Laser photodissociation of ketene at 230 nm

Abstract˜1˜1 Ketene in a molecular beam is excited at the onset of its X A ™ B B absorption band by laser light at 230 nm. The For the latter, the PST calculations lead to an average rotational energy in CO which is not compatible with the measured value, thus suggesting that this channel does not represent an important contribution to the dissociation process. q 1998 Elsevier Science B.V. All rights reserved

Experimental study of the structural effect on the nanosecond nonlinear optical response of O-doped polycyclic aromatic hydrocarbons (PAHs)

The nonlinear optical response of some O-doped PAHs is systematically investigated in the present work aiming to understand the influence of structural effects on their nonlinear optical response. In that view, the third-order nonlinear optical properties of these PAHs were measured under 4 ns, visible (532 nm) and infrared (1064 nm) laser excitation. The O-doped PAHs were found exhibiting large saturable absorption and negative sign nonlinear refraction under visible excitation, both increasing with the addition of naphtalene units and with the number of O-atoms. Their nonlinear optical response was found to be negligible under infrared excitation. Similar measurements performed on thin films of these PAHs have shown that they maintain their large nonlinear optical response even in solid state, confirming their high potential for opto-electronic and photonic applications

Tailoring colors by O-annulation of polycyclic aromatic hydrocarbons

The synthesis of O-doped polyaromatic hydrocarbons, in which two polycyclic aromatic hydrocarbon subunits are bridged through one or two O atoms, has been achieved. This includes high-yielding ring-closure key steps that, depending on the reaction conditions, yield the formation of either furanyl or pyranopyranyl linkages through intramolecular C-O bond formation. Comprehensive photophysical measurements in solution showed that these molecules feature exceptionally high emission yields and tunable absorption properties throughout the UV-vis spectral region. Electrochemical investigations showed that in all cases the O-annulation increases the electron donor capabilities by raising the HOMO energy level with the LUMO energy level being less affected. Moreover, third-order NLO measurements of solutions or thin films containing the dyes displayed very good second hyperpolarizibility values. Importantly, PMMA films containing the pyranopyranyl derivatives displayed weak linear absorption and NLO absorption compared to the nonlinearity and NLO refraction, respectively, revealing to be exceptional organic materials for photonic devices

[60]Fullerene\u2013porphyrin [n]pseudorotaxanes: self-assembly, photophysics and third-order NLO response

By means of different spectroscopic techniques, we investigate a novel series of porphyrin derivatives (H2TPP), connected to dibenzo-24-crown-8 (DB24C8) moieties, which undergo self-assembly with different methano[60]fullerene units bearing dibenzylammonium (DBA) cations. The formation of both [2] and [3]pseudorotaxanes was proved by means of NMR, UV-Vis-NIR absorption and emission spectroscopies. With the support of molecular modelling studies, spectroscopic investigations showed the presence of a secondary interaction between the porphyrin and the C60 chromophores leading to the formation of different types of \u2018\u2018face-to-face\u2019\u2019 assemblies. Remarkably, investigations of the non-linear optical response of these supramolecular systems showed that individual porphyrin and fullerene derivatives exhibit significantly lower second hyperpolarizability values when compared to their pseudorotaxanes functionalised counterparts. This proves that this class of supramolecular materials possesses relevant NLO response, which strongly depends on the structural arrangement of the chromophores in solution. Introductio

Solvent Molding of Organic Morphologies Made of Supramolecular Chiral Polymers

12sihe self-assembly and self-organization behavior of uracil-conjugated enantiopure (R)- or (S)-1,1'-binaphthyl-2,2'-diol (BINOL) and a hydrophobic oligo(p-phenylene ethynylene) (OPE) chromophore exposing 2,6-di(acetylamino)pyridine termini are reported. Systematic spectroscopic (UVvis, CD, fluorescence, NMR, and SAXS) and microscopic studies (TEM and AFM) showed that BINOL and OPE compounds undergo triple H-bonding recognition, generating different organic nanostructures in solution. Depending on the solvophobic properties of the liquid media (toluene, CHCl3, CHCl3/CHX, and CHX/THF), spherical, rod-like, fibrous, and helical morphologies were obtained, with the latter being the only nanostructures expressing chirality at the microscopic level. SAXS analysis combined with molecular modeling simulations showed that the helical superstructures are composed of dimeric double-cable tape-like structures that, in turn, are supercoiled at the microscale. This behavior is interpreted as a consequence of an interplay among the degree of association of the H-bonded recognition, the vapor pressure of the solvent, and the solvophobic/solvophilic character of the supramolecular adducts in the different solutions under static and dynamic conditions, namely solvent evaporation conditions at room temperature.partially_openopenĐorđević, Luka; Marangoni, Tomas; Miletić, Tanja; Rubio-Magnieto, Jenifer; Mohanraj, John; Amenitsch, Heinz; Pasini, Dario; Liaros, Nikos; Couris, Stelios; Armaroli, Nicola; Surin, Mathieu; Bonifazi, DavideĐorđević, Luka; Marangoni, Tomas; Miletic, Tanja; Rubio Magnieto, Jenifer; Mohanraj, John; Amenitsch, Heinz; Pasini, Dario; Liaros, Nikos; Couris, Stelios; Armaroli, Nicola; Surin, Mathieu; Bonifazi, David

Sulfur Detection in Soil by Laser Induced Breakdown Spectroscopy Assisted by Multivariate Analysis

Laser-induced breakdown spectroscopy (LIBS) is used for the detection and determination of sulfur content in some organic soil samples. The most suitable sulfur spectral lines for such tasks were found to occur in the vacuum ultraviolet (VUV) spectral region and they were used for the construction of calibration curves. For the analysis, both univariate and multivariate statistical models were employed. The results obtained by the different analysis techniques are evaluated and compared. The present study demonstrates both the applicability and efficiency of LIBS for fast sulfur detection in soil matrices when aided by multivariate analysis methods improving the accuracy and extending the potential use of LIBS in such applications

Olive Oils Classification via Laser-Induced Breakdown Spectroscopy

The classification of olive oils and the authentication of their geographic origin are important issues for public health and for the olive oil market and related industry. The development of fast, easy to use, suitable for on-line, in-situ and remote operation techniques for olive oils classification is of high interest. In the present work, 36 olive oils from different places in Crete, Greece, are studied using a laser-based technique, Laser-Induced Breakdown Spectroscopy (LIBS), assisted by machine learning algorithms, aiming to classify them in terms of their geographical origin. The excellent classification results obtained demonstrate the great potential of LIBS, which is further extended by the use of machine learning

Tailoring the Nonlinear Optical Response of Some Graphene Derivatives by Ultraviolet (UV) Irradiation

In the present work the impact of in situ photoreduction, by means of ultraviolet (UV) irradiation, on the nonlinear optical response (NLO) of some graphene oxide (GO), fluorographene (GF), hydrogenated fluorographene (GFH) and graphene (G) dispersions is studied. In situ UV photoreduction allowed for the extended modification of the degree of functionalization (i.e., oxidization, fluorination and hydrogenation), leading to the effective tuning of the corresponding sp2/sp3 hybridization ratios. The nonlinear optical properties of the studied samples prior to and after UV irradiation were determined by means of the Z-scan technique using visible (532 nm), 4 ns laser excitation, and were found to change significantly. More specifically, while GO’s nonlinear optical response increases with irradiation time, GF and GFH present a monotonic decrease. The graphene dispersions’ nonlinear optical response remains unaffected after prolonged UV irradiation for more than an hour. The present findings demonstrate that UV photoreduction can be an effective and simple strategy for tuning the nonlinear optical response of these graphene derivatives in a controllable way, resulting in derivatives with custom-made responses, thus more suitable for different photonic and optoelectronic applications

N-doped graphene and N-doped graphene acid: Heteroatom doping for very efficient broad-band optical limiting performance from UV to NIR

The present work reports on the exceptional optical limiting performance of some recently synthesized nitrogen-doped graphene derivatives (NGs) by substitutional heteroatom doping. In particular, the optical limiting performance of NGs having different nitrogen contents and some NG-based quantum dots is investigated in a broad-band spectral range, from 355 to 1850 nm, using 4 ns laser pulses. The obtained results show that the present N-doped graphene derivatives exhibit very efficient broad-band optical limiting performance, attaining record low values of optical limiting onset (OLon), in particular for NIR wavelengths, significantly lower than those of other previously studied graphene derivatives and other families of benchmark materials for optical limiting. The present results demonstrate that tuning the N-doping of graphene acid is a very powerful and efficient strategy for the enhancement of the OL action of graphene, rendering it the strongest currently known optical limiting material, improving dramatically its potential for various optoelectronic and photonic applications.Web of Science12633143451433