Photochemistry and electron-transfer mechanism of transition metal oxalato complexes excited in the charge transfer band.

The photoredox reaction of trisoxalato cobaltate (III) has been studied by means of ultrafast extended x-ray absorption fine structure and optical transient spectroscopy after excitation in the charge-transfer band with 267-nm femtosecond pulses. The Co-O transient bond length changes and the optical spectra and kinetics have been measured and compared with those of ferrioxalate. Data presented here strongly suggest that both of these metal oxalato complexes operate under similar photoredox reaction mechanisms where the primary reaction involves the dissociation of a metal-oxygen bond. These results also indicate that excitation in the charge-transfer band is not a sufficient condition for the intramolecular electron transfer to be the dominant photochemistry reaction mechanism.

Ultrawideband photonic crystal fiber coupler for multiband optical imaging system.

We report a photonic crystal fiber (PCF) coupler having an ultrawide spectral bandwidth keeping single mode operation. The use of the PCF coupler in a fiber-based optical coherence tomography (OCT) system enables us to handle the wide spectral bands of various light sources, including superluminescent diodes (SLDs) at 1300 nm and 820 nm, Ti:sapphire lasers, and white-light sources. The multiband imaging performances of the PCF-based OCT system are demonstrated by obtaining dental images at 1300 nm and 820 nm with the same setup. In addition, we show that the PCF coupler could cover the spectrum over a one octave span and guide both the fundamental wave (1030 nm) and the second harmonic wave (515 nm) simultaneously.

Rotational multiphoton endoscopy with a 1 microm fiber laser system.

We present multiphoton microendoscopy with a rotational probe and a 1 microm fiber-based femtosecond laser. The rotational probe is based on a double-clad photonic crystal fiber, a gradient index lens, a microprism, and a rotational microelectronicmechanical system (MEMS) motor. The MEMS motor has a diameter of 2.2 mm and can provide 360 degrees full-view rotation. The fiber laser provides ultrashort pulses with a central wavelength at 1.034 microm and a repetition rate of 50 MHz. Second-harmonic-generation images of rat-tail tendon and fish scale are demonstrated with the rotational probe-based multiphoton system.

Electron transfer mechanism and photochemistry of ferrioxalate induced by excitation in the charge transfer band.

The photoredox reaction of ferrioxalate after 266/267 nm excitation in the charge transfer band has been studied by means of ultrafast extended X-ray absorption fine structure (EXAFS) analysis, optical transient spectroscopy, and quantum chemistry calculations. The Fe-O bond length changes combined with the transient spectra and kinetics have been measured and in combination with ultrahigh frequency density functional theory (UHF/DFT) calculations are used to determine the photochemical mechanism for the Fe(III) to Fe(II) redox reaction. The present data and the results obtained with 266/267 nm excitations strongly suggest that the primary reaction is the dissociation of the Fe-O bond before intramolecular electron transfer occurs. Low quantum yield electron photodetachment from ferrioxalate has also been observed.

Miniaturized probe based on a microelectromechanical system mirror for multiphoton microscopy.

A factor that limits the use of multiphoton microscopy (MPM) in clinical and preclinical studies is the lack of a compact and flexible probe. We report on a miniaturized MPM probe employing a microelectromechanical system (MEMS) scanning mirror and a double-clad photonic crystal fiber (DCPCF). The use of a MEMS mirror and a DCPCF provides many advantages, such as size reduction, rapid and precise scanning, efficient delivery of short pulses, and high collection efficiency of fluorescent signals. The completed probe was 1 cm in outer diameter and 14 cm in length. The developed probe was integrated into an MPM system and used to image fluorescent beads, paper, and biological specimens.

High-resolution frequency-domain second-harmonic optical coherence tomography.

We used continuum generated in an 8.5 cm long fiber by a femtosecond Yb fiber laser to improve threefold the axial resolution of frequency domain second-harmonic optical coherence tomography (SH-OCT) to 12 microm. The acquisition time was shortened by more than 2 orders of magnitude compared to the time-domain SH-OCT. The system was applied to image biological tissue of fish scales, pig leg tendon, and rabbit eye sclera. Highly organized collagen fibrils can be visualized in the recorded images. Polarization dependence on the SH has been used to obtain polarization resolved images.

Transient structures and kinetics of the ferrioxalate redox reaction studied by time-resolved EXAFS, optical spectroscopy, and DFT.

The photoredox reaction transients of ferrioxalate in water have been studied by means of time-resolved EXAFS and ultrafast optical transient spectroscopy. The transient spectra and kinetics have been measured from the femtosecond to millisecond range, and the Fe-O bond lengths of the ferrioxalate redox reaction transients have been determined with 2 ps time resolution and 0.04 A accuracy. These data in conjunction with quantum-chemistry DFT and UHF calculations were used to formulate a mechanism for the Fe(III) to Fe(II) redox reaction where dissociation precedes electron transfer. In addition, radical scavenging experiments support the mechanism proposed.

Photoelectron detachment and solvated electron dynamics of the cobalt(III) and iron(III) oxalato complexes.

The photochemical redox reaction kinetics of [M(III)(C(2)O(4))(3)](3-) [M = Co, Fe] complexes have been reexamined and studied by time-resolved spectroscopy. The redox mechanisms of the two systems, Co and Fe, were found to be similar to each other, and solvated electrons were observed immediately after 266/267 nm photoexcitation. A reaction mechanism is proposed that involves photoelectron detachment as a primary process. The charge-transfer bands for both complexes, which had been attributed to ligand to metal charge-transfer (LMCT) transitions previously, are reassigned to charge transfer to solvent (CTTS) transitions.

Low-noise broadband light generation from optical fibers for use in high-resolution optical coherence tomography.

Broadband light generation from a single-mode optical fiber was developed for high-resolution optical coherence tomography (OCT). No noise amplification was observed for light broadened by self-phase modulation. The investigation showed that the intensity noise of light broadened by self-phase modulation in a single-mode optical fiber was much lower than that of continuum light from a microstructure fiber (MSF). The spectral width of a femtosecond input laser pulse was successfully broadened by a factor of 11, and a coherence length of 3.7 microm was achieved with this source. The application of light broadened by a single-mode optical fiber and MSF was compared for use in OCT imaging. The results showed that a single-mode fiber with a small core diameter is a useful way to generate low-noise, broadband light for high-resolution OCT imaging.

Ultrafast time-resolved transient structures of solids and liquids by means of extended X-ray absorption fine structure.

Detection of ultrafast transient structures and the evolution of ultrafast structural intermediates during the course of reactions has been a long standing goal of chemists and biologists. This article will be restricted to nanosecond, picosecond and shorter time-resolved extended X-ray absorption fine structure (EXAFS) studies, its aim being to present the progress and problems encounter in measurements and understanding the structure of transients. The recent advances in source technology has stimulated a wide variety of novel experiments using both synchrotrons and smaller laboratory size systems. With more efficient X-ray lenses and detectors many of the previously difficult experiments to perform, because of the exposure time required and weak signals, will now be easily performed. The experimental system for the detection of ultrafast, time-resolved EXAFS spectra of molecules in liquids is described and the method for the analysis of EXAFS spectra to yield transient structures is given. We believe that utilizing our table-top ultrafast X-ray source and the polycapillary optics in conjunction with dispersive spectrometer and charge coupled devices (CCD) we will be able to determine the structure of many reaction intermediates and excited states of chemical and biological molecules in solid and liquid state.

Second harmonic optical coherence tomography.

Second harmonic optical coherence tomography, which uses coherence gating of second-order nonlinear optical response of biological tissues for imaging, is described and demonstrated.

Second-harmonic optical coherence tomography.

Second-harmonic optical coherence tomography, which uses coherence gating of second-order nonlinear optical responses of biological tissues for imaging, is described and demonstrated. Femtosecond laser pulses were used to excite second-harmonic waves from collagen harvested from rat tail tendon and a reference non-linear crystal. Second-harmonic interference fringe signals were detected and used for image construction. Because of the strong dependence of second-harmonic generation on molecular and tissue structures, this technique imparts contrast and resolution enhancement to conventional optical coherence tomography.