Alkali metal ions transfer across a water/1,2-dichloroethane interface facilitated by a novel monoaza-B15C5 derivative

In this paper, a novel monoaza-B15C5 derivative, N-(2-tosylamino)-isopentyl-monoaza-15-crown-5 (L), is used as an ionophore to facilitate alkali metal cations transfer across a water/1,2-dichloroethane (W/DCE) interface. Well-defined voltammetric behaviors are observed at the polarized W/DCE interfaces supported at micro- and nano-pipets except Cs+. The diffusion coefficient of this ionophore in the DCE phase is calculated to be equal to (3.3+/-0.2) x 10(-6) cm(2) s(-1). The experimental results indicate that a 1:1 (metal: ionophore) complex is formed at the interface with a TIC/TID mechanism. The selectivity of this ionophore towards alkali ions follows the sequence Na+ > Li+ > K+ > Rb+ > Cs+. The logarithm of the association constants (log beta(1)(0)) of the LiL+, NaL+, KL+ and RbL+ complexes in the DCE phase are calculated to be 10.6, 11.6, 9.0 and 7.1, respectively. The kinetic parameters are determined by steady-state voltammograms using nanopipets. The standard rate constants (k(0)) for Li+, Na+, K+ and Rb+ transfers facilitated by L are 0.54+/-0.05, 0.63+/-0.09, 0.51+/-0.04 and 0.46+/-0.06 cm s(-1), respectively. The pH values of aqueous solution have little effect on the electrochemical behaviors of these facilitated processes. The results predicate that this new type of ionophore might be useful to fabricate electrochemical sensor of sodium ion.

An organic-inorganic hybrid ultrathin film: preparation and characterization of copper phthalocyanine derivative-ferric oxide nanoparticles

A nanoparticulate ferric oxide-copper tris(2,4-di-tert-amylphenoxy)-8-quinolinolylphthalocyanine hybrid ultrathin film was constructed from alternate layers by the Langmuir-Blodgett technique. The composition, morphology and structure of the film were studied by X-ray photoelectron spectroscopy (XPS), transmission electron microscopy, atomic force microscopy, small-angle X-ray diffraction, visible spectroscopy and polarized UV-Vis spectroscopy. All the above analyses suggest that the thin film is a kind of one-dimensional superlattice, composed of organic and inorganic components. The XPS data reveal that the nanoparticulate ferric oxide exists as an alpha-Fe2O3 phase in the films. Gas-sensing measurements show that the hybrid LB film has very fast response-recovery characteristics towards 2 ppm C2H5OH vapor.

Investigation of ion transfer across the micro-water/nitrobenzene interface facilitated by a fullerene derivative

A functionalized fullerene derivative containing a monoaza-18-crown-6 moiety was investigated by facilitated ion (such as Li+, Na+, K+, NH4+, Mg2+, and Ca2+) transfer across the micro-water/nitrobenzene interface supported at the tip of a micropipet. The current responses were detected by cyclic voltammetry and Osteryoung square wave voltammetry, which demonstrated that the facilitated ion transfer does occur by an interfacial complexation-dissociation process. The diffusion coefficient of this compound in nitrobenzene was approximately (5.90 +/- 0.04) x 10(-7) cm(2) s(-1), which is 1 order of magnitude less than other common ionophores due to the large size of the molecule. The selectivity of this molecule toward the metal ions followed the sequence Na+ > Li+ > K+ > NH4+ > Ca2+ similar to Mg2+. In addition, this compound was also easy to form film at the water/nitrobenzene interface to inhibit the simple ion transfer of tetramethylammonium ion. However, the adsorption of this ionophore has less influence on the facilitated metal ion transfer.

Alternating LB film of ferric oxide nanoparticles-copper phthalocyanine derivative and its gas sensitivity

Nanoparticulate ferric oxide - tris - (2,4-di-t-amylphenoxy) - (8-quinolinolyl) copper phthalocyanine Langmuir-Blodgett Z-type multilayers were obtained by using monodisperse nanoparticle ferric oxide hydrosol as the subphase. XPS data reveal that the nanoparticle ferric oxide exist as alpha -Fe2O3 phase in the films. Transition electron microscopic (TEM) image of the alternating monolayer shows that the film was highly covered by the copper phthalocyanine derivative and the nanoparticles were arranged rather closely. IR and visible spectra all give the results that the nanoparticles were deposited onto the substrate with the copper phthalocyanine derivative. The gas-sensing measurements show that the alternating LB film had very fast response-recovery characteristic to 2 ppm C2H5OH gas, and also sensitive to larger than 200 ppm NH3.

Simulation of characteristic electrochemical behavior of azobenzene derivative self-assembled monolayers

The characteristic electrochemical mechanics of azobenzene derivative self-assembled monolayers is discussed in present paper. It is presented that the structure inhibition is one of the most important factors in the increase of electrochemical reactive energy. A corresponding mathematical model was established based on Levich and Marcus's theory. Moreover, computational program was written to simulate the decrease of apparent rate constant (k(app)) of electron transfer with increasing surface concentration.

Molecular orientation of copper phthalocyanine derivative ins copper phthalocyanine-Fe2O3 nanoparticles alternating LB films

Copper phthalocyanine-Fe2O3 nanoparticles alternating thin films were fabricated by Langmuir-Blodgett technique. Molecular orientation of [4-(4'-benzyloxy phenyl sulfonyl)phenoxy]-tris-4-(2,4-di-t-phenoxy) phthalocyanine copper (II) in its alternating LB films, deposited at different conditions,was studied by polarized UV-Vis spectra. The tilt extent of the copper phthalocyanine molecule omits LB films increases with the surface pressure of the subphase increasing on the same subphase, or with Fe2O3 concentration decreasing at the same pressure. The orientation of the copper phthalocyanine derivative is important for the gas-sensing properties. The bigger the tilt extent of the phthalocyanine molecule is, the greater the sensitivity of the film is.

Structural and optical properties of distyrylbenzene derivative thin films

In order to understand the relationship between the molecular orientation and optical properties of oligophenylenevinylene film, oriented thin films of 1,4-di(p-methoxystyryl)benzene (DSB-1) and 1,4-di(p-methoxystyryl)-2,5-dimethoxybenzene (DSB-2) were fabricated on a potassium bromide (KBr) (001) surface by the vacuum-evaporation method. The structures and optical properties of DSB films have been investigated by transmission electron microscopy (TEM), atomic force microscopy (AFM) and polarized photoluminescence (PL) spectroscopy, respectively. DSB-1 molecules orient obliquely and/or parallel to the substrate surface depending on the substrate temperature. On the other hand, DSB-2 molecules tend to grow epitaxially with the molecular plane parallel to the substrate surface. The anisotropic molecular orientations represent the polarized PL. The epitaxial growth and molecular orientations observed by TEM and AFM at the local and microscopic scale are confirmed by polarized PL measurement on a macroscopic scale. (C) 1999 American Institute of Physics. [S0021-8979(99)01523-6].

Synthesis and enhancement of quantum efficiency of a series of novel PPV derivative copolymers

A series of novel PPV derivative copolymers with good solubility in common organic solvents were synthesized. The emitting color of these copolymers could range from red to blue by adjusting the structures and the compositions of monomers. Investigation on their optical properties showed that the PL quantum efficiency could be increased by energy transfer and conjugation reduction. The PL quantum efficiency of most green/blue copolymer films on slide glass was higher than 80%.

Studies of ferrocene derivative diffusion and heterogeneous kinetics in polymer electrolyte by using microelectrode voltammetry

The heterogeneous electron transfer rate constants (k(s)) of seven ferrocene derivatives were estimated using cyclic voltammograms under mixed spherical/semi-infinite linear diffusion and steady-state voltammetry at a microdisk electrode in polymer electrolyte. The k(s) and diffusion coefficient (D) are both 100 to 1000-fold smaller in polymer solvent than in monomeric solvents, and the D and k(s) decrease with increasing polymer chain length. The results conform to the difference of viscosity (eta) or relaxation time (tau(L)) for these different solvents. The k(s) and D increase with increasing temperature, and the activation barriers of the electrode reaction are obtained. The influences of the substituting group in the ferrocene ring on k(s) and D are discussed. The k(s) are proportional to the D of the ferrocene derivatives, which indicates that solvent dynamics control the electrode reaction. (C) 1998 Elsevier Science S.A.

Formation of heterocyclic C-60 derivative by gas-phase ion/molecule reaction

Ion/molecule reactions of C-60 with vinyl acetate under chemical ionization conditions have been studied here. Compared with C2H3O+ from acetone, C2H3O+ from vinyl acetate undergoes the reactions more easily, a new heterocycle between C-60 and the studied ion is formed The generation of two sigma-bonds and little angle tensile force of pentatomic ring make it more stable.

Study on alternating LB films of charge-transfer complex of octadecyl-TCNQ and copper phthalocyanine derivative

Infrared spectra of alternating LB films of octadecyl-TCNQ/CuPc are studied. Charge-transfer complexes are formed in LB films and conductance increases about three orders than that of pure CuPc LB films.

The exciplex as an intermediate for photocycloaddition of 9-vinyl anthracene and p-N, N-dimethylamino styrene

The appearence of the new fluorescence peak at about 570 nm demonstrates exciplex formation between the singlet states of 9-vinyl anthracene and p-N, N-dimethylamino stytene. With increasing the polarity of solvents t the red-shift of the emission wavelength occurs and the fluorescence quantum yield of the exciplex decreases. For example t the fluorescence peak is at 550 nm in totuene and at 595 nm in butanone. The fluorescence quatum yields in totuene and in butanone are 0.053 and O respectively. Both the relative yield of the photocycloaddition dimer and the ratio of the relative yields of the trans and cis dimers decrease with increasing the polarity of solvents. For example, the relative yields of the dimer are 1.0 in totuene and 0.04 in butanone respectively. The ratio of the relative yields of traits and cis dimers are 0.54 and 0 in totuene and butanones t respectively. In addition, the exciplex intermediate mechanism was suggested for the photocycloaddition between 9-vinyl anthracene and 9-N, N-dimethylamino styrene.

Ac voltammetric and square wave voltammetric study of the self-assembled monolayers of thiol-functionalized viologen derivative

Electroactive self-assembled monolayers (SAMs) containing viologen group are formed through the adsorption of thiol-functionalized viologen compound CH3(CH2)(9)V2+(CH2)(8)SH, where V2+ is N,N'-dialkylbipyridinium (i.e. a viologen group), onto gold electrodes from methanol/water solution and its electrochemical behavior is investigated ty Ac voltammetry and square wave voltammetry, which have the high sensitivity against background charging. The viologen SAM formed is a sub-monolayer and the normal potentials corresponding to the two successive one-electron transfer processes of the active centers (viologen) are -360 mV and -750 mV (vs. Ag/AgCl) in 0.1 mol/L phosphate buffer solutions (pH 6.96) respectively, and the standard electron transfer rate constant is 9.0 s(-1). The electrochemical behavior of this SAM in various solutions has been preliminarily discussed.

GAS-PHASE SYNTHESIS OF DERIVATIVE OF C-60-C60S+

Gas phase ion-molecular reactions of C-60 with the ion system of CS2 have been studied in the ion source of mass spectrometer. It was found for the first time that the sulfuric derivative of C-60-C60S+ was the main ions in the ion source, they did not react with C-60 to form adduct ions due to their highly saturated structures. According to the dynamic analysis, the product ion came from the reaction of C-60 with the fragment ion S+. The adduct ion may have the structure of epsulfide that is advantageous in energy.

COMPARATIVE-STUDY OF KALMAN FILTERING, SYNCHRONOUS EXCITATION AND NUMERICAL DERIVATIVE TECHNIQUES IN FLUOROMETRY

The performance of Kalman filtering, synchronous excitation and numerical derivative techniques for the resolution of overlapping emission spectra in spectrofluorimetry was studied. The extent of spectrum overlap was quantitatively described by the separation degree D(s), defined as the ratio of the peak separation to the full width at half-maximum of the emission spectrum of the interferent. For the system of Rhodamine B and Rhodamine 6G with a large D(s) of about 0.4, both Kalman filtering and synchronous techniques are able to resolve the overlapping spectra well and to give satisfactory results while the derivative spectra are still overlapped with each other. Moreover, the sensitivities are greatly decreased in derivative techniques. For more closely spaced spectra emitted by the complexes of Al and Zn with 7-iodo-8-hydroxyquinoline-5-sulphonic acid (Ferron)-hexadecyltrimethylammonium bromide, the synchronous excitation technique cannot completely separate the overlapping peaks, although it increases the separation degree from 0.25 in the conventional spectra to 0.37 in the synchronous spectra. On the other hand, Kalman filtering is capable of resolving this system. When the Al/Zn intensity ratio at the central wavelength of Al was > 1, however, the accuracy and precision of the estimates for Zn concentration produced by the Kalman filter became worse. In this event, the combination of synchronous excitation and Kalman filtering can much improve the analytical results.