Fabrication of a tunable photothermal actuator via in situ oxidative polymerization of polydopamine nanoparticles in hydrogel bilayers.

Photothermally triggered actuation enables the remote and local control of a material. The complex actuation can be achieved by controlling the photothermal efficiency of the material, which is crucial for the development of soft actuators. In this study, the photothermal efficiency of a hydrogel bilayer actuator consisting of a passive agarose/alginate double-network hydrogel layer and an active poly(N-isopropylacrylamide) (PNIPAm) layer was controlled via in situ oxidative polymerization of polydopamine nanoparticles (PDA NPs). Highly concentrated PDA NPs were successfully incorporated into the hydrogel bilayer without interrupting or weakening the polymer network during polymerization. The photothermal efficiency of the actuator was controlled using the number of polymerization cycles. Upon light irradiation, the heat generated by the photothermal effect of PDA NPs caused the shrinkage of the PNIPAm layer, resulting in the shape-morphing of the bilayer. The broad light absorption properties of PDA NPs allowed the bilayer to actuate under sunlight or visible light. Finally, we demonstrated controlled photothermal actuation using a pinwheel-shaped actuator consisting of four panels with different photothermal efficiencies.

Shape-Changing DNA-Linked Nanoparticle Films Dictated by Lateral and Vertical Patterns.

The self-assembly of nanoscale building blocks into complex nanostructures with controlled structural anisotropy can open up new opportunities for realizing active nanomaterials exhibiting spatiotemporal structural transformations. Here, a combination of bottom-up DNA-directed self-assembly and top-down photothermal patterning is adopted to fabricate free-standing nanoparticle films with vertical and lateral heterogeneity. This approach involves the construction of multicomponent plasmonic nanoparticle films by DNA-directed layer-by-layer (LbL) self-assembly, followed by on-demand lateral patterning by the direct photothermal writing method. The distinct plasmonic properties of nanospheres and nanorods constituting the multidomain films enable photopatterning in a selective domain with precisely controlled vertical depths. The photopatterned films exhibit complex morphing actions instructed by the lateral and vertical patterns inscribed in the film as well as the information carried in DNA.

Thermogelling Behaviors of Aqueous Poly(N-Isopropylacrylamide-co-2-Hydroxyethyl Methacrylate) Microgel-Silica Nanoparticle Composite Dispersions.

Gelation behaviors of hydrogels have provided an outlook for the development of stimuli-responsive functional materials. Of these materials, the thermogelling behavior of poly(N-isopropylacrylamide) (p(NiPAm))-based microgels exhibits a unique, reverse sol-gel transition by bulk aggregation of microgels at the lower critical solution temperature (LCST). Despite its unique phase transition behaviors, the application of this material has been largely limited to the biomedical field, and the bulk gelation behavior of microgels in the presence of colloidal additives is still open for scrutinization. Here, we provide an in-depth investigation of the unique thermogelling behaviors of p(NiPAm)-based microgels through poly(N-isopropylacrylamide-co-2-hydroxyethyl methacrylate) microgel (p(NiPAm-co-HEMA))-silica nanoparticle composite to expand the application possibilities of the microgel system. Thermogelling behaviors of p(NiPAm-co-HEMA) microgel with different molar ratios of N-isopropylacrylamide (NiPAm) and 2-hydroxyethyl methacrylate (HEMA), their colloidal stability under various microgel concentrations, and the ionic strength of these aqueous solutions were investigated. In addition, sol-gel transition behaviors of various p(NiPAm-co-HEMA) microgel systems were compared by analyzing their rheological properties. Finally, we incorporated silica nanoparticles to the microgel system and investigated the thermogelling behaviors of the microgel-nanoparticle composite system. The composite system exhibited consistent thermogelling behaviors in moderate conditions, which was confirmed by an optical microscope. The composite demonstrated enhanced mechanical strength at gel state, which was confirmed by analyzing rheological properties.

Real-time pressure monitoring system for microfluidic devices using deformable colloidal crystal membrane.

Understanding the hydrodynamic behavior in microfluidic devices is crucial for utilization of these systems in lab-on-a-chip applications. However, hydrodynamic capacitance in microfluidic devices causes a delay and mismatch between the applied pressure and actual pressure in the microchannel. Therefore, real-time monitoring of the site-specific internal pressure in microchannels is important for designing the operating conditions of the system. We introduce a deformable colloidal crystal membrane composed of polystyrene (PS) colloidal crystals and poly(dimethylsiloxane) (PDMS) and its integration into a PDMS microfluidic device. As pressure is applied to the device, the optical intensity reflected back from the colloidal crystal membrane changes due to membrane deformation. The optical signal originating from structural deformation of the colloidal crystal membrane allows the realization of a real-time pressure monitoring system, as no external apparatus or powering devices are required for signal processing. The internal pressure in microfluidic devices was also monitored to investigate the effect of the hydrodynamic capacitance during pressure application.

Agarose/Spherical Activated Carbon Composite Gels for Recyclable and Shape-Configurable Electrodes.

Soft electrodes have been known as a key component in the engineering of flexible, wearable, and implantable energy-saving or powering devices. As environmental issues are emerging, the increase of electronic wastes due to the short replacement cycle of electronic products has become problematic. To address this issue, development of eco-friendly and recyclable materials is important, but has not yet been fully investigated. In this study, we demonstrated hydrogel-based electrode materials composed of agarose and spherical activated carbon (agar/SAC) that are easy to shape and recycle. Versatile engineering processes were applied thanks to the reversible gelation of the agarose matrix which enables the design of soft electrodes into various shapes such as thin films with structural hierarchy, microfibers, and even three-dimensional structures. The reversible sol-gel transition characteristics of the agar matrix enables the retrieval of materials and subsequent re-configuration into different shapes and structures. The electrical properties of the agar/SAC composite gels were controlled by gel compositions and ionic strength in the gel matrix. Finally, the composite gel was cut and re-contacted, forming conformal contact to show immediate restoration of the conductivity.

DNA-Functionalized 100 nm Polymer Nanoparticles from Block Copolymer Micelles.

DNA-mediated self-assembly of colloidal particles is one of the most promising approaches for constructing colloidal superstructures. For nanophotonic materials and devices, DNA-functionalized colloids with diameters of around 100 nm are essential building blocks. Here, we demonstrate a strategy for synthesizing DNA-functionalized polymer nanoparticles (DNA-polyNPs) in the size range of 55-150 nm using block copolymer micelles as a template. Diblock copolymers of polystyrene- b-poly(ethylene oxide) with an azide end group (PS- b-PEO-N3) are first formed into spherical micelles. Then, the micelle cores are swollen with the styrene monomer and polymerized, thus producing PS NPs with PEO brushes and azide functional end groups. DNA strands are conjugated onto the ends of the PEO brushes through a strain-promoted alkyne-azide cycloaddition reaction, resulting in a DNA density of more than one DNA strand per 12.6 nm2 for 70 nm particles. The DNA-polyNPs with complementary sequences enable the formation of CsCl-type colloidal superstructure by DNA binding.

Hydrogel micropost-based qPCR for multiplex detection of miRNAs associated with Alzheimer's disease.

Quantitative polymerase chain reaction (qPCR) renders profiling of genes of interest less time-consuming and cost-effective. Recently, multiplex profiling of miRNAs has enabled identifying or investigating predominant miRNAs for various diseases such as cancers and neurodegenerative diseases. Conventional multiplex qPCR technologies mostly use colorimetric measurements in solution phase, yet not only suffer from limited multiplexing capacity but also require target-screening processes due to non-specific binding between targets and primers. Here, we present hydrogel micropost-based qPCR for multiplex detection of miRNAs associated with Alzheimer's disease (AD). Our methodology promises two key advantages compared with the conventional solution-based PCR: 1) nearly no non-specific crosstalks between targets and primers, and 2) practically valuable multiplexing by spatial encoding within a single microchamber. Specifically, we immobilized hydrogel microposts (~ 400µm in diameter) within commercially available polycarbonate PCR chips by multi-step ultraviolet (UV, 365nm) exposure. We optimized this photoimmobilization for thermal cycles of PCR as well. Acrylated forward primers incorporated in polyethylene glycol diacrylate (PEGDA) posts played a crucial role to confine fluorescent signal of cDNA amplification within the PEGDA hydrogel. To demonstrate the potential of our platform, we successfully verified multiplex detection of five miRNAs, which were reported to be highly correlated with AD, from a complex buffer of human plasma.

Inertio-elastic flow instabilities in a 90° bent microchannel.

Biological samples having viscoelastic properties are frequently tested using microfluidic devices. In addition, viscoelastic fluids such as polymer solutions have been used as a suspending medium to spatially focus particles in microchannels. The occurrence of flow instability even at low Reynolds number is a unique property of viscoelastic fluids. In this study, we report the instability in viscoelastic flow for a channel having a 90° bent geometry, which is a characteristic of many microfluidic devices. Interestingly, we observed that the flow instability in aqueous poly(ethylene oxide) (PEO) solution occurs when the concentration of PEO is as low as 50 ppm. We systematically investigated the effects of the polymer concentration, flow rate, and elasticity number on the flow instability. The results show that the flow is stabilized in shear-thinning fluids, whereas the flow instability is amplified when both elastic and inertial effects are pronounced. We believe that this study is useful to design microfluidic devices such as cell-deformability measurement devices based on viscoelastic particle focusing.

Selective Coloration of Melanin Nanospheres through Resonant Mie Scattering.

Black melanin inks are prepared to selectively exhibit colors under strong light, inspired by human hair. High absorbance of melanin suppresses multiple scattering, causing resonant Mie scattering predominant. Various colors can be developed as the resonant wavelength dictated by nanosphere diameter. Therefore, the melanin inks can be used to encrypt and selectively disclose multicolor patterns for anticounterfeiting applications.

Reaction-Diffusion-Mediated Photolithography for Designing Pseudo-3D Microstructures.

Microstructures with 3D features provide advanced functionalities in many applications. Reaction-diffusion process has been employed in photolithography to produce pseudo-3D microstructures in a reproducible manner. In this work, the influences of various parameters on growth behavior of polymeric structures are investigated and the use of the reaction-diffusion-mediated photolithography (RDP) is expanded to a wide range of structural dimensions. In addition, how a lens effect alters the growth behavior of microstructures in conjunction with reaction-diffusion process is studied. For small separation between reaction sites in the array, ultraviolet (UV) exposure time is optimized along with the separation to avoid film or plateau formation. It is further proved that the RDP process is highly reproducible and applicable to various photocurable resins. In a demonstrative purpose, the use of microdomes created by the RDP process as microlens arrays is shown. The RDP process enables the production of pseudo-3D microstructures even with collimated UV light in the absence of complex optical setups, thereby potentially serving as a useful means to create micropatterns and particles with unique structural features.

Shape changing thin films powered by DNA hybridization.

Active materials that respond to physical and chemical stimuli can be used to build dynamic micromachines that lie at the interface between biological systems and engineered devices. In principle, the specific hybridization of DNA can be used to form a library of independent, chemically driven actuators for use in such microrobotic applications and could lead to device capabilities that are not possible with polymer- or metal-layer-based approaches. Here, we report shape changing films that are powered by DNA strand exchange reactions with two different domains that can respond to distinct chemical signals. The films are formed from DNA-grafted gold nanoparticles using a layer-by-layer deposition process. Films consisting of an active and a passive layer show rapid, reversible curling in response to stimulus DNA strands added to solution. Films consisting of two independently addressable active layers display a complex suite of repeatable transformations, involving eight mechanochemical states and incorporating self-righting behaviour.

Microfluidic production of multiple emulsions and functional microcapsules.

Recent advances in microfluidics have enabled the controlled production of multiple-emulsion drops with onion-like topology. The multiple-emulsion drops possess an intrinsic core-shell geometry, which makes them useful as templates to create microcapsules with a solid membrane. High flexibility in the selection of materials and hierarchical order, achieved by microfluidic technologies, has provided versatility in the membrane properties and microcapsule functions. The microcapsules are now designed not just for storage and release of encapsulants but for sensing microenvironments, developing structural colours, and many other uses. This article reviews the current state of the art in the microfluidic-based production of multiple-emulsion drops and functional microcapsules. The three main sections of this paper discuss distinct microfluidic techniques developed for the generation of multiple emulsions, four representative methods used for solid membrane formation, and various applications of functional microcapsules. Finally, we outline the current limitations and future perspectives of microfluidics and microcapsules.

Lithographic Design of Overhanging Microdisk Arrays Toward Omniphobic Surfaces.

Omniphobic surfaces are created by designing an array of overhanging microdisks on a polymer film through two steps of photolithography. Two distinct edges and the large height of the microdisks relative to their separation ensure the formation of an air mat under the microdisks, providing an omniphobic property. Moreover, the freestanding omniphobic films are transparent and flexible, potentially serving as liquid-repellent surfaces in various applications.

Tuning the Mechanical Properties of Recombinant Protein-Stabilized Gas Bubbles Using Triblock Copolymers.

Gas bubbles enhance contrast in ultrasound sonography and can also carry and deliver therapeutic agents. The mechanical properties of the bubble shell play a critical role in determining the physical response of gas bubbles under ultrasound insonation. Currently, few methods allow for tailoring of the mechanical properties of the stabilizing layers of gas bubbles. Here, we demonstrate that blending of poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide) (PEO-PPO-PEO) amphiphilic triblock copolymer with a recombinant protein, oleosin, enables the tuning of the mechanical properties of the bubble stabilizing layer. The areal expansion modulus of gas bubbles, as determined by micropipette aspiration, depends on the structure as well as the concentration of PEO-PPO-PEO triblock copolymers. We believe our method of using a mixture of PEO-PPO-PEO and oleosin can potentially lead to the formation of microbubbles with stabilizing shells that can be functionalized and tailored for specific applications in ultrasound imaging and therapy.

Spatially Selective Nucleation and Growth of Water Droplets on Hierarchically Patterned Polymer Surfaces.

On a hierarchical polymer surface consisting of microposts and nanopillar arrays, water droplets are nucleated and grown selectively in the grooves between the microposts as the vapor pressure increases, whereas water droplets are randomly nucleated on a flat surface and surfaces consisting of microposts or nanopillars only.

Regenerative Astaxanthin Extraction from a Single Microalgal (Haematococcus pluvialis) Cell Using a Gold Nano-Scalpel.

Milking of microalgae, the process of reusing the biomass for continuous production of target compounds, can strikingly overcome the time and cost constraints associated with biorefinery. This process can significantly improve production efficiency of highly valuable chemicals, for example, astaxanthin (AXT) from Haematococcus pluvialis. Detailed understanding of the biological process of cell survival and AXT reaccumulation after extraction would be of great help for successful milking. Here we report extraction of AXT from a single cell of H. pluvialis through incision of the cell wall by a gold nanoscalpel (Au-NS), which allows single-cell analysis of wound healing and reaccumulation of AXT. Interestingly, upon the Au-NS incision, the cell could reaccumulate AXT at a rate two times faster than the control cells. Efficient extraction as well as minimal cellular damage, keeping cells alive, could be achieved with the optimized shape and dimensions of Au-NS: a well-defined sharp tip, thickness under 300 nm, and 1-3 µm of width. The demonstration of regenerative extraction of AXT at a single cell level hints toward the potential of a milking process for continuous recovery of target compounds from microalgae while keeping the cells alive.

Magnetic-Nanoflocculant-Assisted Water-Nonpolar Solvent Interface Sieve for Microalgae Harvesting.

Exploitation of magnetic flocculants is regarded as a very promising energy-saving approach to microalgae harvesting. However, its practical applicability remains limited, mainly because of the problem of the postharvest separation of magnetic flocculants from microalgal flocs, which is crucial both for magnetic-flocculant recycling and high-purity microalgal biomasses, but which is also a very challenging and energy-consuming step. In the present study, we designed magnetic nanoflocculants dually functionalizable by two different organosilane compounds, (3-aminopropyl)triethoxysilane (APTES) and octyltriethoxysilane (OTES), which flocculate negatively charged microalgae and are readily detachable at the water-nonpolar organic solvent (NOS) interface only by application of an external magnetic field. APTES functionalization imparts a positive zeta potential charge (29.6 mV) to magnetic nanoflocculants, thereby enabling microalgae flocculation with 98.5% harvesting efficiency (with a dosage of 1.6 g of dMNF/g of cells). OTES functionalization imparts lipophilicity to magnetic nanoflocculants to make them compatible with NOS, thus effecting efficient separation of magnetic flocculants passing through the water-NOS interface sieve from hydrophilic microalgae. Our new energy-saving approach to microalgae harvesting concentrates microalgal cultures (∼1.5 g/L) up to 60 g/L, which can be directly connected to the following process of NOS-assisted wet lipid extraction or biodiesel production, and therefore provides, by simplifying multiple downstream processes, a great potential cost reduction in microalgae-based biorefinement.

Dynamic designing of microstructures by chemical gradient-mediated growth.

Shape is one of the most important determinants of the properties of microstructures. Despite of a recent progress on microfabrication techniques, production of three-dimensional micro-objects are yet to be fully achieved. Nature uses reaction-diffusion process during bottom-up self-assembly to create functional shapes and patterns with high complexity. Here we report a method to produce polymeric microstructures by using a dynamic reaction-diffusion process during top-down photolithography, providing unprecedented control over shape and composition. In radical polymerization, oxygen inhibits reaction, and therefore diffusion of oxygen significantly alters spatial distribution of growth rate. Therefore, growth pathways of the microstructures can be controlled by engineering a concentration gradient of oxygen. Moreover, stepwise control of chemical gradients enables the creation of highly complex microstructures. The ease of use and high controllability of this technology provide new opportunities for microfabrication and for fundamental studies on the relationships between shape and function for the materials.

Nanocrystalline calcitic lens arrays fabricated by self-assembly followed by amorphous-to-crystalline phase transformation.

Natural calcium carbonate-based nanocomposites often have superior physical properties and provide a comprehensive source for bioinspired synthetic materials. Here we present thermodynamically stable, transparent CaCO3 microlens arrays (MLA) produced by transforming an amorphous CaCO3 phase into nanocrystalline calcite. We analyze the structure and properties of crystallized MLA by X-ray scattering, transmitted and polarized light microscopy, and electron microscopy and find that MLA are crystallized in spherulite-like patterns without changing the shape of the microlens. The key finding is that nanocrystallinity of the calcite formed diminishes structural anisotropy on the wavelength scale and results in greatly reduced birefringent effects. The remnant preferred orientation of the optical axes of calcite crystals in the plane of the microlens arrays leads to some directionality of optical properties, which may be beneficial for technical applications.