Piotr Piotrowiak

Photoinduced electron transfer in molecular systems: recent developments

Highlights of new findings in electron transfer studies, in which elegant synthetic model systems were used to address important fundamental questions, are briefly described. The selected examples include: (i) efficient long distance electron transfer mediated by hydrogen bonds; (ii) energy and electron transfer through the walls of hemicarcerands; (iii) the influence of internal electric fields on the rate of electron transfer in α-helical peptides; (iv) construction of a biomimetic proton pump driven by photoinduced electron transfer. The review underscores the increasing role of synthesis in modern physical chemistry research.

Femtosecond Kerr-gated wide-field fluorescence microscopy

We present a Kerr-gated microscope capable of collecting diffraction-limited 2D fluorescence images with sub-100 fs time resolution. The concept is based on the insertion of a solid-state optical Kerr gate into a wide-field microscope. In addition to the considerably improved temporal resolution, the wide-field design allows for simultaneous tracking of several objects and ultrafast fluorescence lifetime imaging of doped and heterogeneous surfaces. The ultrafast fluorescence dynamics of gold nanoparticles is presented as an example of the capabilities of the instrument.

Electron and excitation transfer in hetero-supramolecular assemblies and at molecule­nanoparticle interfaces

Encapsulation of chromophores within Cram-type hemicarcerands allowed the investigation of fundamental photophysical phenomena, such as long-range triplet energy transfer, electron transfer, and the remote heavy atom effect. Furthermore, novel water-soluble hemicarcerands are being used to develop unique hybrid materials composed of semiconductor nanoparticles and host–guest assemblies. Photoinduced charge injection from the “incarcerated” guest into the conduction band of the semiconductor has been demonstrated.

Electrostatic docking of a supramolecular host-guest assembly to cytochrome c probed by bidirectional photoinduced electron transfer.

A water-soluble octacarboxyhemicarcerand was used as a shuttle to transport redox-active substrates across the aqueous medium and deliver them to the target protein. The results show that weak multivalent interactions and conformational flexibility can be exploited to reversibly bind complex supramolecular assemblies to biological molecules. Hydrophobic electron donors and acceptors were encapsulated within the hemicarcerand, and photoinduced electron transfer (ET) between the Zn-substituted cytochrome c (MW = 12.3 kD) and the host-guest complexes (MW = 2.2 kD) was used to probe the association between the negatively charged hemicarceplex and the positively charged protein. The behavior of the resulting ternary protein-hemicarcerand-guest assembly was investigated in two binding limits: (1) when K(encaps) ≫ K(assoc), the hemicarcerand transports the ligand to the protein while protecting it from the aqueous medium; and (2) when K(assoc) > K(encaps), the hemicarcerand-protein complex is formed first, and the hemicarcerand acts as an artificial receptor site that intercepts ligands from solution and positions them close to the active site of the metalloenzyme. In both cases, ET mediated by the protein-bound hemicarcerand is much faster than that due to diffusional encounters with the respective free donor or acceptor in solution. The measured ET rates suggest that the dominant binding region of the host-guest complex on the surface of the protein is consistent with the docking area of the native redox partner of cytochrome c. The strong association with the protein is attributed to the flexible conformation and adaptable charge distribution of the hemicarcerand, which allow for surface-matching with the cytochrome.

Excitons and excess electrons in nanometer size molecular polyoxotitanate clusters: electronic spectra, exciton dynamics, and surface states.

The behavior of excitons and excess electrons in the confined space of a molecular polyoxotitanate cluster Ti17(μ4-O)4(μ3-O)16(μ2-O)4(OPr(i))20 (in short Ti17) was studied using femtosecond pump-probe transient absorption, pulse radiolysis, and fluorescence spectroscopy. Due to pronounced quantum size effects, the electronic spectra of the exciton, Ti17*, and the excess electron carrying radical anion, Ti17(•-), are blue-shifted in comparison with bulk TiO2 and have maxima at 1.91 and 1.24 eV, respectively. The 0.7 eV difference in the position of the absorption maxima of Ti17* and Ti17(•-) indicates the presence of strong Coulomb interaction between the conduction band electron and the valence band hole in the ∼1 nm diameter cluster. Ground state Raman spectra and the vibronic structure of the fluorescence spectrum point to the importance of the interfacial ligand modes in the stabilization and localization of the fully relaxed exciton. Four pentacoordinate Ti sites near the surface of the cluster appear to play a special role in this regard. Solvent polarity has only a minor influence on the spectral behavior of Ti17*. Exciton recombination in Ti17 is faster than in anatase nanoparticles or mesoporous films. The kinetics exhibits three components, ranging from less than 1 ps to 100 ps, which are tentatively assigned to the geminate recombination within the core of the cluster and to the decay of the surface stabilized charge transfer exciton. A persistent long-lived component with τ > 300 ps may indicate the involvement of intraband dark states, i.e., triplet excitons (3)Ti17*.

Efficiency and temporal response of crystalline Kerr media in collinear optical Kerr gating

Optical Kerr gating is widely used in ultrafast measurements ranging from pulse characterization to spectroscopy and microscopy. We examined the efficiency and the temporal response of three cubic lattice Kerr media, YAG, GGG and BGO, and compared them with the well studied fused silica (fast response, low efficiency) and STO (high efficiency, slow response). YAG and GGG emerged as superior materials for ultrafast spectroscopy and microscopy applications thanks to their fast Kerr response and considerably higher gating efficiency than silica at low gating energies. Importantly, it was found that in collinear geometry all tested materials except STO are capable of reaching nearly 100% transmission.

Ion-pairing effects in intramolecular electron transfer

Abstract The effect of electrolyte on the rate of intramolecular electron transfer (ET) was analyzed within the framework of ionic association. A unified approach combining the ionic atmosphere and specific ion pairing contributions to the reorganization energy has been developed. The weighing of the free ion and ion pairing contributions is based on the appropriate mass action law. In the limit of weak association the model converges to the Debye–Huckel–Bjerrum picture of electrolytes. In the limit of strong association the ion-pairing dominates. In accordance with experiment, this results in a remarkable decrease of ET rates even at very low electrolyte concentrations.

Generation Dependent Ultrafast Charge Separation and Recombination in a Pyrene-Viologen Family of Dendrons.

The ability of a dendritic network to intercept electrons and extend the lifetime of a short-lived photoinduced charge separated (CS) state was investigated in a homologous family of methyl viologen (MV(2+)) dendrons spanning four generations, G0 through G3. The CS state in the parent pyrene-methylene-viologen G0 system with a single acceptor exhibits an extremely short lifetime of τ = 0.72 ps. The expansion of the viologen network introduces slower components to the recombination kinetics by allowing the injected electron to migrate further away from the donor. The long-lived fraction of the population increases monotonically in the order G3 > G2 > G1 > G0, while the respective recombination rates decrease. In the highest generation of the dendron ∼14% of the CS state population experiences a 10-fold or greater lifetime extension. Long range tunneling across multiple viologen units and sequential site-to-site hopping both contribute to the overall effect. The large excess energy deposited in the apical viologen upon charge separation and the presence of an extended network of low lying π-orbitals likely facilitate shuttling the electron further down the dendron.

CHAPTER 7:Ultrafast Optical Imaging and Microspectroscopy

Ultrafast microscopy combines the capabilities of femtosecond pump probe spectroscopy with the ability to image and monitor individual objects, down to the single particle and single molecule level. This combination of temporal, spatial and spectral resolution is necessary when studying charge and energy transfer processes in heterogeneous and nanostructured materials, which are increasingly common in the fields of photovoltaics and photocatalysis. Acquisition of images evolving on the femtosecond timescale, similarly to the acquisition of femtosecond photoluminescence and absorption spectra, must rely on optical gating techniques as there are no electronic devices capable of operating in this time domain. In this chapter we describe two all-optical realizations of femtosecond microscopy which are most general and straightforward to implement: wide-field Kerr-gated fluorescence microscopy (KGFM) and scanning pump probe transient absorption microscopy (PPTAM).

Zinc-substituted cytochrome P450cam: characterization of protein conformers F420 and F450 by photoinduced electron transfer.

Metal substitution of heme proteins is widely applied in the study of biologically relevant electron transfer (ET) reactions. It has been shown that many modified proteins remain in their native conformation and can provide useful insights into the molecular mechanism of electron transfer between the native protein and its substrates. We investigated ET reactions between zinc-substituted cytochrome P450(cam) and small organic compounds such as quinones and ferrocene, which are capable of accessing the proteins hydrophobic channel and binding close to the active site, like its native substrate, camphor. Following the substitution method developed by Gunsalus and co-workers [Wagner, G. C., et al. (1981) J. Biol. Chem. 256, 6262-6265], we have identified two dominant forms of the zinc-substituted protein, F450 and F420, that exhibit different photophysical and photochemical properties. The ET behavior of F420 suggests that hydrophobic redox-active ligands are able to penetrate the hydrophobic channel and place themselves in the direct vicinity of the Zn-porphyrin. In contrast, the slower ET quenching rates observed in the case of F450 indicate that the association is weak and occurs outside of the protein channel. Therefore, we conclude that F420 corresponds to the open structure of the native cytochrome P450(cam) while F450 has a closed or partially closed channel that is characteristic of the camphor-containing cytochrome P450(cam). The existence of two distinct conformers of Zn-bound P450(cam) is consistent with the findings of Goodin and co-workers [Lee, Y.-T., et al. (2010) Biochemistry 49, 3412-3419] and has significant consequences for future electron transfer studies on this popular metalloenzyme.