Electropolishing of Aluminum at Room Temperature Using a Green DES of Choline Chloride and Propylene Glycol.

For applications of aluminum where the smoothness or reflectivity of the aluminum matters, electropolishing is necessary to polish the aluminum surface sufficiently. This electropolishing is traditionally done with hazardous solutions in non-ideal conditions, such as low-temperature perchloric acid-ethanol mixtures. Here, we describe electropolishing of aluminum using a deep eutectic system composed of propylene glycol and choline chloride, with polishing accomplished at room temperature and using an inexpensive apparatus. This polishing was performed using both 99.5 and 99.99% pure aluminum, and scanning electron microscopy images show substantial improvement with both purities of aluminum. In addition, reflectivity measurements show significant improvement over sanding of aluminum. This method provides a simple, green method for electropolishing aluminum that can be used in any research where careful polishing of aluminum is necessary.

Multiphoton fabrication.

Chemical and physical processes driven by multiphoton absorption make possible the fabrication of complex, 3D structures with feature sizes as small as 100 nm. Since its inception less than a decade ago, the field of multiphoton fabrication has progressed rapidly, and multiphoton techniques are now being used to create functional microdevices. In this Review we discuss the techniques and materials used for multiphoton fabrication, the applications that have been demonstrated, as well as those being pursued. We also consider the outlook for this field, both in the laboratory and in industrial settings.

Selective functionalization of 3-D polymer microstructures.

We demonstrate the selective functionalization of 3-D polymer microstructures that were created using multiphoton absorption polymerization. By fabricating different portions of the structures with acrylic and methacrylic polymers, we are able to take advantage of the differential reactivities of these materials to perform functionalization chemistry on a single polymeric component. We demonstrate the selective deposition of metal to create structures, such as a functional microinductor. Our strategy is quite general and can be extended readily to the deposition of materials, such as metal oxides and biomolecules.

Highly efficient multiphoton-absorption-induced luminescence from gold nanoparticles.

We demonstrate that highly efficient photoluminescence is generated from gold nanoparticles as small as a few nanometers in diameter upon irradiation with sub-100-fs pulses of 790-nm light. Strong emission is observed at excitation intensities comparable to or less than those typically used for multiphoton imaging of fluorescently labeled biological samples. The particles have polarized emission, can radiate more efficiently than single molecules, do not exhibit significant blinking, and are photostable under hours of continuous excitation. These observations suggest that metal nanoparticles are a viable alternative to fluorophores or semiconductor nanoparticles for biological labeling and imaging.

In situ observation of molecular diffusion in solid supports using two-photon fluorescence microscopy.

We demonstrate that two-photon fluorescence microscopy is a useful tool for monitoring the diffusion of molecules through polymeric solid supports. As a proof of principle, TentaGel beads were bound to a cover slip, and diffusion of Rhodamine 6G through single beads was observed in real time. Diffusion experiments performed in 40 different beads indicate that there is a considerable degree of heterogeneity in diffusion rates from bead to bead.

Optical Kerr effect spectroscopy using time-delayed pairs of pump pulses with orthogonal polarizations.

We characterize in detail a recently introduced technique in which perpendicularly polarized pulses with controllable intensities and timing are used for the excitation step in optical Kerr effect spectroscopy. We examine the ratio of pump pulse intensities required to cancel the contribution of reorientational diffusion or of a Raman-active intramolecular vibration to the signal as a function of the delay time between excitation pulses. These results indicate that the signal can be described well as arising from the sum of independent third-order responses initiated by each pump pulse. This conclusion is further supported by using data obtained with a single pump pulse to model decays obtained with two pump pulses.

Ultrafast orientational dynamics of nanoconfined benzene.

Ultrafast optical Kerr effect spectroscopy has been used to study the orientational dynamics of benzene and benzene-d(6) confined in nanoporous sol-gel glass monoliths with a range of average pore sizes. All of the observed orientational diffusion of confined benzene is found to occur on a slower time scale than in the bulk, even in pores with diameters that are significantly larger than a benzene molecule. The orientational dynamics of benzene-d(6) are found to be inhibited to a lesser extent than those of benzene, which is attributed to the differences in wetting properties of the two liquids on silica. The decays are fit well by a sum of two exponentials, the faster of which depends on pore size. Similar results are found in pores that have been modified with trimethylsilyl groups, although the relaxation is faster than in unmodified pores. Comparison to Raman line width data for confined benzene-d(6) suggests that the liquid exhibits significant structuring at the pore walls, with the benzene molecules lying flat on the surfaces of unmodified pores.

Orientational dynamics of liquids confined in nanoporous sol-gel glasses studied by optical kerr effect spectroscopy.

When a liquid is restricted to volumes on a molecular distance scale, its orientational and translational dynamics are perturbed strongly by the confinement. Nanoporous sol-gel glasses are an excellent model system for studying the effects of confinement on the behavior of liquids, and in this Account we review experiments in which ultrafast optical Kerr effect spectroscopy has been used to study the orientational dynamics of liquids confined in these media. We contrast the effects of confinement on the orientational dynamics of weakly wetting, strongly wetting, and networked liquids, and we discuss the influence of factors such as pore size, molecular shape, and surface chemistry.

Production, analysis, and application of spatially resolved shells in solid-phase polymer spheres.

Two-photon fluorescence microscopy has been used to interrogate the interior functionality of polymer resin beads. By employing this technique, the spatial distribution of the initial functionality contained within the polymer matrix has been determined. Spatially resolved, concentric shells were then produced synthetically in these polymer spheres via a series of protection/deprotection reactions in which two-photon fluorescence microscopy was employed to monitor each successive step. To demonstrate the potential utility of these techniques in combinatorial screening, a set of beads was prepared containing a unique tripeptide sequence in each of the three concentric shells within each individual bead. The set was then screened for the binding affinity of each tripeptide toward a fluorescent ligand.

Immobilization of Olefin Metathesis Catalysts on Monolithic Sol-Gel: Practical, Efficient, and Easily Recyclable Catalysts for Organic and Combinatorial Synthesis.

Glass-bound Ru-based catalysts! Ru-containing glass pellets efficiently promote olefin metathesis reactions and are easily employed in syntheses of compound libraries. These robust catalysts are active in air and commercially available solvents, can be recycled up to 16 times, and removed from reaction mixtures with a simple pair of tweezers (minimal solvent waste).