Surface charge influence on the surface plasmon absorbance of electroactive thiol-protected gold nanoparticles

Gold nanoparticles (3.1-5.0 nm in size) surface-derivatized with both electroactive and nonelectroactive self-assembled monolayers were synthesized. The surface-derivatized electroactive particles can be easily oxidized/reduced at an electrode surface based on the diffusion-controlled current-voltage curve observed in cyclic voltammetry measurements. Spectroelectrochemical investigation demonstrated that the maximum absorbance of the nanoparticles in their oxidized state red-shifted compared with their reduced state to a different extent according to their size distribution. In the case of the particles surface-derivatized with nonelectroactive monolayers, much less shift was observed. This study showed that surface plasmon absorbance of gold nanoparticles was not only related to core charge states but was also influenced by surface charge states as well.

Conducting probe atomic force microscopy investigation of anisotropic charge transport in solution cast PBD single crystals induced by an external field

2-(4-Biphenylyl)-5-(4-tert-butylphenyl)-1,3,4-oxdiazole (PBD) is a good electron-transporting material and can form single crystals from solution. In this work, solution cast PBD single crystals with different crystallographic axes (b, c) perpendicular to the Au/S substrates in large area are achieved by controlling the rate of solvent evaporation in the presence and absence of external electrostatic field, respectively. The orientation of these single crystals on Au/S substrate was characterized by transmission electron microscopy (TEM) and atomic force microscopy (AFM). Conducting probe atomic force microscopy (CP-AFM) was used to measure the charge transport characteristics of PBD single crystals grown on Au/S substrates. Transport was measured perpendicular to the substrate between the CP-AFM tip and the Au/S substrate. The electron mobility of 3 x 10(-3) cm(2)/(V s) for PBD single crystal along crystallographic b-axis is determined. And the electron mobility of PBD single crystal along the c-axis is about 2 orders of magnitude higher than that along the b-axis due to the anisotropic charge transport at the low voltage region.

Effect of dye concentration on the charge carrier transport in molecularly doped organic light-emitting diodes

The effect of the concentration of 4-(dicyanomethylene)-2-t-butyl-6-(1,1,7, 7-tetramethyljulolidyl-9-enyl)-4H-pyran (DCJTB) as dopant in tris(8-quinolinolato) aluminum (Alq(3)) on the charge carrier transport in Alq(3):DCJTB was investigated by measuring the steady current-voltage characteristics and the transient electroluminescence. The dopant concentration dependence of the current-voltage relationship clearly indicates the carrier trapping by the DCJTB molecule. The DCJTB concentration significantly affects the electron mobility in Alq(3):DCJTB. The mobility has a nontrivial dependence on the doping level. For relatively low doping levels, less than 1%, the electron mobility of Alq(3):DCJTB decreases with the doping level. An increasing mobility is then observed if the dopant concentration is further increased, followed by a decrease for doping levels larger than similar to2%. The change of the electron mobility with the DCJTB concentration in Alq(3) is attributed to the additional energetic disorder due to potential fluctuations caused by the dipole-dipole interaction of random distribution dopant at the relatively low doping concentration, and to the phase separation at the high doping concentration.

Dependence of charge transfer energy on crystal structure and composition in Eu3+-doped compounds

We report a method for estimating the positions of charge transfer (CT) bands in Eu3+-doped complex crystals. The environmental factor ( he) influencing the CT energy is presented. he consists of four chemical bond parameters: the covalency, the bond volume polarization, the presented charge of the ligand in the chemical bond, and the coordination number of the central ion. These parameters are calculated with the dielectric theory of complex crystals. The relationship between the experimental CT energies and calculated environmental factors was established by an empirical formula. The calculated values are in good agreement with the experimental results. Such a relationship was confirmed by detailed analysis. In addition, our method is also useful to predict the charge-transfer position of any other rare earth ion.

Effect of DNA flanking sequence on charge transport in short DNA duplexes

Several factors can influence charge transport (CT)-mediated DNA, such as sequence, distance, base stacking, base pair mismatch, conformation, tether length, etc. However, the DNA context effect or how flanking sequences influence redox active drugs in the DNA CT reaction and later in DNA enzymatic repair and synthesis is still not well understood. The set of seven DNA molecules in this study have been characterized well for the study of flanking sequence effects. These DNA duplexes are formed from self-complementary strands and contain the common central four-base sequence 5'-A-G-C-T-3', flanked on both sides by either (AT)(n) or (AA)(n) (n = 2, 3, or 4) or AA(AT)(2). UV-vis, fluorescence, UV melting, circular dichroism, and cyclic voltammetry experiments were used to study the flanking sequence effect on CT-mediated DNA by using daunomycin or adriamycin cross-linked with these seven DNA molecules. Our results showed that charge transport was related to the flanking sequence, DNA melting free energy, and ionic strength. For (AA)(n) or (AT)(n) species of the same length, (AA)(n) series were more stable and more efficient CT was observed through the (AA)(n) series. The same trend was observed for (AA)(n) and (AT)(n) series at different ionic strengths, further supporting the idea that flanking sequence can result in different base stacking and modulate charge transport through these seven DNA molecules.

Performance improvement by charge trapping of doping fluorescent dyes in organic memory devices

We studied the memory effect in the devices consisting of dye-doped N, N'-di(naphthalene-1-yl)-N, N'-diphenyl-benzidine sandwiched between indium-tin oxide and Ag electrodes. It was found that the on/off current ratio was greatly improved by the doped fluorescent dyes compared with nondoping devices. A mechanism of charge trapping was demonstrated to explain the improvement of the memory effect. For the off state, the conduction process is dominated by the trapping current, which is a characteristic of the space-charge limited current, whereas the on state is dominated by the detrapping current, and interpreted by Poole-Frenkel emission.

Study on charge transfer reactions at multilayers of polyoxometalates clusters and poly(allylamine hydrochloride) (Grotthuss-018)

Multilayers of anionic phosphotungstic acid (PTA) clusters and positively charged protonated poly(allylamine hydrochloride) (PAH) were assembled by layer-by-layer self-assembled method on Au electrode modified by 3-mercaptopropionic acid (3-MPA). The effect of the charge of the surface of the multilayer assembly on the kinetics of the charge transfer reaction was studied by using the redox probes [Fe(CN)(6)](3-)/(4-) [Ru(NH3)(6)](2+/3+). The cyclic voltammetry experiments showed that the peak currents and peak-to-peak potential differences changed after assembling different layers on the electrode surface indicating that the charge of the surface has a significant effect on the kinetics of the studied charge transfer reactions. These reactions were studied in more detail by electrochemical impedance spectroscopy. When [Fe(CN)(6)](3-/-) was used as the redox label, multilayers that terminated with negatively charged PTA showed a high charge transfer resistance but multilayers that terminated with positively charged PAH showed lower charge transfer resistance. With [Ru(NH3)(6)](2+/3+) as the redox label, the charge transfer resistance at multilayers that terminated with positively charged PAH was much higher than at the multilayer terminated by the negatively charged PTA.

Effect of dye-doped concentration on the charge carrier recombination in molecularly doped organic light-emitting devices

The effect of the concentration of 4-(dicyanomethylene)-2-t-butyl-6(1,1,7,7-tetramethyljulolidyl- 9-enyl)-4H-pyran(DCJTB) as dopant in tris(8-hydroxyquinoline) aluminium (Alq(3)) on the charge carrier recombination was studied by transient electroluminescence (EL). The electron-hole recombination coefficient (gamma) was determined from the long-time component of the temporal decay of the EL intensity after a rectangular voltage pulse was turned off. It was found that the coefficient monotonically decreased with an increase in the DCJTB-doping concentration. The monotonic decrease is attributed to concentration quenching on the excitons and coincided well with the reduction of the EL efficiency.

Investigation of charge-carrier injection characteristics in NPB/Alq3 heterojunction devices

The effect of copper phthalocyanine (CuPc) and LiF interfacial layers on the charge-carrier injection in NN'-di(naphthalene-l-yl)N,N'-diphenyl-benzidine (NPB)/tris(8-hydroxyquinoline) aluminium (Alq(3)) organic heterojunction devices have been studied through the analysis of current-voltage characteristics. The investigation clearly demonstrated that the hole injection into NPB from anode is Fowler-Nordheim (FN) tunneling and the electron injection into Alq3 from cathode is Richardson-Schottky (RS) thermionic emission. The barrier heights obtained from the FN and RS models proved that the band alignments for charge-carrier injection are greatly improved by the CuPc and LiF interfacial layers, which should fully clarify the role of the interfacial layer on the improvement of device performance.

Studies of electron-transfer and charge-transfer coupling processes at a liquid/liquid interface by double-barrel micropipet technique

Investigation of a heterogeneous electron-transfer (ET) reaction at the water/1,2-dichloroethane interface employing a double-barrel micropipet technique is reported. The chosen system was the reaction between Fe(CN)(6)(3-) in the aqueous phase (W) and ferrocene in 1,2-dichloroethane (DCE). According to the generation and the collection currents as well as collection efficiency, the ET-ion-transfer (IT) coupling process at such an interface and competing reactions with the organic supporting electrolyte in the organic phase can be studied. In addition, this technique has been found to be an efficient method to distinguish and measure the charge-transfer coupling reaction between two ions (IT-IT) processes occurring simultaneously at a liquid/liquid interface. On this basis, the formal Gibbs energies of transfer of some ions across the W/DCE interface, such as NO3-, NO2-, Cl-, COO-, TBA(+), IPAs+, Cs+, Rb+, K+, Na+, and Li+, for which their direct transfers are usually difficult to obtain because of the IT-IT coupling processes, were quantitatively evaluated.

Studies on charge transfer across the micro-liquid/liquid interface supported at a double-barrel micropipette

In this paper, the charge transfer across the micro-liquid/liquid interface supported at the orifice of a double-barrel micropipette, namely, a theta-pipette, is reported. Simple ion transfer(TMA(+)), facilitated ion transfer (potassium ion transfer facilitated by DB18C6), and electron transfer (ferrocene and ferri/ferrocyanide system) have been investigated by cyclic voltammetry. The experimental results show that a very thin aqueous film, linking both barrels filled with the aqueous solution and the organic solution respectively, can spontaneously be formed on the outer glass surface of such a double-barrel micropipette to construct a micro-liquid/liquid interface, which provides the asymmetry of diffusion field. Such device is demonstrated experimentally which can be employed as one of the simplest electrochemical cells to investigate the charge transfer across the liquid/liquid interface.

Charge carrier injection and transport in PVK: Alq(3) blend films

We have investigated the current-voltage and electroluminescent (EL) characteristics of single-layer organic devices based on poly(9-vinylcarbazole) (PVK) and tris(8-hydroxyquinoline)aluminium (Alq(3)) blend with different PVK : Alq(3) concentrations. The experimental results from the observed thickness and temperature dependence clearly demonstrate that the current at low voltage is due to the holes injected at the anode and is space-charge limited, whereas the current at the high voltage that steeply increases is explained as the electron tunnelling injection at the cathode. The hole mobility is directly determined by space-charge-limited current at the low voltage region and decreases with increasing Alq(3) content in the blend. The EL efficiency shows concentration dependence, which is attributed to the change of the transport of electrons and holes in the blend film.

Charge transfer across the water/nitrobenzene interface by three-electrode system

A droplet of aqueous solution containing a certain molar ratio of redox couple is first attached onto a platinum electrode surface, then the resulting drop electrode is immersed into the organic solution containing very hydrophobic electrolyte. Combined with reference and counter electrodes, a classical three-electrode system has been constructed, Ion transfer (IT) and electron transfer (ET) are investigated systematically using three-electrode voltammetry. Potassium ion transfer and electron transfer between potassium ferricyanide in the aqueous phase and ferrocene in nitrobenzene are observed with potassium ferricyanide/potassium ferrocyanide as the redox couple. Meanwhile, the transfer reactions of lithium, sodium, potassium, proton and ammonium ions are obtained with ferric sulfate/ferrous sulfate as the redox couple. The formal transfer potentials and the standard Gibbs transfer energy of these ions are evaluated and consistent with the results obtained by a four-electrode system and other methods.

Synthesis, properties and X-ray crystal structure of a new heteropolyacid supermolecular charge-transfer complex [(VB1)(2)DMFHPMo12O40 center dot 5DMF]

The title complex [(VB1)(2)DMFHPMo12O40.5DMF, VB1 = vitamin B-1 (thiamine chloride), DMF = N,N-dimethylformamide] has been synthesized and characterized by elemental analysis, IR, UV-Vis, electron spin resonance, X-ray photoelectron spectroscopy and cyclic voltammetry methods. The X-ray crystal structure revealed that there is one independent molecule in the unit cell of the title complex that contains one mixed-valence heteropolyanion, two VB1+ cations and six DMF molecules. The title complex possesses a centrosymmetrical arrangement in the unit cell, with the P atom at the symmetry center of the heteropolyanion and with eight O atoms surrounding the central P atom, such that two sets of PO4 tetrahedra are formed. The PO4 tetrahedra and MoO66-(7-) octahedra are disordered in the heteropolyanion. The bond distances of P-O-a and Mo=O-d are in the ranges 1.57 (4)-1.70 (4) Angstrom and 1.61 (2)-1.67 (2) Angstrom, respectively.

Synthesis, characterization and crystal structure of a charge transfer salt based on 1.3-cyclopentadiene tetrabutylammoniumdodecamolybdosilicoate

A charge transfer salt, (Bu4N)(4) (C5H6)[(HSiMo11MoO40)-Mo-VI-O-V] has been photochemically synthesized from (Bu4N)(4)SiMo12O40 and 1.3-cyclopentadiene and Characterized, by elemental analysis, IR spectra, solid diffusion reflectance electronic spectra, CV and ESR. The X-ray crystal structure revealed that the title complex crystal data are as follows: triclinic, space group P (1) over bar, a = 14.347(3), b = 14.423(3), c = 27.158(5) Angstrom, alpha = 96.90(3), beta = 104.18(3), gamma = 98.20(3)degrees, V = 5322(2) Angstrom (3), Z = 2, M-r = 2855. 30, D-c = 1.782g.cm(-3), F(000) = 2860, R = 0.0719, wR = 0.198. The title compound is composed of 1.3-cyclopentadiene, four tetrabutylammonium and [(SiMo11MoO40)-Mo-VI-O-V](4-) anion.