First events in the coil-to-globule transition of PVME in water: An ultrafast temperature jump - time-resolved elastic light scattering study.

HYPOTHESIS: The coil-to-globule transition is an essential phenomenon in protein and polymer solutions. Late stages of such transitions, >1 µs, have been thoroughly studied. Yet, the initial ones are a matter of speculations. Here, we present the first observation of a sub-nanosecond stage of the coil-to-globule transition of poly (vinyl methyl ether), PVME, in water. EXPERIMENTS: The detection of an early stage of the coil-to-globule transition has been possible thanks to a novel experimental approach - time-resolved elastic light scattering study, following an ultrafast temperature jump. We identified a molecular process active in the observed stage of the transition with use of broadband dielectric spectroscopy. FINDINGS: In the experiment's time window, from a few ps to around 600 ps, we observed an increase in the light scattering intensity 300-400 ps after the temperature jump that heated the sample above its lower critical solution temperature (LCST). The observed time coincides with the time of segmental relaxation of PVME, determined by broadband dielectric spectroscopy in the temperature range of the LCST of the PVME/water mixture. This coincidence strongly suggests that the observed herein stage of coil-to-globule transition is the rapid formation of local nuclei along the polymer chain. Those nuclei may grow and aggregate in later stages of the process, which are out of our experimental time window.

Spontaneous versus Stimulated Surface-Enhanced Raman Scattering of Liquid Water.

We have observed for the first time the surface-enhanced (SE) signal of water in an aqueous dispersion of silver nanoparticles in spontaneous (SERS) and femtosecond stimulated Raman (SE-FSRS) processes with different wavelengths of the Raman pump (515, 715, and 755 nm). By estimating the fraction of water molecules that interact with the metal surface, we have calculated enhancement factors (EF): 4.8 × 106 for SERS and (3.6-3.7) × 106 for SE-FSRS. Furthermore, we have tested the role of simultaneous plasmon resonance and Raman resonance conditions for the aν 1 + bν3 overtone mode of water (755 nm) in SE-FSRS signal amplification. When the wavelength of the Raman pump is within the plasmon resonance of the metal nanoparticles, the Raman resonance has a negligible effect on the EF. However, the Raman resonance with the aν 1 + bν3 mode strongly enhances the signal of the fundamental OH stretching mode of water.

Femtosecond infrared pump-stimulated Raman probe spectroscopy: the first application of the method to studies of vibrational relaxation pathways in the liquid HDO/D2O system.

We have proposed and constructed a setup for a novel method of ultrafast vibrational spectroscopy: femtosecond infrared pump-stimulated Raman probe spectroscopy. This is the first time-resolved spectroscopy providing simultaneously a sub-100 fs time resolution, a spectral resolution better than 10 cm-1 and a spectral window covering an extremely broad range of molecular vibrations (at least: 200-4000 cm-1) with a "single laser shot". The new method was applied to study vibrational relaxation pathways in the liquid HDO/D2O system. We determined the lifetimes of OH stretching vibrations to be in the range 310-500 fs depending on the isotopic dilution, which is in good agreement with the results from pump-probe femtosecond infrared spectroscopy. Moreover, we observed a strong coupling of OH stretch to OD stretch vibrations and possibly also to the librational modes of water.

Diverse nature of femtosecond laser ablation of poly(L-lactide) and the influence of filamentation on the polymer crystallization behaviour.

Over the past few years we have witnessed growing interest in ultrafast laser micromachining of bioresorbable polymers for fabrication of medical implants and surface modification. In this paper we show that surface structuring of poly(L-lactide) with 300 fs laser pulses at 515 and 1030 nm wavelength leads to formation of defects inside the polymer as a result of laser beam filamentation. Filament-induced channels have diameter around 1 µm and length of hundreds of micrometers. SEM images of microchannels cross-sections are presented. The influence of wavelength and pulse spacing on bulk modification extent was investigated and parameters limiting filamentation were determined. We show that filamentation can be used for controlling properties of PLLA. The presence of filament-induced modifications such as empty microchannels and pressure wave-induced stress lead to increased ability of polymer to crystallize at lower temperature. Crystallization behaviour and crystal morphology after laser treatment was investigated in details using different analytical techniques such as WAXD, DSC and FTIR/ATR. Hydrolytic degradation experiment was performed. Presented method can be applied for controllable, spatially distributed modification of polymer crystallinity, crystalline phase structure and hydrolytic degradation profile.

Generation-Collection Electrochemistry Inside a Rotating Droplet.

In this work, we explore generation-collection electrochemistry in a rotating droplet hydrodynamic system, where a 70 µL droplet containing a redox active species (ferrocyanide) is sandwiched between an upper rotating rod and bottom nonmoving generator and collector planar electrodes. In such a system, we studied the effect of the counter electrode reaction on the recorded generator current, and the effect of the generator-collector distance (ranging from 3 to ca. 500 µm) on the collection efficiencies obtained at rotation rates ranging from 50 to 1100 rpm. We found that the counter electrode reaction competes with the collector reaction for the regeneration of the electroactive species; thus, collection efficiencies of 100% are probably impossible to obtain with this system geometry. We found that the collection efficiency increases with the droplet rotation rate and decreases with the generator-collector distance. The highest collection efficiency we obtained is 62% for the generator-collector distance of 3 µm, which is more than two times higher than that for typical bulk experiments with a commercial rotating ring disk electrode. We show that the increased collection efficiency can be successfully used in epinephrine detection for filtering out signals from ascorbic acid and uric acid interferents.

Full 3D modelling of pulse propagation enables efficient nonlinear frequency conversion with low energy laser pulses in a single-element tripler.

Although new optical materials continue to open up access to more and more wavelength bands where femtosecond laser pulses can be generated, light frequency conversion techniques are still indispensable in filling the gaps on the ultrafast spectral scale. With high repetition rate, low pulse energy laser sources (oscillators) tight focusing is necessary for a robust wave mixing and the efficiency of broadband nonlinear conversion is limited by diffraction as well as spatial and temporal walk-off. Here we demonstrate a miniature third harmonic generator (tripler) with conversion efficiency exceeding 30%, producing 246 fs UV pulses via cascaded second order processes within a single laser beam focus. Designing this highly efficient and ultra compact frequency converter was made possible by full 3-dimentional modelling of propagation of tightly focused, broadband light fields in nonlinear and birefringent media.

Influence of the excitation light intensity on the rate of fluorescence quenching reactions: pulsed experiments.

The effect of multiple light excitation events on bimolecular photo-induced electron transfer reactions in liquid solution is studied experimentally. It is found that the decay of fluorescence can be up to 25% faster if a second photon is absorbed after a first cycle of quenching and recombination. A theoretical model is presented which ascribes this effect to the enrichment of the concentration of quenchers in the immediate vicinity of fluorophores that have been previously excited. Despite its simplicity, the model delivers a qualitative agreement with the observed experimental trends. The original theory by Burshtein and Igoshin (J. Chem. Phys., 2000, 112, 10930-10940) was created for continuous light excitation though. A qualitative extrapolation from the here presented pulse experiments to the continuous excitation conditions lead us to conclude that in the latter the order of magnitude of the increase of the quenching efficiency upon increasing the light intensity of excitation, must also be on the order of tens of percent. These results mean that the rate constant for photo-induced bimolecular reactions depends not only on the usual known factors, such as temperature, viscosity and other properties of the medium, but also on the intensity of the excitation light.

Spectral compression of femtosecond pulses using chirped volume Bragg gratings.

In this Letter, we demonstrate a 360 fold spectral bandwidth reduction of femtosecond laser pulses using the method of sum frequency generation of pulses with opposite chirps. The reduction has been achieved in a compact setup in which a single chirped volume Bragg grating replaces conventional stretcher and compressor units. Starting with 180 fs pulses, we have obtained, with a 30% overall efficiency, pulses longer than 100 ps with the spectral bandwidth of 0.23 cm-1 (7 GHz). We also discuss our method on theoretical grounds.

Efficient spectral shift and compression of femtosecond pulses by parametric amplification of chirped light.

We present a method for an efficient spectral shift and compression of pulses from a femtosecond laser system. The method enables generation of broadly tunable (615-985 nm) narrow bandwidth (≈10 cm(-1)) pulses from the femtosecond pulses at 1030 nm. It employs a direct parametric amplification--without spectral filtering--of highly chirped white light by a narrow bandwidth (<5 cm(-1)) 515 nm pump pulse. The system, when pumped with just 200 µJ of the fundamental femtosecond pulse energy, generates pulses with energies of 3-9 µJ and an excellent beam quality in the entire tuning range.

Ground and excited state double hydrogen transfer in symmetric and asymmetric potentials: comparison of 2,7,12,17-tetra-n-propylporphycene with 9-acetoxy-2,7,12,17-tetra-n-propylporphycene.

Analysis of time-resolved anisotropy of transient absorption enabled determination of room temperature ground and excited state rate constants for intramolecular double hydrogen transfer in two similar porphycenes, one of them with symmetric and the other, with asymmetric character of a double minimum potential for hydrogen motion. The perturbation preserves a quasi-symmetric minimum in S(0), but the rate decreases approximately two times. In S(1), the perturbed potential becomes strongly asymmetric, and the downhill hydrogen transfer occurs with a rate higher than that observed for a symmetrical compound.