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.

Hydrogen-deuterium exchange reactions of cis- and trans-cyclopropane derivatives with D2O and CD3OD in the gas phase

Gas-phase hydrogen-deuterium (H/D) exchange reactions involving four isomeric cyclopropane derivatives were investigated under chemical ionization (CI) conditions, using D2O and CD3OD as reagent gases. There are abundant ions at [M + 1](+), [M + 2](+) and [M + 3](+) in the D2O and CD3OD positive-ion CI mass spectra of the two isomer pairs 1, 2 and 3, 4, Their CI mass spectra are identical with each pair, and so are the collision-induced dissociation (CID) spectra of ions [M + 1](+), [M + 2](+) and [M + 3](+) of each of the two isomer pairs. The CID spectra of [M + 1](+) ions indicate that they have common D/H exchange reactions within each pair, which take place between molecular ions and deuterium-labeling reagents to form the [M - H + D](+) ions. Those of their [M + 2](+) ions show that they have common D/H exchange reactions within each pair, which form the [M-d1 + H](+) ions. Those of their [M + 3](+) ions show that they have common D/H exchange reactions within each pair, which take place between the [M-d1] and deuterium-labeling reagents to produce [Md-2 + H](+) for the isomer pair 1, 2 and [M-d1 + D](+) for the Isomer pair 3, 4. The number and position, and active order of the active hydrogen atoms of the isomer pairs 1, 2 and 3, 4 were determined. Copyright (C) 2000 John Wiley & Sons, Ltd.

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.

H/D exchange reaction of cyclopropane derivatives in the ion system of CD3OD

The fragmentation properties of the product ions [M + 1](+), [M + 2](+) and [M + 3](+) formed by ion-molecule reaction of four cyclopropane derivatives with the ion system of CD3OD were investigated by using collision-induced dissocation technique. The experiment results indicated that the product ions were produced via the H/D exchange reaction between reactants and reactive reagent ions of CD3OD. There are two exchangable hydrogen atoms on the ring of compounds 1 and 2, and only one for compound 3 and 4.

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.

Ion-molecule reactions of cis- and trans-cyclopropane derivatives with methane, acetone and vinyl acetate under chemical ionization conditions

Ion-molecule reactions of four isomeric cyclopropane derivatives were investigated under chemical ionization(CI) conditions, using methane, acetone and vinyl acetate as reagent gases, The methane positive-ion CI mass spectra of each of two isomer pairs 1,2 and 3,4 are identical, and so are the collision-induced dissociation (CTD) spectra of the protonated molecules of each of the two isomer pairs, The protonation reactions for the isomer pairs 1,2 and 3,4 occurred on the sites of the carboxyl groups and the R groups, respectively, Differences between isomers 1 and 2 are observed in their acetone (A) positive-ion CI mass spectra and in the CID spectra of their adduct ions ([M+H+A](+)), The adduct ions of compounds 2, 3 and 4 with protonated acetone and with protonated acetone dimer are observed in their CI mass spectra, However, only the adduct ions of compound 1 with protonated acetone appear in its CI mass spectrum, The protonated dimers of each of the four compounds are found in their vinyl acetate positive-ion CI mass spectra, and the CID spectra of these dimers for isomers 1 and 2 can also reflect their stereostructural difference. (C) 1998 John Wiley & Sons, Ltd.

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.

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.