Marcus Motzkus

Chemoselective imaging of mouse brain tissue via multiplex CARS microscopy.

The fast and reliable characterization of pathological tissue is a debated topic in the application of vibrational spectroscopy in medicine. In the present work we apply multiplex coherent anti-Stokes Raman scattering (MCARS) to the investigation of fresh mouse brain tissue. The combination of imaginary part extraction followed by principal component analysis led to color contrast between grey and white matter as well as layers of granule and Purkinje cells. Additional quantitative information was obtained by using a decomposition algorithm. The results perfectly agree with HE stained references slides prepared separately making multiplex CARS an ideal approach for chemoselective imaging.

Acceleration of Singlet Fission in an Aza-Derivative of TIPS-Pentacene.

The influence of the carbon to nitrogen substitution on the photoinduced dynamics of TIPS-pentacene was investigated by ultrafast transient absorption measurements on spin-coated thin films in the visible and in the near-infrared spectral region. A global target analysis was performed to provide a detailed picture of the excited-state dynamics. We found that the chemical modification has a high impact on the triplet formation and leads to shorter dynamics; hence it speeds up the singlet fission process. A faster relaxation from the singlet into the triplet manifold implies a higher efficiency because other relaxation channels are avoided. The air-stable aza-derivatives have the potential to exceed the energy conversion efficiency of TIPS-pentacene.

Direct Observation of a Dark State in Lycopene Using Pump-DFWM

We apply pump-degenerate four-wave-mixing (pump-DFWM) for the investigation of the ultrafast internal relaxation of the excited states of lycopene. A unique feature in the pump-DFWM signal, appearing at small temporal delays between the initial pump pulse and the DFWM sequence, provides direct evidence for the participation of an additional excited state located between the S(2) and S(1) states. Our experimental findings are corroborated by a detailed numerical simulation of lycopenes pump-DFWM signal using the Brownian oscillator model. A very fast dynamics directly after excitation of the S(2) state manifests as a component populated with a time constant of about 20 fs and which decays to S(1) with a lifetime of 110 fs. This ultrafast dynamics is discussed under the light of several different models suggested for the relaxation pathway of carotenoids. In this context, we show that the dynamics can be explained in terms of a dark electronic state between the S(2) and S(1) states.

Ground- and Excited-State Vibrational Coherence Dynamics in Bacteriorhodopsin Probed With Degenerate Four-Wave-Mixing Experiments

Vibrational coherence dynamics in the all-trans retinal chromophore in Bacteriorhodopsin (BR) are investigated by means of temporally and spectrally resolved degenerate four-wave-mixing experiments. The coherence dynamics depend on the excitation wavelength when BR samples are excited at different wavelengths in a spectral range between 520 nm to above 620 nm. The trends in the dynamics observed by tuning of the excitation wavelength allow an assignment of the wave packet dynamics to ground- and excited-state potential energy surfaces. Specifically, the intensity of so-called out-of-plane modes of polyene-chain substituents increases for excitation wavelengths near 500 nm. It is shown that this is consistent with the assignment of out-of-plane modes to excited-state coherence dynamics. Moreover, intense low-frequency coherence dynamics around 200 cm(-1) are observed for signal detection in two different spectral regions of excited-state absorption. These modulations are assigned to excited-state dynamics due to the observed dependence on the excitation wavelength. In addition, we show that generally high-frequency modes (>1010 cm(-1)) originate from wave packet motion in the electronic ground state of all-trans retinal.

Multidimensional Time-Resolved Spectroscopy of Vibrational Coherence in Biopolyenes

Multidimensional femtosecond time-resolved vibrational coherence spectroscopy allows one to investigate the evolution of vibrational coherence in electronic excited states. Methods such as pump-degenerate four-wave mixing and pump-impulsive vibrational spectroscopy combine an initial ultrashort laser pulse with a nonlinear probing sequence to reinduce vibrational coherence exclusively in the excited states. By carefully exploiting specific electronic resonances, one can detect vibrational coherence from 0 cm(-1) to over 2,000 cm(-1) and map its evolution. This review focuses on the observation and mapping of high-frequency vibrational coherence for all-trans biological polyenes such as β-carotene, lycopene, retinal, and retinal Schiff base. We discuss the role of molecular symmetry in vibrational coherence activity in the S1 electronic state and the interplay of coupling between electronic states and vibrational coherence.

Coherent High-Frequency Vibrational Dynamics in the Excited Electronic State of All-Trans Retinal Derivatives

Coherent vibrational dynamics of retinal in excited electronic states are of primary importance in the understanding of photobiology. Using pump-DFWM, we demonstrate for the first time the existence of coherent double-bond high-frequency modulations (>1300 cm(-1)) in the excited electronic state of different retinal derivatives. All-trans retinal as well as retinal Schiff bases exhibit a partial frequency downshift of the C═C double-bond mode from ∼1580 cm(-1) in the ground state to 1510 cm(-1) in the excited state. In addition, a new vibrational band at ∼1700 cm(-1) assigned to the C═N stretching mode in retinal Schiff bases in the excited state is detected. The newly reported bands are observed only in specific spectral regions of excited-state absorption. Implications regarding the observation of vibrational coherences in naturally occurring retinal protonated Schiff bases in rhodopsins are discussed.

Unveiling Singlet Fission Mediating States in TIPS-pentacene and its Aza Derivatives

Femtosecond pump-depletion-probe experiments were carried out in order to shed light on the ultrafast excited-state dynamics of triisopropylsilylethynyl (TIPS)-pentacene and two nitrogen-containing derivatives, namely, diaza-TIPS-pentacene and tetraaza-TIPS-pentacene. Measurements performed in the visible and near-infrared spectral range in combination with rate model simulations reveal that singlet fission proceeds via the extremely short-lived intermediate (1)TT state, which absorbs in the near-infrared spectral region only. The T1 → T3 transition probed in the visible region shows a rise time that comprises two components according to a consecutive reaction (S1 → (1)TT → T1). The incorporation of nitrogen atoms into the acene structure leads to shorter dynamics, but the overall triplet formation follows the same kinetic model. This is of particular importance, since experiments on tetraaza-TIPS-pentacene allow for investigation of the triplet state in the visible range without an overlapping singlet contribution. In addition, the pump-depletion-probe experiments show that the triplet absorption in the visible (T1 → T3) and near-infrared (T1 → T2) regions occurs from the same initial state, which was questioned in previous studies. Furthermore, an additional ultrafast transfer between the excited triplet states (T3 → T2) is identified, which is also in agreement with the rate model simulation. By applying depletion pulses, which are resonant with higher vibrational levels, we gain insight into internal vibrational energy redistribution processes within the triplet manifold. This additional information is of great relevance regarding the study of loss channels within these materials.

Evidence for the Two-State-Two-Mode model in retinal protonated Schiff-bases from pump degenerate four-wave-mixing experiments.

We apply spectrally-resolved pump degenerate four-wave-mixing for the characterization of excited state low-frequency vibrational coherences during the initial events in excited state double-bond isomerization of retinal protonated Schiff-bases. A set of low-frequency coherences in the energetic range of 100-350 cm(-1) appears in the dynamics already for very early delays after initial excitation (<100 fs). The modulations are rapidly damped (<800 fs) and detectable only in a certain time window after initial excitation (<0.6 ps). Following the initial relaxation process, which leads the molecule to a stationary point in the S(1) state, it is not possible to re-excite the coherences in the excited state. Based on our observations, we conclude that the activation of the coherences is only possible to occur in a well-defined region of the excited state potential near the Franck-Condon region. Our results give direct experimental indication for the validity of the Two-State-Two-Mode model, frequently applied for the interpretation of retinal isomerization dynamics.

Enhancement of coherent anti-Stokes Raman signal via tailored probing in spectral focusing

A novel approach for spectral focusing using a single-beam coherent anti-Stokes Raman scattering setup with a pulse shaper controlling the phase and amplitude is presented. By identifying the frequencies acting as the pump, Stokes, and probe, the high degree of control can be exploited in order to specifically and independently tailor the spectral region to act only as probe to achieve the highest signal intensity. While maintaining the optimal excitation of the vibrational coherence, a signal increase by a factor of six in comparison with usual spectral focusing schemes is readily obtained. The signal improvement and contrast is demonstrated on human skin tissue.

Exploring the potential of tailored spectral focusing

We introduce an advanced and flexible spectral focusing coherent anti-Stokes Raman scattering (CARS) microspectroscopy scheme based on the independent control of pump, Stokes, and probe frequencies offered by a pulse shaper. Adjusting the instantaneous bandwidth of 10 fs pulses in the focus of a microscope to different Raman linewidths assures high spectral resolution and signal intensities from the CH-bond to the fingerprint region. Experimental results are confirmed by simulations based on the CARS signal generation process. By delaying the probe, increased signal intensity and minimized nonresonant background are achieved while enabling time-dependent measurements. Contrast based on the difference of decoherence times is established and used to distinguish initially overlapping CH resonances of sunflower oil. Because of the transform-limited nature of the tailored probe, enhanced instantaneous nonlinear signals enable simultaneous multimodal imaging and molecule-specific CARS contrast as demonstrated on human skin tissue.