Chemical force microscopy (CFM) in water was used to map the surface hydrophobicity of UV/ozone-treated poly(dimethylsiloxane) (PDMS; Sylgard 184) as a function of the storage/recovery time. In addition to CFM pull-off force mapping, we applied indentation mapping to probe the changes in the normalized modulus. These experiments were complemented by results on surface properties assessed on the micrometer scale by X-ray photoelectron spectroscopy and water contact-angle measurements. Exposure times of < or = 30 min resulted in laterally homogeneously oxidized surfaces, which are characterized by an increased modulus and a high segmental mobility of PDMS. As detected on a sub-50-nm level, the subsequent "hydrophobic recovery" was characterized by a gradual increase in the pull-off forces and a decrease in the normalized modulus, approaching the values of unexposed PDMS after 8-50 days. Lateral imaging on briefly exposed PDMS showed the appearance of liquid PDMS in the form of droplets with an increasing recovery time. Longer exposure times (60 min) led to the formation of a hydrophilic silica-like surface layer. Under these conditions, a gradual surface reconstruction within the silica-like layer occurred with time after exposure, where a hydrophilic SiOx-enriched phase formed < 100-nm-sized domains, surrounded by a more hydrophobic matrix with lower normalized modulus. These results provide new insights into the lateral homogeneity of oxidized PDMS with a resolution in the sub-50-nm range.

Long-term noninvasive cell tracing by fluorescent probes is of great importance to life science and biomedical engineering. For example, understanding genesis, development, invasion and metastasis of cancerous cells and monitoring tissue regeneration after stem cell transplantation require continual tracing of the biological processes by cytocompatible fluorescent probes over a long period of time. In this work, we successfully developed organic far-red/near-infrared dots with aggregation-induced emission (AIE dots) and demonstrated their utilities as long-term cell trackers. The high emission efficiency, large absorptivity, excellent biocompatibility, and strong photobleaching resistance of the AIE dots functionalized by cell penetrating peptides derived from transactivator of transcription proteins ensured outstanding long-term noninvasive in vitro and in vivo cell tracing. The organic AIE dots outperform their counterparts of inorganic quantum dots, opening a new avenue in the development of fluorescent probes for following biological processes such as carcinogenesis.

Ultrabright organic dots with aggregation-induced emission characteristics (AIE dots) are prepared and shown to exhibit a high quantum yield, a, large two-photon absorption cross-section, and low in vivo toxicity. Real-time two-photon intravital blood vascular imaging in various tissues substantiates that the AIE dots are effective probes for in vivo vasculature imaging in a deep and high-contrast manner.

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Molecular electronic control over plasmons offers a promising route for on-chip integrated molecular plasmonic devices for information processing and computing. To move beyond the currently available technologies and to miniaturize plasmonic devices, molecular electronic plasmon sources are required. Here, we report on-chip molecular electronic plasmon sources consisting of tunnel junctions based on self-assembled monolayers sandwiched between two metallic electrodes that excite localized plasmons, and surface plasmon polaritons, with tunnelling electrons. The plasmons originate from single, diffraction-limited spots within the junctions, follow power-law distributed photon statistics, and have well-defined polarization orientations. The structure of the self-assembled monolayer and the applied bias influence the observed polarization. We also show molecular electronic control of the plasmon intensity by changing the chemical structure of the molecules and by bias-selective excitation of plasmons using molecular diodes.S urface plasmon polaritons (SPPs) confine and enhance local electromagnetic fields near surfaces of metallic nanostructures at optical frequencies and have the ability to propagate along subdiffractive metallic waveguides, thereby opening up new perspectives for integrated optoelectronic circuits at the nanoscale 1-4 . However, almost all these applications use large external light sources such as monochromatic lasers. To minimize the size of the light sources and ultimately the size of the plasmonic devices, plasmons have been excited on-chip using electrically driven light sources such as (organic) light-emitting diodes (LEDs) 5-8 , laser diodes 9 , silicon spheres 10 and single carbon nanotubes 11 instead of bulky lasers. Surface plasmons have also been directly excited by tunnelling electrons in metal-insulator-metal junctions based on metal oxides 12-14 or scanning tunnelling microscopes (STMs) using vacuum or molecular tunnelling barriers [15][16][17][18][19][20][21][22][23][24][25] . During the tunnelling process, most of the electrons tunnel elastically, but some tunnel inelastically and couple to a plasmon mode. Direct excitation of plasmons by tunnelling electrons is attractive because not only is no background light generated but potentially it is also fast 26 (on the timescale of quantum tunnelling) as no slow electron-hole recombination processes are required as is the case for electroluminescent (nano)light sources 5-11 . Here, we report a direct electronic plasmon source based on molecular tunnel junctions operating via throughmolecular-bond tunnelling, where the plasmonic properties can be electrically controlled at the molecular level (without the need for optical antennas 27,28 ).In molecular electronic devices, the tunnelling barrier height is defined by the electronic energy levels of the molecule(s) bridging two electrodes. The tunnelling barrier width is defined by the length of the bridging molecule. Hence, the tunnelling gaps in molecular electronic devices are always exact...

Ttrioctylphosphine oxide (TOPO) stabilized CdSe/ZnS quantum dots (QD) were modified with 6-ferrocenyl-1-hexanethiol (FcHT) or 11-ferrocenyl-1-undecanethiol (FcUT) via ligand exchange. The presence of ferrocenyl thiol ligands on the surface of the QDs was proven by diffusion ordered NMR spectroscopy. Upon replacement of the initial TOPO ligand with ferrocene derivatives the emission of the QDs decreased. Phase transfer of ferrocene-modified QDs from organic solvents into water was achieved by complexation reactions with beta-cyclodextrin (beta-CD). The QDs coated with ferrocene thiols are soluble in nonpolar solvents and are transferred into the aqueous phase upon formation of host-guest complexes between the ferrocene units and the cavity of beta-CD. The reversibility of the phase transfer was probed by the addition of naphthalene and adamantane derivatives to the aqueous phase containing QD-[Fc-CD] adduct.

We present a single molecule fluorescence study that allows one to probe the nanoscale segmental dynamics in amorphous polymer matrices. By recording single molecular lifetime trajectories of embedded fluorophores, peculiar excursions towards longer lifetimes are observed. The asymmetric response is shown to reflect variations in the photonic mode density as a result of the local density fluctuations of the surrounding polymer. We determine the number of polymer segments involved in a local segmental rearrangement volume around the probe. A common decrease of the number of segments with temperature is found for both investigated polymers, poly(styrene) and poly(isobutylmethacrylate). Our novel approach will prove powerful for the understanding of the nanoscale rearrangements in functional polymers.

Monitoring and understanding long-term fate and regenerative therapy of administrated stem cells in vivo is of great importance. Herein we report organic nanodots with aggregation-induced emission characteristics (AIE dots) for long-term tracking of adipose-derived stem cells (ADSCs) and their regenerative capacity in living mice. The AIE dots possess high fluorescence (with a high quantum yield of 25±1%), excellent biological and photophysical stabilities, low in vivo toxicity, and superb retention in living ADSCs with negligible interference on their pluripotency and secretome. These AIE dots also exhibit superior in vitro cell tracking capability compared to the most popular commercial cell trackers, PKH26 and Qtracker 655. In vivo quantitative studies with bioluminescence and GFP labeling as the controls reveal that the AIE dots can precisely and quantitatively report the fate of ADSCs and their regenerative capacity for 42 days in an ischemic hind limb bearing mouse model.