No abstract

Activity and autonomous motion are fundamental in living and engineering systems. This has stimulated the new field of "active matter" in recent years, which focuses on the physical aspects of propulsion mechanisms, and on motility-induced emergent collective behavior of a larger number of identical agents. The scale of agents ranges from nanomotors and microswimmers, to cells, fish, birds, and people. Inspired by biological microswimmers, various designs of autonomous synthetic nano-and micromachines have been proposed. Such machines provide the basis for multifunctional, highly responsive, intelligent (artificial) active materials, which exhibit emergent behavior and the ability to perform tasks in response to external stimuli. A major challenge for understanding and designing active matter is their inherent nonequilibrium nature due to persistent energy consumption, which invalidates equilibrium concepts such as free energy, detailed balance, and time-reversal symmetry. Unraveling, predicting, and controlling the behavior of active matter is a truly interdisciplinary endeavor at the interface of biology, chemistry, ecology, engineering, mathematics, and physics.

The formation of nanoassemblies of CdSe/ZnS quantum dots (QD) and pyridyl-substituted free-base porphyrin (H(2)P) molecules has been spectroscopically identified by static and time-resolved techniques. The formation of nanoassemblies has been engineered by controlling the type and geometry of the H(2)P molecules. Pyridyl functionalization gives rise to a strong complex formation accompanied by QD photoluminescence (PL) quenching. For some of the systems, this quenching is partly related to fluorescence resonance energy transfer (FRET) from the QD to H(2)P and can be explained according to the Förster model. The quantitative interpretation of PL quenching due to complexation reveals that (i) on average only about (1)/(5) of the H(2)P molecules at a given H(2)P/QD molar ratio are assembled on the QD and (ii) only a limited number of "vacancies" accessible for H(2)P attachment exist on the QD surface.

Combining quantitative photothermal microscopy and light scattering microscopy as well as accurate MIE scattering calculations on single gold nanoparticles, we reveal that the mechanism of photothermal single-molecule/particle detection is quantitatively explained by a nanolensing effect. The lensing action is the result of the long-range character of the refractive index profile. It splits the focal detection volume into two regions. Our results lay the foundation for future developments and quantitative applications of single-molecule absorption microscopy.

A simple scheme is presented for remotely maneuvering individual microscopic swimmers by means of ondemand photo-induced actuation, where a laser gently and intermittently pushed the swimmer along its body axis (photon nudging) through a combination of radiation-pressure force and photophoretic pull.The proposed strategy utilized rotational random walks to reorient the micro-swimmer and turned on its propulsion only when the swimmer was aligned with the target location (adaptive control). A Langevin-type equation of motion was formulated, integrating these two ideas to describe the dynamics of the stochastically controlled swimmer. The strategy was examined using computer simulations and illustrated in a proof-of-principle experiment steering a gold-coated Janus micro-sphere moving in three dimensions. The physical parameters relevant to the two actuating forces under the experimental conditions were investigated theoretically and experimentally, revealing that a $7 K temperature differential on the micro-swimmer surface could generate a propelling photophoretic strength of $0.1 pN. The controllability and positioning error were discussed using both experimental data and Langevin dynamics simulations, where the latter was further used to identify two key unitless control parameters for manipulation accuracy and efficiency; they were the number of random-walk turns the swimmer experienced on the experimental timescale (the revolution number) and the photonnudge distance within the rotational diffusion time (the propulsion number). A comparison of simulation and experiment indicated that a near-optimal micron-precision motion control was achieved.

We derive the markovian description for the nonequilibrium brownian motion of a heated nanoparticle in a simple solvent with a temperature-dependent viscosity. Our analytical results for the generalized fluctuation-dissipation and Stokes-Einstein relations compare favorably with measurements of laser-heated gold nanoparticles and provide a practical rational basis for emerging photothermal tracer and nanoparticle trapping and tracking techniques.

We report on the first micro-scale observation of the velocity field imposed by a non-uniform heat content along the solid/liquid boundary. We determine both radial and vertical velocity components of this thermo-osmotic flow field by tracking single tracer nanoparticles. The measured flow profiles are compared to an approximate analytical theory and to numerical calculations. From the measured slip velocity we deduce the thermo-osmotic coefficient for both bare glass and Pluronic F-127 covered surfaces. The value for Pluronic F-127 agrees well with Soret data for polyethylene glycol, whereas that for glass differs from literature values and indicates the complex boundary layer thermodynamics of glass-water interfaces.

Time-resolved Stokes shift measurements and steady-state absorption and fluorescence measurements of Coumarin 153 (C153) at different temperatures were used to explore the solvation dynamics of binary mixtures of alcohols and alkanes at various alcohol concentrations. These solvent mixtures show even at alcohol concentrations as low as 0.3% a strong Stokes shift of about 1200 cm -1 . Depending on alcohol concentration, this Stokes shift takes place on a time scale ranging from 300 ps up to several nanoseconds. These characteristic times are 2 orders of magnitude longer than the relaxation times typically found in alcohols, which is attributed to rotational reorientation of the solvent molecules. A monoexponential temporal behavior of the Stokes shift and a linear dependence of the time constants on the alkane viscosity are observed. These results and temperature dependent static fluorescence measurements strongly support a diffusion-controlled process of solvation in these mixtures.