Materials that can be switched between low and high thermal conductivity states would advance the control and conversion of thermal energy. Employing in situ time-domain thermoreflectance (TDTR) and in situ synchrotron X-ray scattering, we report a reversible, light-responsive azobenzene polymer that switches between high (0.35 W m−1K−1) and low thermal conductivity (0.10 W m−1K−1) states. This threefold change in the thermal conductivity is achieved by modulation of chain alignment resulted from the conformational transition between planar (trans) and nonplanar (cis) azobenzene groups under UV and green light illumination. This conformational transition leads to changes in the π-π stacking geometry and drives the crystal-to-liquid transition, which is fully reversible and occurs on a time scale of tens of seconds at room temperature. This result demonstrates an effective control of the thermophysical properties of polymers by modulating interchain π-π networks by light.

We describe the development and characterization of pneumatically actuated “lifting gate” microvalves and pumps. A fluidic layer containing the gate structure and a pneumatic layer are fabricated by soft-lithography in PDMS and bonded permanently with an oxygen plasma treatment. The microvalve structures are then reversibly bonded to a featureless glass or plastic substrate to form hybrid glass-PDMS and plastic-PDMS microchannel structures. The breakthrough pressures of the microvalve increase linearly up to 65 kPa as the closing pressure increases. The pumping capability of these structures ranges from the nanoliter to microliter scale depending on the number of cycles and closing pressure employed. The micropump structures exhibit up to 86.2% pumping efficiency from flow rate measurements. The utility of these structures for integrated sample processing is demonstrated by performing an automated immunoassay. These lifting gate valve and pump structures enable facile integration of complex microfluidic control systems with a wide range of lab-on-a-chip substrates.

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Amphiphilic in nature, lipids spontaneously self-assemble into a range of nanostructures in the presence of water. Among lipid self-assembled structures, liposomes and supported lipid bilayers have long held scientific interest for their main applications in drug delivery and plasma membrane models, respectively. In contrast, lipid-based multi-layered membranes on solid supports only recently begun drawing scientists’ attention. New studies on lipid films show that the stacking of multiple bilayers on a solid support yields interestingly complex features to these systems. Namely, multiple layers exhibit cooperative structural and dynamic behavior. In addition, the materials enable compartmentalization, templating, and enhanced release of several molecules of interest. Importantly, supported lipid phases exhibit long-range periodic nano-scale order and orientation that is tunable in response to a changing environment. Herein, we summarize current and pertinent understanding of lipid-based film research focusing on how unique structural characteristics enable the emergence of new applications in biotechnology including label-free biosensors, macroscale drug delivery, and substrate-mediated gene delivery. Our very recent contributions to lipid-based films, focusing on the structural characterization at the meso, nano, and molecular-scale, using Small-Angle X-ray Scattering, Atomic Force Microscopy, Photothermal Induced Resonance, and Solid-State NMR will be also highlighted.

Substrate-mediated gene delivery is an emerging technology that enables spatial control of gene expression and localized delivery. This is of particular interest for siRNA where surface-based delivery methods could greatly impact the fields of stem-cell reprograming, wound healing, and medical device coatings in general. However, reports on the use of siRNA for substratemediated delivery are scarce and have suffered from low efficiency. Here, we report an alternative strategy by designing self-assembled substrates that experience stimuli-responsive topological transformations. Specifically, we established a methodology to promote the molecular organization of lipid films having 3D-bicontinuous cubic, 2D-inverted hexagonal, or 1D-lamellar nanostructures encapsulating siRNA. In response to a compositional, temperature, or humidity stimulus the nanostructures evolve from 1D-lamellar to 3D-cubic resulting in efficient siRNA release to human cell cultures. Grazing Incidence X-ray Diffraction reveals that film nanostructures are highly ordered and preferentially aligned. Our results indicate that film structure substantially affects siRNA delivery, with the supported 3D-bicontinuous cubic phase yielding the most effective reduction of gene expression. Subsequent studies suggest this enhanced performance arises due to the ability of this phase to cross cell membranes, particularly those of endocytic compartments. Our work underpins that nanostructure tuning is decisive to the performance of therapeutic films.