Dinitrogen release from arylpentazole: A picosecond time-resolved infrared, spectroelectrochemical, and DFT computational study

p-(Dimethylamino)phenyl pentazole, DMAP-N5 (DMAP = Me2N−C6H4), was characterized by picosecond transient infrared spectroscopy and infrared spectroelectrochemistry. Femtosecond laser excitation at 310 or 330 nm produces the DMAP-N5 (S1) excited state, part of which returns to the ground state (τ = 82 ± 4 ps), while DMAP-N and DMAP-N3 (S0) are generated as double and single N2-loss photoproducts with η ≈ 0.14. The lifetime of DMAP-N5 (S1) is temperature and solvent dependent. [DMAP-N3]+ is produced from DMAP-N5 in a quasireversible, one-electron oxidation process (E1/2 = +0.67 V). Control experiments with DMAP-N3 support the findings. DFT B3LYP/6-311G** calculations were used to identify DMAP-N5 (S1), DMAP-N3 +, and DMAP-N in the infrared spectra. Both DMAP-N5 (S1) and [DMAP-N5]+ have a weakened N5 ring structure.

Direct probing of photoinduced electron transfer in a self- assembled biomimetic [2Fe2S]-hydrogenase complex using ultrafast vibrational spectroscopy

A pyridyl-functionalized diiron dithiolate complex, [μ-(4-pyCH2−NMI-S2)Fe2(CO)6] (3, py = pyridine(ligand), NMI = naphthalene monoimide) was synthesized and fully characterized. In the presence of zinc tetraphenylporphyrin (ZnTPP), a self-assembled 3·ZnTPP complex was readily formed in CH2Cl2 by the coordination of the pyridyl nitrogen to the porphyrin zinc center. Ultrafast photoinduced electron transfer from excited ZnTPP to complex 3 in the supramolecular assembly was observed in real time by monitoring the ν(CO) and ν(CO)NMI spectral changes with femtosecond time-resolved infrared (TRIR) spectroscopy. We have confirmed that photoinduced charge separation produced the monoreduced species by comparing the time-resolved IR spectra with the conventional IR spectra of 3•− generated by reversible electrochemical reduction. The lifetimes for the charge separation and charge recombination processes were found to be τCS = 40 ± 3 ps and τCR = 205 ± 14 ps, respectively. The charge recombination is much slower than that in an analogous covalent complex, demonstrating the potential of a supramolecular approach to extend the lifetime of the chargeseparated state in photocatalytic complexes. The observed vibrational frequency shifts provide a very sensitive probe of the delocalization of the electron-spin density over the different parts of the Fe2S2 complex. The TR and spectro-electrochemical IR spectra, electron paramagnetic resonance spectra, and density functional theory calculations all show that the spin density in 3•− is delocalized over the diiron core and the NMI bridge. This delocalization explains why the complex exhibits low catalytic dihydrogen production even though it features a very efficient photoinduced electron transfer. The ultrafast porphyrin-to-NMIS2−Fe2(CO)6 photoinduced electron transfer is the first reported example of a supramolecular Fe2S2-hydrogenase model studied by femtosecond TRIR spectroscopy. Our results show that TRIR spectroscopy is a powerful tool to investigate photoinduced electron transfer in potential dihydrogen-producing catalytic complexes, and that way to optimize their performance by rational approaches.

Degenerate Two-Photon Absorption in All-Trans Retinal: Nonlinear Spectrum and Theoretical Calculations

In this work we investigate the degenerate two-photon absorption spectrum of all-trans retinal ill ethanol employing the Z-scan technique with femtosecond pulses, The two-photon absorption (2PA) spectrum presents a monotonous increase as the excitation wavelength approaches the one-photon absorption band and it peak at 790 nm. We attribute the 2PA hand to the mixing of states (1)B(u)+-like and vertical bar S(1)>, which are strongly allowed by one- and two-photon, respectively. We modeled the 2PA spectrum by using the sum-over-states approach and obtained spectroscopic parameters of the electronic transitions to vertical bar S >, vertical bar S(2)> (""(1)Bu(+)""), vertical bar S(3)>, and vertical bar S(4)> singlet-excited states. The results were compared with theoretical predictions of one- and two-photon transition calculations using the response Functions formalism within the density functional theory framework with the aid of the CAM-B3LYP functional.

Laser microstructuring of azopolymers via surface relief gratings: controlling hydrophobicity

In this paper the large-scale mass transport mechanism is used to microstructure azopolymeric films, aiming at controllable hydrophobic surfaces. Using an Ar(+) laser with intensity of 70 mW/cm(2), we produced egg-crate-like surfaces with periods from 1.0 to 3.5 mu m that present distinct wetting properties. The static contact angle of water was measured on the microstructured surfaces, and the results revealed an increase of approximately 9 degrees for a surface pattern period of 2 mu m. Our results indicate the use of the microstructuring method described here for the fabrication of devices with controllable hydrophobicity.

Excited-state absorption spectroscopy in oxidized Cytochrome c

This work reports on the excited-state absorption spectrum of oxidized Cytochrome c (Fe(3+)) dissolved in water, measured with the Z-scan technique with femtosecond laser pulses. The excited-state absorption cross-sections between 460 and 560 nm were determined with the aid of a three-energy-level model. Reverse saturable absorption was observed below 520 nm, while a saturable absorption process occurs in the Q-band, located around 530 nm. Above 560 nm, a competition between saturable absorption and two-photon absorption was inferred. These results show that Cytochrome c presents distinct nonlinear behaviors, which may be useful to study electron transfer chemistry in proteins by one- and two-photon absorption. In addition, owing to these nonlinear optical features, this molecule may be employed in applications involving photodynamics therapy and saturable absorbers. (C) 2009 Elsevier B.V. All rights reserved.

Excited State Absorption of Doped and Undoped Polyanyline

Polyaniline is a conducting polymer with appealing electrical and optical properties, arising from the -conjugation along the polymer backbone. The understanding of its excited state absorption is of prime importance for designing and fabricating optical devices. Here, we report on the study of the excited state absorption of doped and undoped PANI by using femtosecond pulses in the spectral range from 450nm up to 850nm. For undoped PANI, we observed saturation of absorption as well as reverse saturable absorption, depending on the excitation wavelength. For doped PANI, however, only saturable absorption was observed.

Nonlinear refractive index of RECOB (RE = Gd and La) crystals

The Z-scan technique is employed to obtain the nonlinear refractive index (n (2)) of the Ca(4)REO(BO(3))(3) (RECOB, where RE = Gd and La) single crystals using 30 fs laser pulses centered at 780 nm for the two orthogonal orientations determined by the optical axes (X and Z) relative to the direction of propagation of the laser beam (k//Y// crystallographic b-axis). The large values of n (2) indicate that both GdCOB and LaCOB are potential hosts for Yb:RECOB lasers operating in the Kerr-lens mode locking (KLM) regime.

Laser microstructuring for fabricating superhydrophobic polymeric surfaces

In this paper we show the fabrication of hydrophobic polymeric surfaces through laser microstructuring. By using 70-ps pulses from a Q-switched and mode-locked Nd:YAG laser at 532 nm, we were able to produce grooves with different width and separation, resulting in square-shaped pillar patterns. We investigate the dependence of the morphology on the surface static contact angle for water, showing that it is in agreement with the Cassie-Baxter model. We demonstrate the fabrication of a superhydrophobic polymeric surface, presenting a water contact angle of 157 degrees. The surface structuring method presented here seems to be an interesting option to control the wetting properties of polymeric surfaces. (C) 2010 Elsevier B.V. All rights reserved.

Third-order nonlinearity of Er(3+)-doped lead phosphate glass

The third-order optical susceptibility and dispersion of the linear refractive index of Er(3+)-doped lead phosphate glass were measured in the wavelength range between 400 and 1940 nm by using the spectrally resolved femtosecond Maker fringes technique. The nonlinear refractive index obtained from the third-order susceptibility was found to be five times higher than that of silica, indicating that Er(3+)-doped lead phosphate glass is a potential candidate to be used as the base component for the fabrication of photonic devices. For comparison purposes, the Z-scan technique was also employed to obtain the values of the nonlinear refractive index of Er(3+)-doped lead phosphate glass at several wavelengths, and the values obtained using the two techniques agree to within 15%.

Intrachain Energy Migration to Weak Charge-Transfer State in Polyfluorene End-Capped with Naphthalimide Derivative

Polyfluorene end-capped with N-(2-benzothiazole)-1 8-naphthalimide (PF-BNI) is a highly fluorescent material with fluorescence emission modulated by solvent polarity Its low energy excited state is assigned as a mixed configuration state between the singlet S(1) of the fluorene backbone (F) with the charge transfer (CI) of the end group BNI The triexponential fluorescence decays of PF-BNI were associated with fast energy migration to form an intrachain charge-transfer (ICCT) state polyfluorene backbone decay and ICCT deactivation Time-resolved fluorescence anisotropy exhibited biexponential relaxation with a fast component of 12-16 ps in addition to a slow one in the range 0 8-1 4 ns depending on the solvent showing that depolarization occurs from two different processes energy migration to form the ICCT state and slow rotational diffusion motion of end segments at a longer time Results from femtosecond transient absorption measurements agreed with anisotropy decay and showed a decay component of about 16 ps at 605 nm in PF BNI ascribed to the conversion of S(1) to the ICCT excited state From the ratio of asymptotic and initial amplitudes of the transient absorption measurement the efficiency of intrachain ICCT formation is estimated in 0 5 which means that on average, half of the excited state formed in a BNI-(F)(n)-BNI chain with n = 32 is converted to its low energy intrachain charge-transfer (ICCT) state

Two-photon absorption in perylene derivatives

This work reports on the two-photon absorption (2PA) cross-section for bis (n-butylimido) perylene (BuPTCD), bis (benzimidazo) perylene (AzoPTCD), bis (benzimidazo) thioperylene (Monothio BZP), bis (phenethylimido) perylene (PhPTCD), bis (benzylimido) perylene (BePTCD) and n-pentylimido-benzimidazo perylene (PAzoPTCD) solutions measured using the Z-scan technique with femtosecond laser pulses at 775 nm. All perylene derivatives studied present large 2PA cross-sections, only comparable to the best ones reported in the literature. The experimental 2PA cross-sections obtained for each PTCD compound are in good agreement with a simplified sum-over-state calculation. The results of the present work indicates perylene derivatives as promising materials for two-photon applications. (C) 2003 Elsevier B.V. B.V. All rights reserved.

Shear bond strength of repairs in porcelain conditioned with laser

The aim of this study was to evaluate the shear bond strength of repairs in porcelain conditioned with laser. Sixty porcelain discs were made and six groups were formed (n = 10): G1: conditioning with laser with potency 760 mW; G2: conditioning with laser with potency 760 mW and application of 37% phosphoric acid for 15 s; G3: conditioning with laser with potency 900 mW; G4: conditioning with laser with potency 900 mW and application of 37% phosphoric acid for 15 s; G5: application of 37% phosphoric acid for 15 s (group control) and G6: application of 10% hydrofluoric acid for 2 min. The composite resin was insert of incremental layers at the porcelain surface aided with a metal matrix, and photoactivation for 20 s each increment. The specimens were submitted to a thermal cycling by 1000 cycles of 30 s in each bath with temperature between 5 and 55 degrees C. After the thermal cycling, specimens were submitted to the shear bond strength. The results were evaluated statistically through analysis of variance and Tukey's tests with 5% significance. The averages and standard deviation founded were: G1, 11.25 (+/- 3.10); G2, 12.32 (+/- 2.65); G3, 14.02 (+/- 2.38); G4, 13.44 (+/- 2,07); G5, 9.91 (-/+ 2,18); G6, 12.74 (+/- 2.67). The results showed that the femtosecond laser produced a shear bond strength of repairs in porcelain equal to the hydrofluoric acid and significantly superior to the use of phosphoric acid. Microsc. Res. Tech., 2012. (C) 2012 Wiley Periodicals, Inc.

NIR luminescent Er3+/Yb3+ co-doped SiO2-ZrO2 nanostructured planar and channel waveguides: Optical and structural properties

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Bulk photochromism in a tungstate-phosphate glass: A new optical memory material?

In this work, we present a new photochromic tungstate based glass which have both absorption coefficient and refractive index modified under laser exposure. The photosensitive effect is superficial under ultraviolet (UV) irradiation but occurs in the entire volume of the glass under visible irradiation. The effect can be obtained in any specific point inside the volume using an infrared femtosecond laser. In addition, the photosensitive phenomenon can be erased by specific heat treatment. This glass can be useful to substitute actual data storage supports and is a promising material for 3-dimensional (3D) and holographic optical storage.

Nonlinear optical properties of tungstate fluorophosphate glasses

The optical nonlinearity of tungstate fluorophosphate glasses, synthesized in the NaPO3-BaF2-WO3 system, was investigated through experiments based on the third-order susceptibility, chi((3)). Nonlinear (NL) refraction and NL absorption measurements in the picosecond regime were performed using the Z-scan technique at 532 nm. NL refractive index, n(2)proportional toRe chi((3)), ranging from 0.4x10(-14) cm(2)/W to 0.6x10(-14) cm(2)/W were determined. The two-photon absorption coefficient, alpha(2)proportional toIm chi((3)), for excitation at 532 nm, vary from 0.3 to 0.5 cm/GW. Light induced birefringence experiments performed in the femtosecond regime indicate that the response time of the nonlinearity at 800 nm is faster than 100 fs. The experiments show that chi((3)) is enhanced when the WO3 concentration increases and this behavior is attributed to the hyperpolarizabilities associated to W-O bonds. (C) 2004 American Institute of Physics.