface assembly was characterized by tapping mode atomic force microscopy (AFM), observing the physisorbed molecules in their chain-like conformation with an average height of 0.4 nm.

Turn-on fluorescent cyanide sensor based on copper ion-modified CdTe quantum dots

A new fluorescent sensor for the sensitive and selective detection of cyanide (CN-) in aqueous media was developed herein. The sensing approach is based on CN--modulated quenching behavior of Cu2+ toward the photoluminescence (PL) of CdTe quantum dots (QDs). In the presence of CN-, the PL of QDs that have been quenched by Cu2+ was found to be efficiently recovered, which then allows the detection of CN- in a very simple approach. Experimental results showed that the pH of the buffer solution, concentration of copper ions, and size of CdTe QDs all influenced the response of the sensor to CN-. Under the optimal conditions, a good linear relationship between the PL intensity and the concentration of CN- can be obtained in the range of 3.0 x 10(-7) to 1.2 x 10(-5) M, with a detection limit as low as 1.5 x 10(-7) M. In addition, the present fluorescent sensor possesses remarkable selectivity for cyanide over other anions, and negligible influences were observed on the cyanide detection by the coexistence of other anions or biological species (such as albumin and typical blood constituents).

Controlled Synthesis of Ln(3+) (Ln = Tb, Eu, Dy) and V5+ Ion-Doped YPO4 Nano-/Microstructures with Tunable Luminescent Colors

YPO4 nano/microcrystals with multiform crystal phases and morphologies, such as hexagonal nano/submicroprisms, spherical-like nanoparticles, and nanorods with different length/diameter ratios as well as tetragonal nanospindles, have been synthesized via a facile hydrothermal route. A series of controlled experiments indicate that the pH values in the initial solution, phosphorus sources, and the organic additive trisodium citrate (Cit(3-)) are responsible for crystal phase and shape determination of final products. It is found that Cit(3-) as a ligand and shape modifier has the dynamic effect by adjusting the growth rate of different facets under different experimental conditions, resulting in the formation of various geometries of the final products. The possible formation mechanisms for products with diverse architectures have been presented.

Oligonucleotide-stabilized Ag nanoclusters as novel fluorescence probes for the highly selective and sensitive detection of the Hg2+ ion

Fluorescent oligonucleotide-stabilized Ag nanoclusters are demonstrated as novel and environmentally-friendly fluorescence probes for the determination of Hg2+ ions with a low detection limit and high selectivity.

Label-Free Colorimetric Detection of Aqueous Mercury Ion (Hg2+) Using Hg2+-Modulated G-Quadruplex-Based DNAzymes

Mercury ion (Hg2+) is able to specifically bind to the thymine-thymine (T-T) base pair in a DNA duplex, thus providing a rationale for DNA-based selective detection of Hg2+ with various means. In this work, we for the first time utilize the Hg2+-mediated T-T base pair to modulate the proper folding of G-quadruplex DNAs and inhibit the DNAzyme activity, thereby pioneering a facile approach to sense Hg2+ with colorimetry. Two bimolecular DNA G-quadruplexes containing many T residues are adopted here, which function well in low- and high-salt conditions, respectively. These G-quadruplex DNAs are able to bind hemin to form the peroxidase-like DNAzymes in the folded state. Upon addition of Hg2+, the proper folding of G-quadruplex DNAs is inhibited due to the formation of T-Hg2+-T complex. Ibis is reflected by the notable change of the Soret band of hemin when investigated by using UV-vis absorption spectroscopy. As a result of Hg2+ inhibition, a sharp decrease in the catalytic activity toward the H2O2-mediated oxidation of 2,2'-azino-bis(3-ethylbenzothiazoline-6-sulfonic acid)diammonium salt (ABTS) is observed, accompanied by a change in solution color. Through this approach, aqueous Hg2+ can be detected at 50 nM (10 ppb) with colorimetry in a facile way, with high selectivity against other metal ions.

Preparation and electrical properties of new oxide ion conductors Ce6-xDyxMoO15-delta (0.0 <= x <= 1.8)

Ce6-xDyxMoO15-delta (0.0 <= x <= 1.8) were synthesized by modified sol-gel method. Structural and electrical properties were investigated by means of X-ray diffraction (XRD), Raman, X-ray photoelectron spectroscopy (XPS) and electrochemical impedance spectroscopy (EIS). The XRD patterns showed that the materials were single phase with a cubic fluorite structure. Impedance spectroscopy measurement in the temperature range between 350 degrees C and 800 degrees C indicated a sharp increase in conductivity for the system containing small amount of Dy2O3. The Ce5.6Dy0.4MoO15-delta detected to be the best conducting phase with the highest conductivity (sigma(t) = 8.93 x 10(-3) S cm(-1)) is higher than that of Ce5.6Sm0.4MoO15-delta (sigma(t) = 2.93 x 10(-3) S cm(-1)) at 800 degrees C, and the corresponding activation energy of Ce5.6Dy0.4MoO15-delta (0.994 eV) is lower than that of Ce5.6Sm0.4MoO15-delta (1.002 eV).

Preparation and Electrical Properties of New Oxide Ion Conductors Ce6-xGdxMoO15-delta (0.0 <= x <= 1.8)

A series of oxide ion conductors Ce6-xGdxMoO15-delta (0.0 <= x <= 1.8) have been prepared by the sol-gel method. Their properties were characterized by differential thermal analysis/thermogravimetry (DTA/TG), X-ray diffraction (XRD), Raman, IR, X-ray photoelectron spectroscopy (XPS), and AC impedance spectroscopy. The XRD patterns showed that the materials were single phase with a cubic fluorite structure. The conductivity of Ce6-xGdxMoO15-delta increases as x increases and reaches the maximum at x = 0.15. The conductivity of Ce4.5Gd1.5MoO15-delta is sigma(t) = 3.6 x 10(-3) S/cm at 700 degrees C, which is higher than that of Ce4.5/6Gd1.5/6O2-delta (sigma(t) = 2.6 x 10(-3) S/cm), and the corresponding activation energy of Ce4.5Gd1.5MoO15-delta (0.92 eV) is lower than that of Ce4.5/6Gd1.5/6O2-delta (1.18 eV).