Rationalizing In Situ Active Repair in Hydrogen Evolution Photocatalysis via Non-Invasive Raman Spectroscopy.

Currently, most photosensitizers and catalysts used in the field of artificial photosynthesis are still based on rare earth metals and should thus be utilized as efficiently and economically as possible. While repair of an inactivated catalyst is a potential mitigation strategy, this remains a challenge. State-of-the-art methods are crucial for characterizing reaction products during photocatalysis and repair, and are currently based on invasive analysis techniques limiting real-time access to the involved mechanisms. Herein, we use an innovative in situ technique for detecting both initially evolved hydrogen and after active repair via advanced non-invasive rotational Raman spectroscopy. This facilitates unprecedently accurate monitoring of gaseous reaction products and insight into the mechanism of active repair during light-driven catalysis enabling the identification of relevant mechanistic details along with innovative repair strategies.

Atomistic View of the Energy Transfer in a Fluorophore-Functionalized Gold Nanocluster.

Understanding the dynamics of Förster resonance energy transfer (FRET) in fluorophore-functionalized nanomaterials is critical for developing and utilizing such materials in biomedical imaging and optical sensing applications. However, structural dynamics of noncovalently bound systems have a significant effect on the FRET properties affecting their applications in solutions. Here, we study the dynamics of the FRET in atomistic detail by disclosing the structural dynamics of the noncovalently bound azadioxotriangulenium dye (KU) and atomically precise gold nanocluster (Au25(p-MBA)18, p-MBA = para-mercaptobenzoic acid) with a combination of experimental and computational methods. Two distinct subpopulations involved in the energy transfer process between the KU dye and the Au25(p-MBA)18 nanoclusters were resolved by time-resolved fluorescence experiments. Molecular dynamics simulations revealed that KU is bound to the surface of Au25(p-MBA)18 by interacting with the p-MBA ligands as a monomer and as a π-π stacked dimer where the center-to-center distance of the monomers to Au25(p-MBA)18 is separated by ∼0.2 nm, thus explaining the experimental observations. The ratio of the observed energy transfer rates was in reasonably good agreement with the well-known 1/R6 distance dependence for FRET. This work discloses the structural dynamics of the noncovalently bound nanocluster-based system in water solution, providing new insight into the dynamics and energy transfer mechanism of the fluorophore-functionalized gold nanocluster at an atomistic level.

Laser-induced tuning of graphene field-effect transistors for pH sensing.

Here we demonstrate, using pulsed femtosecond laser-induced two-photon oxidation (2PO), a novel method of locally tuning the sensitivity of solution gated graphene field-effect transistors (GFETs) without sacrificing the integrity of the carbon network of chemical vapor deposition (CVD) grown graphene. The achieved sensitivity with 2PO was (25 ± 2) mV pH-1 in BIS-TRIS propane HCl (BTPH) buffer solution, when the oxidation level corresponded to the Raman peak intensity ratio I(D)/I(G) of 3.58. Sensitivity of non-oxidized, residual PMMA contaminated GFETs was 20-22 mV pH-1. The sensitivity decreased initially by 2PO to (19 ± 2) mV pH-1 (I(D)/I(G) = 0.64), presumably due to PMMA residue removal by laser irradiation. 2PO results in local control of functionalization of the CVD-grown graphene with oxygen-containing chemical groups enhancing the performance of the GFET devices. The GFET devices were made HDMI compatible to enable easy coupling with external devices for enhancing their applicability.

Diversity at the nanoscale: laser-oxidation of single-layer graphene affects Fmoc-phenylalanine surface-mediated self-assembly.

We report the effects of a laser-oxidized single layer graphene (SLG) surface on the self-assembly of amphiphilic gelator N-fluorenylmethoxycarbonyl-L-phenylalanine (Fmoc-Phe) towards an gel-SLG interface. Laser oxidation modulates the levels of hydrophobicity/hydrophilicity on the SLG surface. Atomic force, scanning electron, helium ion and scattering scanning nearfield optical microscopies (AFM, SEM, HIM, s-SNOM) were employed to assess the effects of surface properties on the secondary and tertiary organization of the formed Fmoc-Phe fibres at the SLG-gel interface. S-SNOM shows sheet-like secondary structures on both hydrophobic/hydrophilic areas of SLG and helical or disordered structures mainly on the hydrophilic oxidized surface. The gel network heterogeneity on pristine graphene was observed at the scale of single fibres by s-SNOM, demonstrating its power as a unique tool to study supramolecular assemblies and interfaces at nanoscale. Our findings underline the sensitivity of assembled structures to surface properties, while our characterization approach is a step forward in assessing surface-gel interfaces for the development of bionic devices.

Nanoscale Probing of the Supramolecular Assembly in a Two-Component Gel by Near-Field Infrared Spectroscopy.

The design of soft biomaterials requires a deep understanding of molecular self-assembly. Here a nanoscale infrared (IR) spectroscopy study of a two-component supramolecular gel is introduced to assess the system's heterogeneity and supramolecular assembly. In contrast to far-field IR spectroscopy, near-field IR spectroscopy revealed differences in the secondary structures of the gelator molecules and non-covalent interactions at three distinct nano-locations of the gel network. A ß-sheet arrangement is dominant in single and parallel fibres with a small proportion of an α-helix present, while the molecular assembly derives from strong hydrogen bonding. However, at the crossing point of two fibres, only the ß-sheet motif is observed, with an intense π-π stacking contribution. Near-field nanospectroscopy can become a powerful tool for the nanoscale distinction of non-covalent interactions, while it is expected to advance the existing spectroscopic assessments of supramolecular gels.

Shaping graphene with optical forging: from a single blister to complex 3D structures.

Properties of graphene, such as electrical conduction and rigidity can be tuned by introducing local strain or defects into its lattice. We used optical forging, a direct laser writing method, under an inert gas atmosphere, to produce complex 3D patterns of single layer graphene. We observed bulging of graphene out of the plane due to defect induced lattice expansion. By applying low peak fluences, we obtained a 3D-shaped graphene surface without either ablating it or deforming the underlying Si/SiO2 substrate. We used micromachining theory to estimate the single-pulse modification threshold fluence of graphene, which was 8.3 mJ cm-2, being an order of magnitude lower than the threshold for ablation. The control of exposure parameters allowed the preparation of blisters with various topographies. The optically forged structures were studied with atomic force microscopy and Raman spectroscopy. Optically forged blisters act as building blocks in the formation of more complex structures. We found a simple geometric rule that helps to predict the shape of complex patterns which are created by the overlapping multiple exposures. Optical forging enables writing of extended patterns with diffraction unlimited features, which makes this method promising in the production of nanodevices with locally induced surface modifications.

Tuning protein adsorption on graphene surfaces via laser-induced oxidation.

An approach for controlled protein immobilization on laser-induced two-photon (2P) oxidation patterned graphene oxide (GO) surfaces is described. Selected proteins, horseradish peroxidase (HRP) and biotinylated bovine serum albumin (b-BSA) were successfully immobilized on oxidized graphene surfaces, via non-covalent interactions, by immersion of graphene-coated microchips in the protein solution. The effects of laser pulse energy, irradiation time, protein concentration and duration of incubation on the topography of immobilized proteins and consequent defects upon the lattice of graphene were systemically studied by atomic force microscopy (AFM) and Raman spectroscopy. AFM and fluorescence microscopy confirmed the selective aggregation of protein molecules towards the irradiated areas. In addition, the attachment of b-BSA was detected by a reaction with fluorescently labelled avidin-fluorescein isothiocyanate (Av-FITC). In contrast to chemically oxidized graphene, laser-induced oxidation introduces the capability for localization on oxidized areas and tunability of the levels of oxidation, resulting in controlled guidance of proteins by light over graphene surfaces and progressing towards graphene microchips suitable for biomedical applications.

Photoactive Yellow Protein Chromophore Photoisomerizes around a Single Bond if the Double Bond Is Locked.

Photoactivation in the Photoactive Yellow Protein, a bacterial blue-light photoreceptor, proceeds via photoisomerization of the double C═C bond in the covalently attached chromophore. Quantum chemistry calculations, however, have suggested that in addition to double-bond photoisomerization, the isolated chromophore and many of its analogues can isomerize around a single C-C bond as well. Whereas double-bond photoisomerization has been observed with X-ray crystallography, experimental evidence of single-bond photoisomerization is currently lacking. Therefore, we have synthesized a chromophore analogue, in which the formal double bond is covalently locked in a cyclopentenone ring, and carried out transient absorption spectroscopy experiments in combination with nonadiabatic molecular dynamics simulations to reveal that the locked chromophore isomerizes around the single bond upon photoactivation. Our work thus provides experimental evidence of single-bond photoisomerization in a photoactive yellow protein chromophore analogue and suggests that photoisomerization is not restricted to the double bonds in conjugated systems. This insight may be useful for designing light-driven molecular switches or motors.

Optically Forged Diffraction-Unlimited Ripples in Graphene.

In nanofabrication, just as in any other craft, the scale of spatial details is limited by the dimensions of the tool at hand. For example, the smallest details of direct laser writing with far-field light are set by the diffraction limit, which is approximately half of the used wavelength. In this work, we overcome this universal assertion by optically forging graphene ripples that show features with dimensions unlimited by diffraction. Thin sheet elasticity simulations suggest that the scaled-down ripples originate from the interplay between substrate adhesion, in-plane strain, and circular symmetry. The optical forging technique thus offers an accurate way to modify and shape 2D materials and facilitates the creation of controllable nanostructures for plasmonics, resonators, and nano-optics.

Three-Dimensional Printing of Nonlinear Optical Lenses.

In the current paper, a series of nonlinear optical (NLO) active devices was prepared by utilizing stereolithographic three-dimensional printing technique. Microcrystalline NLO active component, urea, or potassium dihydrogen phosphate was dispersed in a simple photopolymerizable polyacrylate-based resin and used as the printing material to fabricate highly efficient transparent NLO lenses. The nonlinear activity of the printed lenses was confirmed by second-harmonic generation measurements using a femtosecond laser-pumped optical parametric amplifier operating at a wavelength of 1195 nm. The three-dimensional printing provides a simple method to utilize a range of NLO active compounds without tedious crystal growing and processing steps. Furthermore, introducing NLO additives in the printing material provides an easy and cost-efficient way to manufacture lenses with NLO functionality.

Optical Forging of Graphene into Three-Dimensional Shapes.

Atomically thin materials, such as graphene, are the ultimate building blocks for nanoscale devices. But although their synthesis and handling today are routine, all efforts thus far have been restricted to flat natural geometries, since the means to control their three-dimensional (3D) morphology has remained elusive. Here we show that, just as a blacksmith uses a hammer to forge a metal sheet into 3D shapes, a pulsed laser beam can forge a graphene sheet into controlled 3D shapes in the nanoscale. The forging mechanism is based on laser-induced local expansion of graphene, as confirmed by computer simulations using thin sheet elasticity theory.

Time-Resolved Coherent Anti-Stokes Raman Scattering of Graphene: Dephasing Dynamics of Optical Phonon.

We report dynamics of the G-mode in graphene probed with time-resolved coherent anti-Stokes Raman scattering measurements. By applying BOXCARS excitation geometry with three different excitation wavelengths, various nonlinear processes can be selectively detected due to energy and momentum conservation and temporal sequence of the pulses. The Raman signal due to resonant coherent excitation of the G-mode shows exponential decay with lifetime of ∼325 ± 50 fs. This decay time is shorter than expected based on the line width of the G-mode in the Raman spectrum. We propose that the unexpectedly short dephasing time is a result of dynamic variation of nonadiabatic coupling of the photoexcited electron distribution and the G-mode.

Molecule-like photodynamics of Au102(pMBA)44 nanocluster.

Photophysical properties of a water-soluble cluster Au102(pMBA)44 (pMBA = para-mercaptobenzoic acid) are studied by ultrafast time-resolved mid-IR spectroscopy and density functional theory calculations in order to distinguish between molecular and metallic behavior. In the mid-IR transient absorption studies, visible or near-infrared light is used to electronically excite the sample, and the subsequent relaxation is monitored by studying the transient absorption of a vibrational mode in the ligands. Based on these studies, a complete picture of energy relaxation dynamics is obtained: (1) 0.5-1.5 ps electronic relaxation, (2) 6.8 ps vibrational cooling, (3) intersystem crossing from the lowest triplet state to the ground state with a time constant 84 ps, and (4) internal conversion to the ground state with a time constant of ∼3.5 ns. A remarkable finding based on this work is that a large cluster containing 102 metal atoms behaves like a small molecule in a striking contrast to a previously studied slightly larger Au144(SC2H4Ph)60 cluster, which shows relaxation typical for metallic particles. These results therefore establish that the transition between molecular and metallic behavior occurs between Au102 and Au144 species.

Role of vibrational dynamics in electronic relaxation of Cr(acac)3.

Ultrafast energy relaxation of Cr(acac)3 dissolved in tetrachloroethylene (TCE) is studied by time-resolved infrared (TRIR) spectroscopy by using electronic and vibrational excitation. After electronic excitation at 400 or 345 nm, the ground state recovers in two time scales: 15 ps (major pathway) and 800 ps (minor pathway), corresponding to fast electronic transition to the ground state and intermediate trapping on the long-lived (2)E state followed by intersystem crossing (ISC) to the ground state. The quantum yield for the fast recovery of the ground state depends on the excitation wavelength, being higher for 345 nm. Vibrational cooling (VC) occurs on the electronic excited states with a time constant of ∼7 ps and on the ground electronic state with a time constant of ∼12 ps. A kinetic model that explains the observed dynamics is presented. The key point of the model is that the ground-state recovery occurs via thermally activated back-intersystem-crossing (b-ISC) to the quartet manifold presumably via multiple curve crossings that are sampled while the system is vibrationally hot. This underlines the importance of vibrational cooling as a determining factor for the electronic relaxation chain. Vibrational excitation of the νC═C and νCO vibrations also revealed a subpicosecond (300-700 fs) intramolecular vibrational redistribution (IVR) process from the localized vibrational states to the bath of vibrational excitations.

Local photo-oxidation of individual single walled carbon nanotubes probed by femtosecond four wave mixing imaging.

Photo-oxidation of individual, air-suspended single walled carbon nanotubes (SWCNTs) is studied by femtosecond laser spectroscopy and imaging. Individual SWCNTs are imaged by four wave mixing (FWM) microscopy under an inert gas (Ar or N2) atmosphere. When imaging is performed in an ambient air atmosphere, the decay of the FWM signal takes place. Electron microscopy shows that SWCNTs are not destroyed and the process is attributed to photoinduced oxidation reactions which proceed via a non-linear excitation mechanism, when irradiation is performed with ∼30 fs pulses in the visible spectral region (500-600 nm). Photo-oxidation can be localized in specific regions of SWCNTs within optical resolution (∼300 nm). The effect of photo-oxidation on Raman spectra was studied by irradiating a local spot on an individual SWCNT and comparing the spectra of irradiated and non-irradiated regions of the same tube. It is shown at an individual nanotube level that oxidation leads to a decrease of the intensity of the Raman signal and an upshift of the G-band.

Patterning and tuning of electrical and optical properties of graphene by laser induced two-photon oxidation.

We demonstrate a simple all-optical patterning method for graphene, based on laser induced two-photon oxidation. By tuning the intensity and dose of irradiation, the level of oxidation is controlled, the band gap is introduced and electrical and optical properties are continuously tuned. Complex patterning is performed for air-suspended monolayer graphene and for graphene on substrates. The presented concept allows development of all-graphene electronic and optoelectronic devices with an all-optical method.

Chemically selective imaging of overlapping C-H stretching vibrations with time-resolved coherent anti-stokes Raman scattering (CARS) microscopy.

Chemically selective imaging of spectrally overlapping compounds is studied with a time-resolved, femtosecond approach on coherent anti-Stokes Raman scattering (CARS) microscopy taking advantage of time-dependent oscillating CARS amplitude which is sensitive to different chemical components at different time points. Chemically selective imaging is demonstrated for composite material of polypropylene (PP) matrix and om-POSS (octamethyl polyhedral oligomeric silsesquioxane) microparticles having partly overlapping CH stretching vibrations. Inverse Fourier transformation (IFT) was applied to Raman spectra of PP and om-POSS, indicating that the oscillatory structures of the vibrational decays differ markedly and allow selective imaging, with minimally using one time point per spatial point, which is also confirmed by the CARS measurements. CARS decays measured additionally for lipid films of cholesterol and DOPC (1,2-dioleyl-sn-glycero-3-phosphocholine) indicate selective detection of cholesterol at a specific probe delay time. The results of this study show that the tr-CARS technique has potential for chemically selective, nonresonant background free imaging using overlapping vibrations.

Electronic spectroscopy of I(2)-Xe complexes in solid Krypton.

In the present work, we have studied ion-pair states of matrix-isolated I(2) with vacuum-UV absorption and UV-vis-NIR emission, where the matrix environment is systematically changed by mixing Kr with Xe, from pure Kr to a more polarizable Xe host. Particular emphasis is put on low doping levels of Xe that yield a binary complex I(2)-Xe, as verified by coherent anti-Stokes Raman scattering (CARS) measurements. Associated with interaction of I(2) with Xe we can observe strong new absorption in vacuum-UV, redshifted 2400 cm(-1) from the X → D transition of I(2). Observed redshift can be explained by symmetry breaking of ion-pair states within the I(2)-Xe complex. Systematic Xe doping of Kr matrices shows that at low doping levels, positions of I(2) ion-pair emissions are not significantly affected by complexation with Xe, but simultaneous increase of emissions from doubly spin-excited states indicates non-radiative relaxation to valence states. At intermediate doping levels ion-pair emissions shift systematically to red due to change in the average polarizability of the environment. We have conducted spectrally resolved ultrafast pump-probe ion-pair emission studies with pure and Xe doped Kr matrices, in order to reveal the influence of Xe to I(2) dynamics in solid Kr. Strikingly, relaxed emission from the ion-pair states shows no indication of complex presence. It further indicates that the complex escapes detection due to a non-radiative relaxation.

Excitation energy transfer in isolated chlorosomes from Chlorobaculum tepidum and Prosthecochloris aestuarii.

Excitation energy transfer in chlorosomes from photosynthetic green sulfur bacteria, Chlorobaculum (Cba.) tepidum and Prosthecochloris (Pst.) aestuarii, have been studied at room temperature by time-resolved femtosecond transient absorption spectroscopy. Bleach rise times from 117 to 270 fs resolved for both chlorosomes reflect extremely efficient intrachlorosomal energy transfer. Bleach relaxation times, from 1 to 3 ps and 25 to 35 ps, probed at 758 nm were tentatively assigned to intrachlorosomal energy transfer based on amplitude changes of the global fits and model calculations. The anisotropy decay constant of about 1 ps resolved at 807 nm probe wavelength for the chlorosomes from Chloroflexus aurantiacus, Pst. aestuarii and Cba. tepidum was related to energy transfer between bacteriochlorophyll a molecules of the baseplate and partly to intrachlorosomal energy transfer. The longer anisotropy components 6.6, 8.8 and 12.1 ps resolved for the three chlorosomes, respectively, were assigned to chlorosome to baseplate energy transfer. Global fits of magic-angle data also revealed longer chlorosome to baseplate energy transfer components from 95 to 135 ps, in accord with results from simulations.