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Ling Zang

Publications and source records attributed to Ling Zang.

14 recordsLinked to original sources
PubMed2006

Linearly polarized emission of an organic semiconductor nanobelt.

Linearly polarized emission has been observed for the nanobelts fabricated from a perylene diimide molecule through both solution-based and surface-supported self-assembling. The measurement of polarized emission was performed over single nanobelts with use of a near-field scanning optical microscope (NSOM) adapted with emission polarization (by putting a planar polarizer before the detector). Rotating the emission polarizer (from 0 degrees to 180 degrees) changed the emission intensity in a way depending on the relative angle between the long axis of the belt and the polarizer with a minimum of intensity detected at ca. 78 degrees, which is indicative of the tilted stacking of molecules along the belt direction.

Journal Article↗
PubMed2006

Effect of side-chain substituents on self-assembly of perylene diimide molecules: morphology control.

Effect of side-chain substitutions on the morphology of self-assembly of perylene diimide molecules has been studied with two derivatives modified with distinctly different side-chains, N,N'-di(dodecyl)-perylene-3,4,9,10-tetracarboxylic diimide (DD-PTCDI) and N,N'-di(nonyldecyl)-perylene-3,4,9,10-tetracarboxylic diimide (ND-PTCDI). Due to the different side-chain interference, the self-assembly of the two molecules results in totally different morphologies in aggregate: one-dimensional (1D) nanobelt vs zero-dimensional (0D) nanoparticle. The size, shape, and topography of the self-assemblies were extensively characterized by a variety of microscopies including SEM, TEM, AFM, and fluorescence microscopy. The distinct morphologies of self-assembly have been obtained from both the solution-based processing and surface-supported solvent-vapor annealing. The nanobelts of DD-PTCDI fabricated in solution can feasibly be transferred to both polar (e.g., glass) and nonpolar (e.g., carbon) surfaces, implying the high stability of the molecular assembly (due to the strong pi-pi stacking). The side-chain-dependent molecular interaction was comparatively investigated using various spectrometries including UV-vis absorption, fluorescence, X-ray diffraction, and differential scanning calorimetry. Compared to the emission of ND-PTCDI aggregate, the emission of DD-PTCDI aggregate was significantly red-shifted (ca. 30 nm) and the emission quantum yield decreased about three times, primarily due to the more favorable molecular stacking for DD-PTCID. Moreover, the aggregate of DD-PTCDI shows a pronounced absorption band at the longer wavelength, whereas the absorption of ND-PTCDI aggregate is not significant in the same wavelength region. These optical spectral observations are reminiscent of the previous theoretical investigation on the side-chain-modulated electronic properties of PTCDI assembly.

Journal Article↗
PubMed2006

Nanofibril self-assembly of an arylene ethynylene macrocycle.

Nanofibril structures have been fabricated from an arylene ethynylene macrocycle (AEM), which consists of a square frame corner-joined by four carbazole moieties. The fabrication was performed through a gelating process by cooling a warm, homogeneous solution in cyclohexane at high temperature (e.g., 100 degrees C) to room temperature. During the gelation, the molecules become organized, with optimal pi-pi stacking in cooperation with the side-chain association. The favorable pi-pi stacking facilitates the 1D growth of molecular assembly.

Alkynes↗
PubMed2006

Visible photooxidation of dibenzothiophenes sensitized by 2-(4-methoxyphenyl)-4, 6-diphenylpyrylium: an electron transfer mechanism without involvement of superoxide.

We report here on a new electron-transfer mechanism for visible-light photooxidation of sulfides in which no superoxide ion is involved. Visible-light irradiation of 2-(4-methoxyphenyl)-4, 6-diphenylpyrylium tetrafluoroborate (MOPDPP(+)BF(4)(-)) in an O(2)-saturated acetonitrile solution containing dibenzothiophene (DBT) results in nearly 100% conversion to oxygenated products, DBT sulfoxide and sulfone. The photooxidation of DBT is initiated by a photoinduced electron-transfer process, where the excited MOPDPP(+) traps an electron from the ground-state DBT to form MOPDPP(*) and DBT radical cation. Such a mechanism is consistent with the studies of laser flash photolysis, electron spin resonance, and fluorescence quenching of the irradiated system. The photogenerated DBT radical cation undergoes a coupling reaction with O(2) to produce the intermediate responsible for the formation of the oxygenated products. The presence of O(2) has no effect on the decay kinetics of the transient absorption of MOPDPP(*), indicating that no redox reaction occurs between MOPDPP(*) and O(2), and thus no superoxide ion (O(2)(*-)) is formed. Moreover, the ESR signal of MOPDPP(*) was significantly enhanced in the presence of O(2), consistent with the assumption that the photogenerated DBT radical cation couples with O(2) to form the oxygen-adduct, which is subject to further reactions (Scheme 3) leading to the final oxygenated products. Similar results have been obtained when using 10-methylacridine hexafluorophosphate (AcrH(+)PF(6)(-), which has similar reduction potential in the ground state as MOPDPP(+)) as the sensitizer. This finding provides a possibility for the photooxidation of sulfides with dioxygen utilizing visible light (solar energy) and is also of significance in clarification of the reaction mechanism.

Electron Spin Resonance Spectroscopy↗
PubMed2006

Fenton degradation of organic pollutants in the presence of low-molecular-weight organic acids: cooperative effect of quinone and visible light.

The influence of low-molecular-weight organic acids (LMWOAs), such as malonic acid, ethylenediaminetetraacetic acid, and oxalic acid, on the Fenton degradation of organic pollutants was examined under visible irradiation (lambda > 450 nm). The Fenton degradation of malachite green in the dark was completely blocked in the presence of LMWOAs. It was found that either visible light irradiation or the addition of hydroquinone could initiate the dye degradation, but the mineralization yield was almost zero. An important result was that the dye mineralization in the presence of LMWOAs could be achieved when both visible irradiation and hydroquinone were introduced. Similar results were obtained with colorless pollutants, such as benzyltrimethylammonium chloride and 2,4,5-trichlorophenol. We concluded that coupling visible irradiation and hydroquinone could be a strong and universal driving force in the Fenton reaction for the complete degradation and mineralization of organic pollutants, even in the presence of LMWOAs.

Benzoquinones↗
PubMed2006

Controlling charge transport in single molecules using electrochemical gate.

We have studied charge transport through single molecules covalently bound to two gold electrodes in electrolytes by applying a voltage between the two electrodes and a reference electrode (gate). This electrochemical gating can effectively control the current through the molecules, depending on the electronic properties of the molecules. For electrochemically inactive molecules, such as 4,4'-bipyridine and 1,4'-benzenedithiol, the gate voltage influences the transport current only slightly (less than 30%). This lack of significant gate effect is attributed to the large LUMO-HOMO gaps of the molecules and the screening of the gate field by the two electrodes. For nitro-oligo(phenylene ethynylene) (OPE-NO2), which undergoes multiple irreversible reductions at negative gate voltages, the current through the molecules can be modulated several folds by the gate. This gate effect is irreversible and associated with the reduction of the NO2 group to different products that have different electron withdrawing capabilities from the conjugate backbone of the molecule. The most interesting molecules are perylene tetracarboxylic diimide compounds (PTCDI), which exhibit fully reversible redox reactions. The current through PTCDI can be reversibly varied and controlled over three orders of magnitude with the gate. Such a large gate effect is related to a redox state-mediated electron transport process.

Journal Article↗
PubMed2005

Degradation of dye pollutants by immobilized polyoxometalate with H2O2 under visible-light irradiation.

A Keggin polyoxometalate (POM, i.e., PW12O40(3-)) and its lacunary derivative are immobilized on an anionic exchange resin through electrostatic interaction at pH 4.6 in an aqueous dispersion. The resin-supported POM thus obtained catalyzes the efficient degradation of cationic dye pollutants in the presence of H2O2 under visible-light irradiation. To evaluate the photocatalytic system, degradation of a rhodamine B (RB) dye was investigated in detail using UV-visible spectroscopy, high performance liquid chromatography, and gas chromatography/mass spectrometry techniques to identify the intermediates and final products. Fluorescence lifetime measurements revealed the electron transfer from the visible-light-excited RB molecules to the POMs. Electron paramagnetic resonance measurements, investigation of the effects of *OH and *OOH scavengers on the photoreaction kinetics, and IR analysis indicated that de-ethylation of RB was due to *OOH radicals, but the decomposition of the conjugated xanthene structure was caused by the peroxo species formed by interaction of H2O2 with the lacunary POM loaded on the resin. A total organic carbon removal of ca. 22% was achieved, and the recycle experiment suggested excellent stability and reusability of the heterogeneous catalyst. On the basis of the experimental results, a photocatalytic mechanism is discussed.

Catalysis↗
PubMed2005

Nanobelt self-assembly from an organic n-type semiconductor: propoxyethyl-PTCDI.

Nanobelt structures have been fabricated for an n-type semiconductor molecule, N,N'-di(propoxyethyl)perylene-3,4,9,10-tetracarboxylic diimide (PTCDI). The short alkyloxy side chain not only affords effective pi-pi stacking in polar solvents for self-assembling but also provides sufficient solubility in nonpolar solvents for solution processing. As revealed by both AFM and electron microscopies, the nanobelts have an approximately rectangular cross section, with a typical thickness of about 100 nm and a width in the range of 300-500 nm. The length of the nanobelts ranges from 10 to a few tens of micrometers. The highly organized molecular packing (uniaxial crystalline phase) has been deduced from the measurement of electron diffraction and polarized microscopy imaging. The detected optical axis is consistent with the one-dimensional stacking of the molecules.

Journal Article↗
PubMed2005

Photooxidation of dibenzothiophene and 4,6-dimethyldibenzothiophene sensitized by N-methylquinolinium tetrafluoborate: mechanism and intermediates investigation.

Photooxidation of dibenzothiophene (DBT) and 4,6-dimethyldibenzothiophene (DMDBT) sensitized by N-methylquinolinium tetrafluoborate (NMQ(+)BF4-) has been investigated in O2-saturated acetonitrile solutions. Nearly 100% oxidation of DBT and DMDBT was observed, and the oxidized products are predominantly composed of sulfoxides and sulfones, which are formed via photoinduced electron transfer (ET). Such ET processes were studied with fluorescence quenching of NMQ+, time-resolved transient absorption measurement, and ESR experiments. The fluorescence of NMQ+ is efficiently quenched by DBT and DMDBT via diffusion-controlled processes, with bimolecular quenching constants of 1.6 x 10(10) M(-1) s(-1) for DBT and 2.3 x 10(10) M(-1) s(-1) for DMDBT. The electron-transfer nature of the quenching is evidenced by the transient absorption measurement of the neutral radical NMQ*, which is formed by electron transfer from the substrates (DBT or DMDBT) to the excited singlet state of NMQ+. The ESR spectra of the superoxide radical anion (O2*-) trapped by 5,5-dimethyl-1-pyrroline N-oxide (DMPO) in the photooxygenation of DBT and DMDBT as well as their sulfoxides manifest that O2 traps an electron from NMQ* to form O2*-. The fact that the formation of sulfoxides and sulfones is greatly suppressed in the presence of benzoquinone (BQ), an efficient electron trap for NMQ* and O2*-, further indicates an ET process in the photooxidation of DBT and DMDBT. As inferred from the control experiments, the role of singlet oxygen (1O2) in the photooxidation is negligible. The intermediates responsible for the formation of sulfoxides and sulfones have been examined in detail.

Borates↗
PubMed2005

Large gate modulation in the current of a room temperature single molecule transistor.

We have demonstrated a single molecule field effect transistor (FET) which consists of a redox molecule (perylene tetracarboxylic diimide) covalently bonded to a source and drain electrode and an electrochemical gate. By adjusting the gate voltage, the energy levels of empty molecular states are shifted to the Fermi level of the source and drain electrodes. This results in a nearly 3 orders of magnitude increase in the source-drain current, in the fashion of an n-type FET. The large current increase is attributed to an electron transport mediated by the lowest empty molecular energy level when it lines up with the Fermi level.

Journal Article↗
PubMed2004

Studying and switching electron transfer: from the ensemble to the single molecule.

We report here on the systematic investigation of photoinduced intramolecular electron transfer (IET) in a series of donor-bridge-acceptor molecules as a means of understanding electron transport through the bridge. Perylenebisimide chromophores connected by various oligophenylene bridges are studied because their electron-transfer behavior can readily be monitored by following changes in the fluorescence intensity. We find dramatic switching of the IET behavior as the solvent polarity (dielectric constant) is increased. By combining steady-state and time-resolved fluorescence spectroscopy in a variety of solvents at multiple temperatures with standard theories of electron transfer, we determine parameters governing the IET behavior of these dimers, such as the electronic coupling through the bridges. We also deploy available ab initio quantum chemical methods to calculate the through-space component of the electronic coupling matrix element. Single-molecule investigations of the electron-transfer behavior also show that IET can be switched reversibly by a similar mechanism in an isolated individual molecule.

Journal Article↗
PubMed2003

Peptide-protein interactions: photoinduced electron-transfer within the preformed and encounter complexes of a designed metallopeptide and cytochrome c.

Photoinduced electron-transfer (ET) occurs between a negatively charged metallopeptide, [Ru(bpy)(2)(phen-am)-Cys-(Glu)(5)-Gly](3-) = RuCE(5)G, and ferricytochrome c = Cyt c. In the presence of Cyt c, the triplet state lifetime of the ruthenium metallopeptide is shortened, and the emission decays via biexponential kinetics, which indicates the existence of two excited-state populations of ruthenium peptides. The faster decay component displays concentration-independent kinetics demonstrating the presence of a preformed peptide-protein complex that undergoes intra-complex electron-transfer. Values of K(b) = (3.5 +/- 0.2) x 10(4) M(-1) and k(obs)(ET)= (2.7 +/- 0.4) x 10(6) s(-1) were observed at ambient temperatures. The magnitude of k(obs)(ET) decreases with increasing solvent viscosity, and the behavior can be fit to the expression k(obs)(ET) proportional to eta(-alpha) to give alpha = 0.59 +/- 0.05. The electron-transfer process occurring in the preformed complex is therefore gated by a rate-limiting configurational change of the complex. The slower decay component displays concentration-dependent kinetics that saturate at high concentrations of Cyt c. Analysis according to rapid equilibrium formation of an encounter complex that undergoes unimolecular electron-transfer yields K(b)' = (2.5 +/- 0.7) x 10(4) M(-1) and k(obs')(ET)= (7 +/- 3) x 10(5) s(-1). The different values of k(obs)(ET) and k(obs')(ET) suggest that the peptide lies farther from the heme when in the encounter complex. The value of k(obs')(ET) is viscosity dependent indicating that the reaction occurring within the encounter complex is also configurationally gated. A value of alpha = 0.98 +/- 0.14 is observed for k(obs')(ET), which suggests that the rate-limiting gating processes in the encounter complex is different from that in the preformed complex.

Binding Sites↗
PubMed2002

A single-molecule probe based on intramolecular electron transfer.

Detecting structure, dynamics, and chemical reactions at the single-molecule level represents the ultimate degree of sensitivity for sensing and imaging. There is a tremendous need to develop new molecular systems and methodology for single-molecule-based sensing. This work presents for the first time the single-molecule spectroscopy of a new molecular probe which uses an intramolecular electron transfer mechanism to detect binding, local structure, and interfacial processes. Moreover, we show how information about the interaction of these probes with their environment is obtained from an analysis of the intensity, duration and time-varying behavior of the single-molecule fluorescence.

Journal Article↗