Nonradiative decay mechanism of fluoren-9-ylidene malononitrile ambipolar derivatives.

We report recent results on the nonradiative decay (NRD) of fluoren-9-ylidene malononitrile (FM) ambipolar derivatives (FMDs). 2,7- and 3,6-disubstituted FMDs present distinctive photophysics. Charge separation was found dominant for excited state relaxation.

Carbazole-based cyano-stilbene highly fluorescent microcrystals.

Aggregation-induced enhanced emission (AIEE) is reported for 1-cyano-trans-1,2-bis-(4-carbazolyl)phenylethylene (CN-CPE). The weak luminescence of dilute CN-CPE solutions is enhanced upon aggregate formation into 2-3 μm sized crystals. In contrast to general observations, crystal formation of CN-CPE causes a blue-shift in emission and enhances the intensity.

[Effects of erlong zuoci pills and its effective disassembled prescriptions on gentamycin induced hair cell apoptosis].

Objective: To investigate the effects of erlong zuoci (ELZC) pills and its disassembled prescriptions (Shudi-huang-Zexie group and Zexie group) on the enzymatic activity and protein expression changes of the key apoptosis molecules in the gentamycin injured hair cells.

Method: The model of gentamycin induced ototoxicity in mice cochlear primary cultures was copied. Cochlear organotypic cultures of postnatal day 3-5 (P3-P5) mice were treated with gentamycin alone or in combination with ELZC pills, Shudihuang-Zexie group or Zexie group respectively.

Photopolymerization of conductive polymeric metal nanoparticles.

5-Mercapto-2,2'-bithiophene functionalized metal nanoparticles BTSMs [M: copper (Cu), silver (Ag), and gold (Au)] of different diameters (2-8 nm) were synthesized. Conductive polymeric metal nanoparticles were formed from BTSM by UV irradiation. The photopolymerization mechanism was investigated using transient absorption measurements.

Photoinduced hole transfer forming polymer quantum dot nanocomposites.

The study of hole transfer from CdSe QD core to ligands under visible light irradiation and conductive polymer-QD composites formation without conventional photoinitiator.

Photochemical synthesis of 2,3,9,10-tetrabromopentacene: its unusual photodimerization.

The photogeneration of 2,3,9,10-tetrabromopentacene from its precursor dione by photodecarbonylation was investigated. An unusual photodimer, 3,3',9,9',10,10'-hexabromo-2,2'-bipentacene, is produced.

Alpha-bond dissociation of p-phenylbenzoyl derivatives in the higher triplet excited state studied by two-color two-laser flash photolysis.

Photochemical properties in the lowest singlet and triplet excited states (S(1) and T(1)) and in the higher triplet excited states (T(n)) of p-phenylbenzoyl derivatives (PB-X) having C-O and C-S bonds were investigated in solution using a stepwise two-color two-laser flash photolysis technique. PB-Xs (X = OPh and SPh as a leaving group) undergo alpha-bond dissociation in the S(1) state, while the C-O bonds in PB-OH and -OMe were stable upon the 266-nm laser flash photolysis. The T(1)(pi,pi*) states of PB-X were efficiently produced during the 355-nm laser flash photolysis of PB-X in the presence of benzophenone as a triplet sensitizer.

Isomer restriction on a nanoparticle surface and enhanced blue emission.

5-Mercapto-2,2'-bithiophene (BTSH) functionalized copper (Cu), silver (Ag), and gold (Au) nanoparticles (NPs) of various diameters have been synthesized. Emission with a peak around 455 nm is detected on irradiation with UV light. This emission, however, disappears upon photopolymerization of the NPs.

Gold nanoparticle photosensitized radical photopolymerization.

We report the photopolymerization of an acrylic monomer using thiol-stabilized gold nanoparticles (AuNPs) and [4-[(octyloxy)phenyl] phenyl] iodonium hexafluoroantimonate (OPPI) as photoinitiator and coinitiator, respectively. Polymerization occurred only when the AuNPs, in the presence of the iodonium salt, were irradiated at the particle plasmonic absorption region (lambda>450 nm). The AuNPs activate the coinitiator by intermolecular electron transfer since OPPI has no absorption in the visible region.

Photopolymerization of metal nanoparticles on multiwall carbon nanotubes.

A facile method for the functionalization of multiwall carbon nanotubes (MWCNT) by photopolymerization of 5-mercapto-2,2'-bithiophene modified metal (Au or Ag) nanoparticles on the surface of the MWCNT is developed.

Photodecomposition profiles of beta-bond cleavage of phenylphenacyl derivatives in the higher triplet excited states during stepwise two-color two-laser flash photolysis.

Photochemical properties of p-phenylphenacyl derivatives (PP-X) having C-halide, C-S, and C-O bonds in the lowest (T 1) and higher (T n ) triplet excited states were investigated in solution by using single-color and stepwise two-color two-laser flash photolysis techniques. PP-Xs (X = Br, SH, and SPh) undergo beta-bond dissociation in the lowest singlet excited states (S 1) while the C-X bonds of other PP-Xs are stable upon 266-nm laser photolysis. The T 1(pi,pi*) states of PP-X were efficiently produced during 355-nm laser photolysis of benzophenone as a triplet sensitizer.

Carbazole-based donor-acceptor compounds: highly fluorescent organic nanoparticles.

Carbazole-based donor-acceptor compounds 1,2-dicyano-trans-1,2-bis-4-(carbazolyl)phenylethylene (1) and 1,2-dicyano-trans-1,2-bis-4-(3,6-di-tert-butylcarbazolyl)phenylethylene (2) were synthesized. 1 and 2 show negative solvatochromic absorption behavior, but show both positive and negative solvatochromic behavior in the fluorescence spectra. In a water/THF mixture, 1 as well as 2 aggregate into 50-150 nm nanoparticles.

Bimolecular hole transfer from the trimethoxybenzene radical cation in the excited state.

Bimolecular hole transfer quenching of the 1,3,5-trimethoxybenzene radical cation (TMB*+) in the excited state (TMB*+*) by hole quenchers (Q) such as biphenyl (Bp), naphthalene (Np), anisole (An), and benzene (Bz) with higher oxidation potentials than that of TMB was directly observed during the two-color two-laser flash photolysis at room temperature. From the linear relationships between the inverse of the transient absorption changes of TMB*+ during the second 532-nm laser excitation versus the inverse of the concentration of Q, the rate constant of the hole transfer from TMB*+* to Q was estimated to be (8.5 +/- 0.

One-electron oxidation of alcohols by the 1,3,5-trimethoxybenzene radical cation in the excited state during two-color two-laser flash photolysis.

One-electron oxidation of alcohols such as methanol, ethanol, and 2-propanol by 1,3,5-trimethoxybenzene radical cation (TMB*+) in the excited state (TMB*+*) was observed during the two-color two-laser flash photolysis. TMB*+ was formed by the photoinduced bimolecular electron-transfer reaction from TMB to 2,3,5,6-tetrachlorobenzoquinone (TCQ) in the triplet excited-state during the first 355-nm laser flash photolysis. Then, TMB*+* was generated from the selective excitation of TMB*+ during the second 532 nm laser flash photolysis.

Intermolecular electron transfer from excited benzophenone ketyl radical.

The electron transfer from the benzophenone ketyl radical in the excited state (BPH(.-)(D(1))) to several quenchers (Qs) was investigated using nanosecond/picosecond two-color two-laser flash photolysis and nanosecond/nanosecond two-color two-laser flash photolysis. The electron transfer from BPH(.

C-O-bond cleavage of esters with a naphthyl group in the higher triplet excited state during two-color two-laser flash photolysis.

A C-O-bond cleavage of esters having a naphthyl group, NpCO-OR and RCO-ONp (Np=alpha- and beta-naphthyl ((alpha)Np and (beta)Np, respectively), R=Ph and Me), was found during the two-color two-laser flash photolysis in acetonitrile. The C-O-bond cleavage occurred when NpCO-OR and RCO-ONp were excited to the singlet excited states (S1). On the other hand, no reaction occurred from the lowest triplet excited states (T1).

Solvent effect on the deactivation processes of benzophenone ketyl radicals in the excited state.

The solvent effects on ketyl radicals of benzophenone derivatives (BPD) in the excited state (BPDH*(D1)) were investigated. Absorption and fluorescence spectra of BPDH*(D1) in various solvents were measured using nanosecond-picosecond two-color two-laser flash photolysis. The fluorescence peaks from BPDH*(D1) showed a shift due to the dipole-dipole interaction with the solvent molecules.

Properties and reactivity of xanthyl radical in the excited state.

The properties and reactivity of the 9-xanthyl radical (X(*)) in the doublet excited state (X(*)(D(1))) were investigated using nanosecond-picosecond two-color two-laser flash photolysis. The absorption and fluorescence spectra of X(*)(D(1)) were observed for the first time. The reactivity of X(*)(D(1)) toward a series of halogen donors and electron acceptors in acetonitrile and 1,2-dichloroethane (DCE) was investigated.

Photodissociation of naphthalene dimer radical cation during the two-color two-laser flash photolysis and pulse radiolysis-laser flash photolysis.

Photodissociation of naphthalene (Np) dimer radical cation (Np2*+) to give naphthalene radical cation (Np*+) and Np and the subsequent regeneration of Np2*+ by the dimerization of Np*+ and Np were directly observed during the two-color two-laser flash photolysis in solution at room temperature. When Np2*+ was excited at the charge-resonance (CR) band with the 1064-nm laser, the bleaching and recovery of the transient absorption at 570 and 1000 nm, assigned to the local excitation (LE) and CR bands of Np2*+, respectively, were observed together with the growth and decay of the transient absorption at 685 nm, assigned to Np*+. The dissociation of Np2*+ proceeds via a one-photon process within the 5-ns laser flash to give Np*+ and Np in the quantum yield of 3.

Inhibition of the formation and decay of stilbene core radical cations by the dendron during the photoinduced electron transfer.

Formation and decay processes of stilbene core radical cation (ST*+) during the photoinduced electron transfer have been studied for a series of stilbene bearing benzyl ether-type dendrons (D). ST*+ and the radical cation of peripheral dendron (D*+) were generated by intermolecular hole transfer from biphenyl radical cation, which was generated from photoinduced electron transfer from biphenyl to the singlet-excited 9,10-dicyanoanthracene in a mixture of acetonitrile and 1,2-dichloroethane (3:1). An intramolecular dimer radical cation of benzyl groups at the terminal of stilbene dendrimer was indicated as a hole trapping site.

Photophysical properties of oligo(2,3-thienyleneethynylene)s.

Photophysical properties of oligo(2,3-thienyleneethynylene)s (nTE, n denotes the number of thiophene rings, n = 2, 3) in benzene were investigated using steady-state, time-resolved fluorescence, and transient absorption spectroscopies. For 2TE, generation of the radiative S2 and nonradiative S1 states was confirmed. Upon excitation, the S2 state was initially generated and deactivated to the S1 state within 10 ps.

Dual electron transfer pathways from 4,4'-dimethoxybenzophenone ketyl radical in the excited state to parent molecule in the ground state.

Dual intermolecular electron transfer (ELT) pathways from 4,4'-dimethoxybenzophenone (1) ketyl radical (1H*) in the excited state [1H*(D1)] to the ground-state 4,4'-dimethoxybenzophenone [1(S0)] were found in 2-methyltetrahydrofuran (MTHF) by observing bis(4-methoxyphenyl)methanol cation (1H+) and 4,4'-dimethoxybenzophenone radical anion (1*-) during nanosecond-picosecond two-color two-laser flash photolysis. ELT pathway I involved the two-photon ionization of 1H* following the injection of electron to the solvent. The solvated electron was quickly trapped by 1(S0) to produce 1*-.

C-O bond cleavage of benzophenone substituted by 4-CH2OR (R = C6H5 and CH3) with stepwise two-photon excitation.

The C-O bond cleavage from benzophenone substituted with 4-CH2OR (p-BPCH2OR, 1-3), such as p-phenoxymethylbenzophenone (1, R= C6H5) and p-methoxymethylbenzophenone (2, R= CH3), occurred by a stepwise two-photon excitation during two-color, two-laser flash photolysis. On the other hand, no C-O bond cleavage occurred from p-hydroxymethylbenzophenone (3, R = H). The first 355-nm laser excitation of 1-3 generates p-BPCH2OR in the lowest triplet excited state (T1) which has an absorption at 532 nm.

Significant effects of substituents on substituted naphthalenes in the higher triplet excited state.

Substituent effect on the lifetimes of a series of substituted naphthalenes (Np) in the higher triplet excited state (Tn) was studied with transient absorption measurements using the two-color two-laser flash photolysis technique. Lifetimes of Np(Tn) in cyclohexane solution were determined from the triplet energy transfer quenching by carbon tetrachloride to be 0.98-63 ps.