A comprehensive theoretical study of the reaction mechanisms for the conversion between spiropyrans (SPs) and the open form of merocyanines (MCs) has been conducted by theoretical calculations. The reaction mechanisms on the ground-and triplet-state potential energy surfaces (PESs) were investigated using the density functional method. Time-dependent density functional theory (TD-DFT) calculations using the CIS optimized excited-state geometries were carried out to study the reaction mechanisms on the lowest excited singlet-state PES. Two possible reaction mechanisms for the thermal conversion between SPs to MCs were found on the ground-state PES. The geometrical parameter, BLA (Bond Length Alternation), which correlates the strengths of the substituents and the polarities of solvents, was used to explain the changes in the reaction mechanism induced by the different donor-acceptor pairs and solvents. In addition, the reaction mechanisms of spiropyran/merocyanine conversion on the triplet and the lowest excited singlet potential energy surfaces were also studied; several possible reaction mechanisms on the excited-state PESs were proposed. A comprehensive mechanistic view of the ultrafast photochemistry of spiropyrans was revealed and interpreted in terms of the strengths of substituents and the polarity of solvents.

A coating of photoresponsive spiropyran molecules covalently bound to a glass surface along with a mixture of organosilanes to control the surface environment was prepared. The relatively nonpolar spiropyran can be reversibly switched to a polar, zwitterionic merocyanine isomer that has a much larger dipole moment by UV light, and back again by visible light. The contact angle was 11°-14°lower for dry, spiropyrancoated surfaces after irradiation with UV than that for dry, spiropyran-coated surfaces after irradiation with visible light. The light-induced changes observed in the surface energy were correlated to the switching of the surface-bound spiropyran molecule between polar and nonpolar forms by means of fluorescence spectroscopy and epifluorescence microscopy. Water in capillary tubes coated with the photosensitive layer was observed to rise when the wavelength of incident light was switched from visible to UV. The UVinduced rise was of the order of 2.8 mm for a 500 µm diameter capillary. This microfluidic actuation of water in an enclosed capillary or microchannel using light is termed "photocapillarity". Contact angle hysteresis prevented the water from flowing back down the capillary when the light was switched from UV back to visible.

Aqueous suspension droplets of monodisperse latex or latex and gold nanoparticles mixtures assume spherical shape on superhydrophobic substrates. The drying sessile droplets serve as macroscopic templates for assembling microspheres into closed‐packed structures. Upon illumination, the supraparticles display discrete colored rings because of the periodic arrangement of latex particles in the surface layer. The physical origin of the colored patterns is explained in detail.

A rough surface morphology is shown to significantly amplify the light-induced change in water contact angle of a photoresponsive surface. Smooth Si surfaces and fractally rough Si nanowire surfaces grown on a Si substrate were studied, both coated with a hydrophobic monolayer containing photochromic spiropyran molecules. Under visible irradiation the spiropyran is in a closed, hydrophobic form, whereas UV irradiation converts the spiropyran to a polar, hydrophilic form, reducing the contact angle. The superhydrophobic nanowire surface both amplifies the light-induced contact angle change by a factor of 2 relative to a smooth surface and reduces the contact angle hysteresis. As a result the UV-induced advancing contact angle is lower than the receding contact angle under visible irradiation, allowing water drops to be moved solely under the influence of a UV−visible light gradient. The amplification of the reversible light-induced wetting angle change was predicted using the Wenzel model for fractally rough surfaces. The model and amplification effects are expected to apply to other types of stimuli-induced contact angle changes such as that by heat or electrical potentials.

A small-volume heterogeneous immunoassay system is demonstrated in microchannels exploiting magnetic manipulations of small paramagnetic particles (1-2-microm diameter). The small-diameter particles help to create a high surface-area-to-volume ratio that generates the sensitivity for the small detection volumes. Flow characteristics of the magnetically formed packed bed within the channel allow the assay to be carried out quickly (minutes) while passing appropriate volumes of both samples and reagents (microliters to hundreds of nanoliters) through the system. The assay is demonstrated with a direct interaction of fluorescein isothiocyanate (FITC) with an immobilized anti-FITC conjugate in which a small-volume sample (< 1 microL) reaches 90% of maximum signal in 3 min. Heterogeneous sandwich assays are demonstrated with parathyroid hormone (PTH) and interleukin-5 (IL-5). Both the PTH assay and IL-5 assays were carried out on microliter volumes and demonstrated physiologically relevant sensitivity (approximately microg/L).

Microgels with photo-, thermally, and pH-responsive properties in aqueous suspension have been synthesized and characterized using dynamic light scattering and UV-visible spectroscopy. The new route involved first preparing poly(N-isopropylacrylamide) (PNIPAM)-allylamine copolymer microgels and a spiropyran photochrome (SP) bearing a carboxylic acid group. Then the functionalized spiropyran was coupled to the microgel via an amide bond. The dark-equilibrated gel particles feature spiropyran molecules in the polar, merocyanine form. After irradiation of visible light, the particle size becomes smaller because spiropyran changes to the relatively nonpolar, closed spiro form. The PNIPAM-SP microgels undergo a volume phase transition in water from a swollen state to a collapsed state with increasing temperature under all light conditions. However, the transition temperature range of the PNIPAM-SP is much broader than that for the PNIPAM without SP. The PNIPAM-SP microgels are monodisperse and self-assemble into a crystalline lattice while in suspension. The UV-visible spectra of an aqueous suspension of PNIPAM-SP microgel in the dark-adapted, merocyanine form showed both an absorption peak around 512 nm due to the merocyanine (giving a reddish color to the suspension) and two sharp peaks from Bragg diffraction of colloidal crystallites. Upon visible irradiation, the 512-nm band bleached significantly due to spiropyran photoisomerization. The spiropyran photoisomerization and accompanying color changes of the suspension were reversible upon alternating dark, UV, and visible light irradiation. Due to the residues of amine groups, the swelling capability of PNIPAM-SP microgels reduces as the pH value is changed from 7 to 10.

We demonstrate how droplet templates dispensed on superhydrophobic substrates can be used to fabricate both shape-anisotropic ("doughnut") and composition-anisotropic ("patchy magnetic") supraparticles. The macroscopic shape of the closely-packed particle assemblies is guided by the droplet meniscus. Aqueous droplets of monodisperse microsphere suspensions dispensed on the substrates initially acquire near-spherical shape due to a high contact angle. During the solvent evaporation, however, silica suspension droplets undergo shape transitions (concaving) guiding the structure of the final assemblies into doughnut supraparticles. Composition anisotropy is achieved by drying a droplet containing a mixed suspension of latex and magnetic nanoparticles, while exposing it to magnetic field gradients. Depending on the pattern of the magnetic fields, the magnetic nanoparticles segregate into single, bilateral, or trilateral, patched spherical supraparticles. The physical effects leading to the development of anisotropy are discussed. Unlike the conventional wet self-assembly (WSA) methods where the final structures need to be extracted from the liquid environment, this efficient one-step procedure produces ready to use "dry" supraparticles.

The movement of a liquid droplet on a flat surface functionalized with a photochromic azobenzene may be driven by the irradiation of spatially distinct areas of the drop with different UV and visible light fluxes to create a gradient in the surface tension. In order to better understand and control this phenomenon, we have measured the wetting characteristics of these surfaces for a variety of liquids after UV and visible light irradiation. The results are used to approximate the components of the azobenzene surface energy under UV and visible light using the van Oss-Chaudhury-Good equation. These components, in combination with liquid parameters, allow one to estimate the strength of the surface interaction as given by the advancing contact angle for various liquids. The azobenzene monolayers were formed on smooth air-oxidized Si surfaces through 3-aminopropylmethyldiethoxysilane linkages. The experimental advancing and receding contact angles were determined following azobenzene photoisomerization under visible and ultraviolet (UV) light. Reversible light-induced advancing contact-angle changes ranging from 8 to 16 degrees were observed. A large reversible change in contact angle by photoswitching of 12.4 degrees was achieved for water. The millimeter-scale transport of 5 microL droplets of certain liquids was achieved by creating a spatial gradient in visible/UV light across the droplets. A criterion for light-induced motion of droplets is shown to be consistent with the response of a variety of liquids. The type of light-driven fluid movement observed could have applications in microfluidic devices.