Solvent-Induced Aggregation of Self-Assembled Copper-Cysteine Nanoparticles Reacted with Glutathione: Enhancing Linear and Nonlinear Optical Properties.

Copper-thiolate self-assembly nanostructures are a unique class of nanomaterials because of their interesting properties such as hierarchical structures, luminescence, and large nonlinear optical efficiency. Herein, we synthesized biomolecule cysteine (Cys) and glutathione (GSH) capped sub-100 nm self-assembly nanoparticles (Cu-Cys-GSH NPs) with red fluorescence. The as-synthesized NPs show high emission enhancement in the presence of ethanol, caused by the aggregation-induced emission. We correlated the structure and optical properties of Cu-Cys-GSH NPs by measuring the mass, morphology, and surface charge as well as their two-photon excited fluorescence cross-section (σ2PEPL), two-photon absorption cross-section (σTPA) and first hyperpolarizability (ß) of Cu-Cys-GSH NPs in water and water-ethanol using near-infrared wavelength. We found a high ß value as (77 ± 10) × 10-28 esu (in water) compared to the reference medium water. The estimated values of σ2PEPL and σTPA are found to be (13 ± 2) GM and (1.4 ± 0.2) × 104 GM, respectively. We hope our investigations of linear and nonlinear optical properties of copper-thiolate self-assemblies in water and its solvent-induced aggregates will open up new possibilities in designing self-assembled systems for many applications including sensing, drug delivery, and catalysis.

Combining second harmonic generation and multiphoton excited photo-luminescence to investigate TiO2 nanoparticle powders.

Disentangling Second Harmonic Generation (SHG) and Multiphoton Excited Photoluminescence (MEPL) signals in microscopy experiments is not an easy task. Two methods have been so far proposed based either on a time domain or a spectral domain analysis of the collected signals. In this report, a new method based on polarization discrimination is proposed to separate these SHG and MEPL contributions. In order to demonstrate this operation, intensity depth profiles are recorded for an anatase titanium dioxide powder consisting of 22 nm diameter nanoparticles using ultrafast femtosecond laser excitation. Polarization analysis of these intensity depth profiles is therefore performed and demonstrates a polarization angle shift for the SHG intensity contribution as compared to the MEPL one, allowing for the discrimination of the two SHG and MEPL contributions. The fundamental beam is set at two different wavelengths in order to provide a SHG photon energy above and below the anatase TiO2 band-gap of 3.2 eV, leading to a change in the relative intensity weight and a spectral shift between the SHG and MEPL contributions. This operation further demonstrates the potential of the method when the spectral domain disentangling cannot be performed. SHG profiles are by far narrower than those of MEPL. This study where both SHG and MEPL contributions are observed offers perspectives in photonics of powder materials as the different origin and properties of the two processes can be separated.

Hyper Rayleigh scattering from DNA nucleotides in aqueous solution.

Nucleotides are organic compounds consisting of a phosphate group, a nitrogenous base, namely adenine (A), thymine (T), cytosine (C), or guanine (G), and a sugar, here deoxyribose. The magnitude of the first hyperpolarizability ß of these four DNA nucleotides was determined in aqueous solution with the nonlinear optical technique of hyper rayleigh scattering under non resonant conditions at a fundamental wavelength of 800 nm. The smallest value is found to be 1.67 ± 0.15 × 10-30 esu for thymidine-5'-monophosphate and the highest is 1.76 ± 0.16 × 10-30 esu for 2'-guanosine-5'-monophosphate. Polarization resolved studies were also performed to question the symmetry of the first hyperpolarizability tensor and access the ratio of some elements of the first hyperpolarizability tensor. These experimental results were then compared to the theoretical values of these first hyperpolarizabilities obtained with the density functional theory at the level of the PCM-B3LYP/6-31G+(d) basis and taking into account the solvent.

Hyper-Rayleigh scattering of adenine, thymine, and cytosine in neat water.

The first hyperpolarizabilities of the DNA bases thymine and cytosine were determined by hyper-Rayleigh scattering in neat water despite their low solubility. Due to the low intensity levels collected, count statistics were performed instead of the standard dilution procedure. The first hyperpolarizabilities were found to be ßThymine = (2.99 ± 0.44) × 10-30 esu for thymine and ßCytosine = (3.35 ± 0.21) × 10-30 esu for cytosine. Due to its weak solubility, only an upper limit ßAdenine < (1.82 ± 0.10) × 10-30 esu could be set for adenine. The first hyperpolarizability of guanine could not be measured because of its very weak solubility. Theoretical static and 800 nm dynamic first hyperpolarizability tensor elements were also computed with Gaussian 09 for comparison.

Revival of femtosecond laser plasma filaments in air by a nanosecond laser.

Short lived plasma channels generated through filamentation of femtosecond laser pulses in air can be revived after several milliseconds by a delayed nanosecond pulse. Electrons initially ionized from oxygen molecules and subsequently captured by neutral oxygen molecules provide the long-lived reservoir of low affinity allowing this process. A Bessel-like nanosecond-duration laser beam can easily detach these weakly bound electrons and multiply them in an avalanche process. We have experimentally demonstrated such revivals over a channel length of 50 cm by focusing the nanosecond laser with an axicon.

Electric events synchronized with laser filaments in thunderclouds.

We investigated the possibility to trigger real-scale lightning using ionized filaments generated by ultrashort laser pulses in the atmosphere. Under conditions of high electric field during two thunderstorms, we observed a statistically significant number of electric events synchronized with the laser pulses, at the location of the filaments. This observation suggests that corona discharges may have been triggered by filaments.

Kilometer-range nonlinear propagation of femtosecond laser pulses.

Ultrashort, high-power laser pulses propagating vertically in the atmosphere have been observed over more than 20 km using an imaging 2-m astronomical telescope. This direct observation in several wavelength bands shows indications for filament formation at distances as far as 2 km in the atmosphere. Moreover, the beam divergence at 5 km altitude is smaller than expected, bearing evidence for whole-beam parallelization about the nonlinear focus. We discuss implications for white-light Lidar applications.

Non-linear optical properties of gold quantum clusters. The smaller the better.

By developing a new method for synthesizing atomically monodisperse Au15 nanoclusters stabilized with glutathione molecules and using the current state-of-the-art methods for synthesizing monodisperse protected Au25 nanoclusters, we investigated their nonlinear optical (NLO) properties after two-photon absorption. The two-photon emission spectra and the first hyperpolarizabilities of these particles were obtained using, in particular, a hyper-Rayleigh scattering technique. The influence on NLO of the excitation wavelength, the size as well as the nature of the ligands is also explored and discussed. Au15, the smallest stable thiolated gold nanocluster, presents remarkable nonlinear properties with respect to two-photon processes. The two-photon absorption cross-section at 780 nm for Au15 is ∼65,700 GM. This experimental cross-section value points to a quantum yield for two-photon emission of about 3 × 10(-7) at 475 nm for Au15. The first hyperpolarizability ß for Au15 clusters (509 × 10(-30) esu), as compared to Au25 clusters (128 × 10(-30) esu), is larger considering the difference in the number of gold atoms. Also, 10(30) ß per atom values reported for Au15 and Au25 clusters are more than two orders of magnitude larger than the values reported for Au NPs in the size range 10-50 nm, outlining the quantum cluster regime.

Sonographic probing of laser filaments in air.

The acoustic wave emitted from the plasma channel associated with a filament induced by a femtosecond laser pulse in air was detected with a microphone. This sonographic detection provides a new method to determine the length and the spatial profile of the free-electron density of a filament. The acoustic wave is emitted owing to the expansion of the gas in the filament, which is heated through collisions with high-energy photoelectrons generated by multiphoton ionization. Compared with other methods, the acoustic detection is simpler, more sensitive, and with higher spatial resolution, making it suitable for field measurements over kilometer-range distances or laboratory-scale studies on the fine structure of a filament.