Biomedical subjects

Tianquan Lian

Publications and source records attributed to Tianquan Lian.

8 recordsLinked to original sources

PubMed2006

Ultrafast photoinduced charge separation dynamics in polythiophene/SnO2 nanocomposites.

We present a study of photoinduced interfacial electron transfer (ET) dynamics of SnO2 nanocrystalline thin films sensitized by polythiophene derivatives (regioregular poly(3-hexylthiophene) (P3HT) and regiorandom poly(3-undecyl-2,2'-bithiophene) (P3UBT)). ET dynamics were measured by following the dynamics of injected electrons in SnO2 and polarons in the conjugated polymer using ultrafast mid-IR transient absorption spectroscopy. The rate of electron transfer from P3HT and P3UBT to SnO2 films was determined to occur on sub-picosecond time scale (120 +/- 20 fs). In P3HT/SnO2 composite, interchain charge transfer was found to compete with and reduce the quantum efficiency of interfacial electron transfer at high polymer loading. This interchain charge separation processes can be reduced in non-regioregular polymer or at low polymer loading levels.

Journal Article↗

PubMed2006

Vibrational relaxation of CN stretch of pseudo-halide anions (OCN-, SCN-, and SeCN-) in polar solvents.

The vibrational relaxation dynamics of pseudo-halide anions XCN- (X = O, S, Se) in polar solvents were studied to understand the effect of charge on solute-to-solvent intermolecular energy transfer (IET) and solvent assisted intramolecular vibrational relaxation (IVR) pathways. The T1 relaxation times of the CN stretch in these anions were measured by IR pump/IR probe spectroscopy, in which the 0-1 transition was excited, and the 0-1 and 1-2 transitions were monitored to follow the recovery of the ground state and decay of the excited state. For these anions in five solvents, H2O, D2O, CH3OH, CH3CN, and (CH3)2SO, relaxation rates followed the trend of OCN- > SCN- > SeCN-. For these anions and isotopes of SCN-, the relaxation rate was a factor of a few (2.5-10) higher in H2O than in D2O. To further probe the solvent isotope effect, the relaxation rates of S12C14N-, S13C14N-, and S12C15N- in deuterated methanols (CH3OH, CH3OD, CH3OH, CD3OD) were compared. Relaxation rate was found to be affected by the change of solvent vibrational band at the CN- stretching mode (CD3 symmetric stretch) and lower frequency regions, suggesting the presence of both direct IET and solvent assisted IVR relaxation pathways. The possible relaxation pathways and mechanisms for the observed trends in solute and solvent dependence were discussed.

Journal Article↗

PubMed2006

Electron-transfer dynamics from Ru polypyridyl complexes to In2O3 nanocrystalline thin films.

Photoinduced electron injection dynamics from Ru(dcbpy)(2)(X)(2) (dcbpy = 4,4'-dicarboxy-2,2'-bipyridine; X(2) = 2SCN(-), 2CN(-), and dcbpy; referenced as RuN3, Ru505, and Ru470) to In(2)O(3) nanocrystalline thin films were studied using ultrafast transient IR absorption spectroscopy. After 532 nm excitation of the adsorbates, the dynamics of electron injection from their excited states to In(2)O(3) were studied by monitoring the IR absorption of the injected electrons in the semiconductor. The injection kinetics were non-single-exponential. For samples exposed to air, the half rise times, defined as the time of 50% injection yield, were 5 +/- 0.8, 85 +/- 20, and >200 ps for RuN3, Ru505, and Ru470, respectively. For samples in pH 2 buffer, the corresponding half time for injection from these complexes became 6 +/- 1, 105 +/- 20, and 18 +/- 5 ps. The injection kinetics from RuN3 to In(2)O(3) was found to be similar to that to SnO(2). These kinetics traces showed a negligible <100 fs injection component and were very different from those to TiO(2). The dependences of the injection kinetics on adsorbate energetics and the nature of the semiconductors are discussed.

Journal Article↗

PubMed2006

Ultrafast excited-state dynamics in vitamin B12 and related cob(III)alamins.

Femtosecond transient IR and visible absorption spectroscopies have been employed to investigate the excited-state photophysics of vitamin B12 (cyanocobalamin, CNCbl) and the related cob(III)alamins, azidocobalamin (N3Cbl), and aquocobalamin (H2OCbl). Excitation of CNCbl, H2OCbl, or N3Cbl results in rapid formation of a short-lived excited state followed by ground-state recovery on time scales ranging from a few picoseconds to a few tens of picoseconds. The lifetime of the intermediate state is influenced by the sigma-donating ability of the axial ligand, decreasing in the order CNCbl > N3Cbl > H2OCbl, and by the polarity of the solvent, decreasing with increasing solvent polarity. The peak of the excited-state visible absorption spectrum is shifted to ca. 490 nm, and the shape of the spectrum is characteristic of weak axial ligands, similar to those observed for cob(II)alamin, base-off cobalamins, or cobinamides. Transient IR spectra of the upper CN and N3 ligands are red-shifted 20-30 cm(-1) from the ground-state frequencies, consistent with a weakened Co-upper ligand bond. These results suggest that the transient intermediate state can be attributed to a corrin ring pi to Co 3d(z2) ligand to metal charge transfer (LMCT) state. In this state bonds between the cobalt and the axial ligands are weakened and lengthened with respect to the corresponding ground states.

Hydroxocobalamin↗

PubMed2005

pH-dependent electron transfer from re-bipyridyl complexes to metal oxide nanocrystalline thin films.

Photoinduced interfacial electron transfer (ET) from molecular adsorbates to semiconductor nanoparticles has been a subject of intense recent interest. Unlike intramolecular ET, the existence of a quasicontinuum of electronic states in the solid leads to a dependence of ET rate on the density of accepting states in the semiconductor, which varies with the position of the adsorbate excited-state oxidation potential relative to the conduction band edge. For metal oxide semiconductors, their conduction band edge position varies with the pH of the solution, leading to pH-dependent interfacial ET rates in these materials. In this work we examine this dependence in Re(L(P))(CO)3Cl (or ReC1P) [L(P) = 2,2'-bipyridine-4,4'-bis-CH2PO(OH)2] and Re(L(A))(CO)3Cl (or ReC1A) [L(A) = 2,2'-bipyridine-4,4'-bis-CH2COOH] sensitized TiO2 and ReC1P sensitized SnO2 nanocrystalline thin films using femtosecond transient IR spectroscopy. ET rates are measured as a function of pH by monitoring the CO stretching modes of the adsorbates and mid-IR absorption of the injected electrons. The injection rate to TiO2 was found to decrease by 1000-fold from pH 0-9, while it reduced by only a factor of a few to SnO2 over a similar pH range. Comparison with the theoretical predictions based on Marcus' theory of nonadiabatic interfacial ET suggests that the observed pH-dependent ET rate can be qualitatively accounted for by considering the change of density of electron-accepting states caused by the pH-dependent conduction band edge position.

Journal Article↗

PubMed2005

Ultrafast electron transfer between molecule adsorbate and antimony doped tin oxide (ATO) nanoparticles.

Ultrafast transient IR spectroscopy has been used to examine the effect of doping on interfacial electron transfer (ET) dynamics in Re(dpbpy)(CO)(3)Cl (dpbpy = 4,4'-(CH(2)PO(OH)(2))2-2,2'-bipyridine) (ReC1PO(3)) sensitized ATO (Sb:SnO(2)) nanocrystalline thin films. In films consisting of particles with 0%, 2% and 10% Sb dopant, the rates of electron injection from the adsorbate excited state to ATO were independent of and the rates of the recombination increased with the doping level. The observed similar forward electron injection rates were attributed to negligible changes of available accepting states in the conduction band at the doping levels studied. The dependence of the recombination rate on conduction band electron density and a possible mechanism for the recombination process were discussed.

Journal Article↗

PubMed2005

Electron injection dynamics of Ru polypyridyl complexes on SnO2 nanocrystalline thin films.

Ultrafast infrared spectroscopy was utilized to investigate the electron-transfer dynamics from Ru(dcbpy)(2)(X)(2) complexes (dcbpy = 4,4'-dicarboxy-2,2'-bipyridine; X(2) = SCN(-), 2CN(-), and dcbpy; referenced as RuN3, Ru505, and Ru470, respectively) to nanocrystalline SnO(2) films. For both films exposed to air (dry) and submerged in a pH 2 buffer solution, all traces show biphasic dynamics with a small ultrafast component (less than 10%) and nonexponential slow component, indicating that most injection occurs from thermalized excited state of the dye. In the dry film, the injection rate becomes slower, comparing RuN3, Ru505, and Ru470, correlating with decreasing excited-state oxidation potentials in these dyes. However, the variation of injection rate with dye potential is less noticeable at pH 2. The possible reason for the different injection dynamics in these dyes and under different environments are discussed. These injection dynamics are also compared with those on TiO(2) and ZnO.

Journal Article↗

PubMed2005

Ultrafast electron transfer at the molecule-semiconductor nanoparticle interface.

Electron transfer across the molecule-semiconductor interface is a fundamental process that is relevant to many applications of nanoparticles, such as dye-sensitized solar cells and molecular electronics. This review summarizes recent progress in understanding electron transfer dynamics from molecular adsorbates to semiconductor nanoparticles. Photoexcitation of molecular adsorbates to their excited states is followed by electron injection into semiconductor nanoparticles. The products of electron injection (oxidized adsorbate and electrons in semiconductor) are monitored by their electronic and vibrational spectra, allowing direct measurement of injection rate. The dependence of injection rate on the properties of semiconductor nanoparticle, molecular adsorbate, intervening bridging and anchoring group, and interfacial environment are discussed and compared with Marcus theory of interfacial electron transfer.

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