A two-dimensional molecular sieve has been realized. It consists of a host matrix of molecularly engineered building blocks self-assembled at the liquid-solid interface. The simultaneous size- and shape-dependent dynamics of different guest molecules is observed in situ, in real time with submolecular resolution using a scanning tunneling microscope both at the liquid-solid interface and under vacuum. The temperature-dependent dynamics reveals that the diffusion proceeds through thermally activated channeling between single-molecule surface cavities.
Spontaneous formation of hexagonal surface relief patterns (see Figure) occurs upon uniform, coherent laser irradiation of a poly‐(methylmethacrylate) with 35 % of the methyl ester groups replaced by an azo dye. The structures grow at a rate linearly dependent on the light intensity, above a threshold value. Using linearly polarized light, the elongation axis of the structures orients along the polarization direction.
We report on the design and synthesis of two-photon fluorescent triphenylamines bearing two or three vinyl branches terminated by a N-methyl benzimidazolium moiety. The new compounds (TP-2Bzim, TP-3Bzim) are light-up fluorescent DNA probes with a long wavelength emission (>580 nm). Compared to their pyridinium models, the TP-Bzim dyes exhibit a remarkable improvement of both their DNA affinity and fluorescence quantum yield, especially for the two-branch derivative (TP-2Bzim: ΦF = 0.54, Ka = 10(7) M(-1)), resulting in a large fluorescence emission turn-on ratio of up to 140. Concomitantly, the two-photon absorption cross-section of TP-2Bzim is dramatically enhanced upon DNA binding (δ = 1080 vs 110 GM for the free form). This effect of the DNA matrix on the nonlinear absorption is uncovered for the first time. This is attributed to a tight fit of the molecule inside the minor groove of AT-rich DNA which induces geometrical rearrangements in the dye ground state as supported by circular dichroism and molecular modeling data. Consequently, TP-2bzim displays an exceptional two-photon molecular brightness (δ×ΦF = 583 GM), a value unrivalled for a small biofluorophore. These properties enable to image nuclear DNA in fixed cells at submicromolar concentration ([TP-2Bzim] = 100 nM) and to visualize ultrabright foci of centromeric AT-rich chromatin. Finally TP-2Bzim exhibits a high photostability, is live-cell permeant, and does not require RNase treatment. This outstanding combination of optical and biological properties makes TP-2Bzim a bioprobe surpassing the best DNA stainers and paves the way for studying further nonlinear optical processes in DNA.
A series of mono-, bis- and trisvinyl-pyridinium triphenylamines (TP-py) has been synthesised and evaluated for its one- and two-photon absorption (2PA) induced-fluorescence properties under biological conditions. Interestingly, these compounds are only weakly fluorescent in water, whereas their fluorescence emissions are strongly restored (exaltation factors of 20-100) upon binding to double-stranded DNA. Additional measurements in glycerol indicate that the fluorescence increases are the result of immobilisation of the dyes in the DNA matrix, which inhibits rotational de-excitation modes. This particular feature is especially remarkable in the case of the bis and tris derivatives (TP-2 py, TP-3 py), which each display a high affinity (K(d) ~ microM) for dsDNA. TPIF measurements have shown that TP-2 py and TP-3 py each have a large 2PA cross section (delta up to 700 GM) both in glycerol and in the presence of DNA, which ranks them amongst the best 2PA biological fluorophores. Finally, one- and two-photon confocal imaging in cells revealed that these compounds perform red staining (lambda(em)=660-680 nm) of nuclear DNA with excellent contrast. The remarkable optical properties of the TP-py series, combined with their high photostability and their easy synthetic access, make these compounds extremely attractive for use in confocal and 2PA microscopy.
A versatile synthetic strategy to access a set of highly fluorescent pi-conjugated triphenylamines bearing a functional linker at various positions on one phenyl ring is described. These compounds were designed for large two-photon absorption (2PA) and in particular for labeling of biomolecules. The monoderivatized trisformylated or trisiodinated intermediates described herein allow introduction of a large variety of electron-withdrawing groups required for large 2PA as well as a panel of chemical functions suitable for coupling to biomolecules. The monoderivatized three-branched compounds and in particular the benzothiazole (TP-3Bz) series show remarkable linear (high extinction coefficients and high quantum yield) and nonlinear (high 2-photon cross sections) optical properties. Interestingly the presence of functional side chains does not disturb the two-photon absorption. Finally, monoderivatized two-branched derivatives also appear to be valuable candidates. Altogether the good optical properties of the new derivatizable pi-conjugated TPA combined with their small size and their compatibility with bioconjugation protocols suggest that they represent a new chemical class of labels potentially applicable for the tracking of biomolecules using two-photon scanning microscopy.
A nanoengineered surface able to grab selected molecules and further sort them according to their size and shape by diffusion through surface molecular sieves is realized. It consists of a customized self‐assembled network of supramolecular cavities linked by channels. The comparison of the temperature‐dependent hopping dynamics of various guest molecules (arrows in figure indicate their hopping between neighboring cavities; figure width: 7.7 nm) reveals the physical mechanisms of the involved processes.
Submicrometric periodic patterning of an organic solar cell surface is investigated in order to optimize the photovoltaic conversion efficiency of the device. Patterning is achieved using a single-step all-optical technique based on photoinduced mass transport in azopolymer films. The polymer film with a structured surface is used as a substrate for an organic solar cell based on a copper phthalocyanine/C60 heterojunction. The effect of periodic patterning is investigated through the solar-cell optical-absorption properties and external quantum efficiency measurements. The possibility to increase the short circuit current density and the corresponding photovoltaic conversion efficiency is evidenced with one-dimensional periodic structures.
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