Effective techniques to reduce graphene oxide are in demand owing to the multitude of potential applications of this two-dimensional material. A very promising green method to do so is by exposure to ultraviolet irradiation. Unfortunately, the dynamics behind this reduction remain unclear. Here we perform a series of transient absorption experiments in an effort to develop and understand this process on a fundamental level. An ultrafast photoinduced chain reaction is observed to be responsible for the graphene oxide reduction. The reaction is initiated using a femtosecond ultraviolet pulse that photoionizes the solvent, liberating solvated electrons, which trigger the reduction. The present study reaches the fundamental time scale of the ultraviolet photoreduction in solution, which is revealed to be in the picosecond regime.
Förster resonance energy transfer (FRET) is a powerful optical technique to determine intra-molecular distances. However, the dye rotational motion and the linker flexibility complicate the relationship between the measured energy transfer efficiency and the distance between the anchoring points of the dyes. In this study, we present a simple model that describes the linker and dye dynamics as diffusion on a sphere. Single-pair energy transfer was treated in the weak excitation limit, photon statistics and scaffold flexibility were ignored, and different time-averaging regimes were considered. Despite the approximations, our model provides new insights for experimental designs and results interpretation in single-molecule FRET. Monte Carlo simulations produced distributions of the inter-dye distance, the dipole orientation factor, κ(2), and the transfer efficiency, E, which were in perfect agreement with independently derived theoretical functions. Contrary to common perceptions, our data show that longer linkers will actually restrict the motion of dye dipoles and hence worsen the isotropic 2∕3 approximation of κ(2). It is also found that the thermal motions of the dye-linker system cause fast and large efficiency fluctuations, as shown by the simulated FRET time-trajectories binned on a microsecond time scale. A fundamental resolution limit of single-molecule FRET measurements emerges around 1-10 μs, which should be considered for the interpretation of data recorded on such fast time scales.
Keeping harm at bay: In an in vitro strategy to prevent the cellular motility of oncogenic STAT3 protein, protein–membrane anchorage was induced by the use of a rationally designed cholesterol‐based protein–membrane anchor in breast‐tumor cells. (The fluorescence image shows the localization of the protein to the liposome boundary of a multilamellar vesicle.)
A compact electron source specifically designed for time-resolved diffraction studies of free-standing thin films and monolayers is presented here. The sensitivity to thin samples is achieved by extending the established technique of ultrafast electron diffraction to the “medium” energy regime (1–10 kV). An extremely compact design, in combination with low bunch charges, allows for high quality diffraction in a lensless geometry. The measured and simulated characteristics of the experimental system reveal sub-picosecond temporal resolution, while demonstrating the ability to produce high quality diffraction patterns from atomically thin samples.
Reversibility is an important issue that prevents ultrafast studies of chemical reactions in solid state due to product accumulation. Here we present an approach that makes use of spectrally-selected, post-excitation, ultrashort laser pulses to minimise photoproduct build-up, i.e. recover before destroy. We demonstrate that this method enabled us to probe the ultrafast dynamics of the ring opening reaction of spironaphthooxazine thin crystals by means of transient absorption spectroscopy. By extension, this approach should be amenable to other photochromic systems and use with structural probes
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