The room-temperature fluorescence properties of DNA nucleoside and nucleotide aqueous solutions are studied by steady-state and time-resolved spectroscopy. The steady-state fluorescence spectra, although peaking in the near-UV region, are very broad, extending over the whole visible domain. Quantum yields are found to be mostly higher and the fluorescence decays faster than those reported in the literature. The fluorescence spectra of the 2‘-deoxynucleosides are identical to those of the 2‘-deoxynucleotides, with the exception of 2‘-deoxyadenosine, for which a difference in the spectral width is observed. The steady-state absorption and fluorescence spectra do not show any concentration dependence in the range 5 × 10-6 to 2 × 10-3 M. All fluorescence decays are complex and cannot be described by monoexponential functions. From the zero-time fluorescence anisotropies recorded at 330 nm, it is deduced that after excitation at 267 nm the largest modification in the electronic structure is exhibited by 2‘-deoxyguanosine. In the case of purines, the fluorescence decays and quantum yields are the same for 2‘-deoxynucleosides and 2‘-deoxynucleotides. In contrast, for pyrimidines, the fluorescence quantum yields of nucleotides are higher and the fluorescence decays slower as compared to those of the corresponding nucleosides showing that the phosphate moiety affects the excited-state relaxation.

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The relaxation dynamics of charge carriers in 4 nm CdS colloidal quantum dots are studied by means of picosecond time-resolved fluorescence and femtosecond transient absorption experiments. We also studied the effects of the adsorption of viologen derivatives as electron acceptors on the surface of these particles. From these experimental measurements, we reached a model of the electron-hole dynamics in these nanoparticles consistent with previous proposals. In particular, we have confirmed that the electron trapping in these particles is slower than the hole trapping (30 ps versus a few picoseconds). After excitation, rapid formation of an optical hole (bleach) within the lowest energy exciton (band gap) absorption region appears. The maximum of the bleaching band is red-shifted by 20 meV in 2.5 ps, and the bleach intensity recovers in 30 ps. Upon the adsorption of electron acceptors, the rate of the red shift of the optical hole is not affected while the bleach recovery time is reduced to a few picoseconds. This leads to the following conclusions:  (1) the shift in the bleach band results from hole trapping dynamics, and (2) the bleach recovery is rate limited by the electron trapping process in the CdS nanoparticles (30 ps) or by the hole trapping process (a few picoseconds) in the presence of the electron acceptors. The latter conclusion supports a previous proposal by Klimov et al., that the rate of the recovery in CdS nanoparticles is determined by the electron surface trapping process. The electron transfer to the viologen acceptors is found to be very efficient and takes place in 200−300 fs, which efficiently competes with surface trapping and electron-hole recombination processes and thus quenches both the band gap and the deep trap emissions.

The formation of thymine dimers in the single-stranded oligonucleotide, (dT)20, is studied at room temperature by laser flash photolysis using 266 nm excitation. It is shown that the (6-4) adduct is formed within 4 ms via a reactive intermediate. The formation of cyclobutane dimers is faster than 200 ns. The overall quantum yield for the (6-4) formation is (3.7 ± 0.3) × 10-3, and that of the cyclobutane dimers is (2.8 ± 0.2) × 10-2. No triplet absorption is detected, showing that either the intersystem crossing yield decreases by 1 order of magnitude upon oligomerization (<1.4 × 10-3) or the triplet state reacts with unit efficiency in less than 200 ns to yield cyclobutane dimers.

The spectroscopic properties of discotic hexa-alkylthiotriphenylenes are studied in solution and thin films and compared to those of hexa-alkyloxytriphenylenes. The solution properties are analyzed in the light of CS-INDO-CIPSI quantum chemistry calculations. The absorption maximum is assigned to the degenerate S 0 f S 4 transition. The fluorescence of the neat phases is attributed to weakly bound excimers. The phase transition leading from ordered to disordered columnar stacks induces an increase in the oscillator strength of the S 0 f S 1 transition and favors excimer formation. The influence of structural disorder on the properties of the delocalized states is rationalized by using various approximations within the frame of the exciton theory; three models for the calculation of the exciton coupling (point dipole, extended dipole, atomic transition charge distribution) are tested, short and long range interactions are considered, and the introduction of a dielectric constant is discussed. The best agreement between experimental and calculated absorption maxima is obtained using the atomic charge transition model. Off-diagonal disorder is correlated to structural disorder by changing the orientation and the position of the molecules within the aggregate. The case of degenerate molecular states is compared to that of nondegenerate ones. Orientational disorder has a dramatic effect on the energy and the localization of the upper eigenstate when molecular states are nondegenerate. Conversely, the properties of degenerate eigenstates are quite insensitive to orientational disorder. The magnitude of the off-diagonal disorder induced by positional disorder largely depends on the model used in the calculation of the exciton coupling. The results of the numerical calculations are in agreement with the small change observed in the neat phases absorption maxima upon a quasi one-dimensional melting of columnar stacks.

We report a near-field imaging study of colloidal gold nanocubes. This is accomplished through a photochemical imaging method in which molecular displacements are vectorial in nature, enabling sensitivity to the polarization of the optical near-field of the nanocubes. We analyze the confinement of both electromagnetic hot and "cold" spots with a resolution of λ/35 and emphasize the particularly high spatial confinement of cold spots. The concept of a cold spot complements the well-known electromagnetic hot spot but can have significant advantages. The application of the ultraconfined cold spots to high resolution imaging and spectroscopy is discussed.

We report on the angular distribution, polarization, and spectrum of the light emitted from an electrically controlled nanoscale light source. This nanosource of light arises from the local, low-energy, electrical excitation of localized surface plasmons (LSP) on individual gold nanoparticles using a scanning tunneling microscope (STM). The gold nanoparticles (NP) are chemically synthesized truncated bitetrahedrons. The emitted light is collected through the transparent substrate and the emission characteristics (angular distribution, polarization, and spectrum) are analyzed. These three observables are found to strongly depend on the lateral position of the STM tip with respect to the triangular upper face of the gold NP. In particular, the resulting light emission changes orientation when the electrical excitation via the STM tip is moved from the base to the vertex of the triangular face. On the basis of the comparison of the experimental observations with an analytical dipole model and finite-difference time-domain (FDTD) calculations, we show that this behavior is linked to the selective excitation of the out-of-plane and in-plane dipolar LSP modes of the NP. This selective excitation is achieved through the lateral position of the tip with respect to the symmetry center of the NP.

Cytosine methylation, which determines the hot spots for DNA photo-damage, is shown to induce a red-shift of the nucleoside absorption spectrum, making the chromophore more vulnerable to solar radiation, and a tenfold increase of the fluorescence lifetime, making excited statereactions more probable. A femtosecond investigation of the excited state deactivation reveals a quite complex mechanism.