Sparse-coding denoising applied to reversible conformational switching of a porphyrin self-assembled monolayer induced by scanning tunnelling microscopy.

Scanning tunnelling microscopy (STM) was used to induce conformational molecular switching on a self-assembled monolayer of zinc-octaethylporphyrin on a graphite/tetradecane interface at room temperature. A reversible conformational change controlled by applying a tip voltage was observed. Consecutive STM images acquired at alternating tip voltages showed that at 0.4 V the porphyrin monolayer presents a molecular arrangement formed by alternate rows with two different types of structural conformations and when the potential is increased to 0.7 V the monolayer presents only one type of conformation. In this paper, we characterize these porphyrin conformational dynamics by analyzing the STM images, which were improved for better quality and interpretation by means of a denoising algorithm, adapted to process STM images from state of the art image processing and analysis methods. STM remains the best technique to 'see' and to manipulate the matter at atomic scale. A very sharp tip a few angstroms of the surface can provide images of molecules and atoms with a powerful resolution. However, these images are strongly affected by noise which is necessary to correct and eliminate. This paper is about new computational tools specifically developed to denoise the images acquired with STM. The new algorithms were tested in STM images, obtained at room temperature, of porphyrin monolayer which presents reversible conformational change in function of the tip bias voltage. Images with high resolution, acquired in real time, show that the porphyrins have different molecular arrangements whether the tip voltage is 0.4 V or 0.7 V.

Triplet-state and singlet oxygen formation in fluorene-based alternating copolymers.

Data are reported on the triplet states of a series of fluorene-based A-alt-B type alternating copolymers based on pulse radiolysis-energy transfer and flash photolysis experiments. From the pulse radiolysis experiments, spectra are given for eight copolymers involving phenylene, thiophene, benzothiadiazole, and oligothienylenevinylene groups. Quantum yields for triplet-state formation (PhiT) have been obtained by flash photolysis following laser excitation and in one case by photoacoustic calorimetry. In addition, yields of sensitized formation of singlet oxygen have been determined by time-resolved phosphorescence and are, in general, in excellent agreement with the PhiT values. In all cases, the presence of thiophene units is seen to increase intersystem-crossing quantum yields, probably because of the presence of the heavy sulfur atom. However, with the poly[2,7-(9,9-bis(2'-ethylhexyl)fluorene)-alt-1,4-phenylene] (PFP), thiophene S,S-dioxide (PFTSO2) and benzothiadiazole (F8BT) copolymers, low yields of triplet formation are observed. With three of the copolymers, the energies of the triplet states have been determined. With PFP, the triplet energy is virtually identical to that of poly[2,7-(9,9-bis(2'-ethylhexyl)fluorene)]. In contrast, with fluorene-thiophene copolymers PFaT and PF3T, the triplet energies are closer to those of thiophene oligomers, indicating that there is significant conjugation between fluorene and thiophene units but also that there is a more localized triplet state than with the homopolymers.