The electrophoretic mobility of oil droplets, dispersed without any surfactant in the aqueous phase, was measured. Four different oils were studied:  xylene, dodecane, hexadecane, and perfluoromethyldecalin. Special precautions were undertaken to avoid artifacts caused by the presence of surfactant impurities. The results show that the oil droplets are negatively charged and the magnitude of their ζ-potential strongly depends on pH and the ionic strength of the aqueous phase. The electrophoretic mobility is almost independent of the type of specific nonpolar oil. Series of experiments were performed to check different hypotheses about the origin of the spontaneous charging of the oil−water interfaces. The results lead to the conclusion that hydroxyl ions, released by the dissociation−association equilibrium of the water molecules, adsorb at the oil−water interface. The specific adsorption energy was estimated to be 25kT per ion (kT is the thermal energy). The molecular origin and the implications of this phenomenon are discussed. The ζ-potential decreases in magnitude when poly(oxyethylene) chain nonionic surfactants are adsorbed at the interface.

Encapsulation of drugs within nanocarriers that selectively target malignant cells promises to mitigate side effects of conventional chemotherapy and to enable delivery of the unique drug combinations needed for personalized medicine. To realize this potential, however, targeted nanocarriers must simultaneously overcome multiple challenges, including specificity, stability, and a high capacity for disparate cargos. Here we report porous nanoparticle-supported lipid bilayers (protocells) that synergistically combine properties of liposomes and nanoporous particles. Protocells modified with a targeting peptide that binds to human hepatocellular carcinoma (HCC) exhibit a 10,000-fold greater affinity for HCC than for hepatocytes, endothelial cells, and immune cells. Furthermore, protocells can be loaded with combinations of therapeutic (drugs, siRNA, and toxins) and diagnostic (quantum dots) agents and modified to promote endosomal escape and nuclear accumulation of selected cargos. The enormous capacity of the high-surface-area nanoporous core combined with the enhanced targeting efficacy enabled by the fluid supported lipid bilayer allow a single protocell loaded with a drug cocktail to kill a drug-resistant HCC cell, representing a 106-fold improvement over comparable liposomes.

Microsensors and micromachines that are capable of self-propulsion through fluids could revolutionize many aspects of technology. Few principles to propel such devices and supply them with energy are known. Here, we show that various types of miniature semiconductor diodes floating in water act as self-propelling particles when powered by an external alternating electric field. The millimetre-sized diodes rectify the voltage induced between their electrodes. The resulting particle-localized electro-osmotic flow propels them in the direction of either the cathode or the anode, depending on their surface charge. These rudimentary self-propelling devices can emit light or respond to light and could be controlled by internal logic. Diodes embedded in the walls of microfluidic channels provide locally distributed pumping or mixing functions powered by a global external field. The combined application of a.c. and d.c. fields in such devices allows decoupling of the velocity of the particles and the liquid and could be used for on-chip separations.

This report presents a study of electrokinetic transport in a series of integrated macro- to nano-fluidic chips that allow for controlled injection of molecular mixtures into high-density arrays of nanochannels. The high-aspect-ratio nanochannels were fabricated on a Si wafer using interferometric lithography and standard semiconductor industry processes, and are capped with a transparent Pyrex cover slip to allow for experimental observations. Confocal laser scanning microscopy was used to examine the electrokinetic transport of a negatively charged dye (Alexa 488) and a neutral dye (rhodamine B) within nanochannels that varied in width from 35 to 200 nm with electric field strengths equal to or below 2000 V m-1. In the negatively charged channels, nanoconfinement and interactions between the respective solutes and channel walls give rise to higher electroosmotic velocities for the negatively charged dye than for the neutral dye, towards the negative electrode, resulting in an anomalous separation that occurs over a relatively short distance (<1 mm). Increasing the channel widths leads to a switch in the electroosmotic transport behavior observed in microscale channels, where neutral molecules move faster because the negatively charged molecules are slowed by the electrophoretic drag. Thus a clear distinction between "nano-" and "microfluidic" regimes is established. We present an analytical model that accounts for the electrokinetic transport and adsorption (of the neutral dye) at the channel walls, and is in good agreement with the experimental data. The observed effects have potential for use in new nano-separation technologies.