Andrew Salmon

Light-induced actuating nanotransducers.

Significance Scientists have dreamt of nanomachines that can navigate in water, sense their environment, communicate, and respond. Various power sources and propulsion systems have been proposed but they lack speed, strength, and control. We introduce here a previously undefined paradigm for nanoactuation which is incredibly simple, but solves many problems. It is optically powered (although other modes are also possible), and potentially offers unusually large force/mass. This looks to be widely generalizable, because the actuating nanotransducers can be selectively bound to designated active sites. The concept can underpin a plethora of future designs and already we produce a dramatic optical response over large areas at high speed. Nanoactuators and nanomachines have long been sought after, but key bottlenecks remain. Forces at submicrometer scales are weak and slow, control is hard to achieve, and power cannot be reliably supplied. Despite the increasing complexity of nanodevices such as DNA origami and molecular machines, rapid mechanical operations are not yet possible. Here, we bind temperature-responsive polymers to charged Au nanoparticles, storing elastic energy that can be rapidly released under light control for repeatable isotropic nanoactuation. Optically heating above a critical temperature Tc = 32 °C using plasmonic absorption of an incident laser causes the coatings to expel water and collapse within a microsecond to the nanoscale, millions of times faster than the base polymer. This triggers a controllable number of nanoparticles to tightly bind in clusters. Surprisingly, by cooling below Tc their strong van der Waals attraction is overcome as the polymer expands, exerting nanoscale forces of several nN. This large force depends on van der Waals attractions between Au cores being very large in the collapsed polymer state, setting up a tightly compressed polymer spring which can be triggered into the inflated state. Our insights lead toward rational design of diverse colloidal nanomachines.

SERS of Individual Nanoparticles on a Mirror: Size Does Matter, but so Does Shape

Coupling noble metal nanoparticles by a 1 nm gap to an underlying gold mirror confines light to extremely small volumes, useful for sensing on the nanoscale. Individually measuring 10 000 of such gold nanoparticles of increasing size dramatically shows the different scaling of their optical scattering (far-field) and surface-enhanced Raman emission (SERS, near-field). Linear red-shifts of the coupled plasmon modes are seen with increasing size, matching theory. The total SERS from the few hundred molecules under each nanoparticle dramatically increases with increasing size. This scaling shows that maximum SERS emission is always produced from the largest nanoparticles, irrespective of tuning to any plasmonic resonances. Changes of particle facet with nanoparticle size result in vastly weaker scaling of the near-field SERS, without much modifying the far-field, and allows simple approaches for optimizing practical sensing.

Electrostatically Directed Self‐Assembly of Ultrathin Supramolecular Polymer Microcapsules

Supramolecular self-assembly offers routes to challenging architectures on the molecular and macroscopic scale. Coupled with microfluidics it has been used to make microcapsules—where a 2D sheet is shaped in 3D, encapsulating the volume within. In this paper, a versatile methodology to direct the accumulation of capsule-forming components to the droplet interface using electrostatic interactions is described. In this approach, charged copolymers are selectively partitioned to the microdroplet interface by a complementary charged surfactant for subsequent supramolecular cross-linking via cucurbit[8]uril. This dynamic assembly process is employed to selectively form both hollow, ultrathin microcapsules and solid microparticles from a single solution. The ability to dictate the distribution of a mixture of charged copolymers within the microdroplet, as demonstrated by the single-step fabrication of distinct core–shell microcapsules, gives access to a new generation of innovative self-assembled constructs.

Monitoring Early-Stage Nanoparticle Assembly in Microdroplets by Optical Spectroscopy and SERS.

Microfluidic microdroplets have increasingly found application in biomolecular sensing as well as nanomaterials growth. More recently the synthesis of plasmonic nanostructures in microdroplets has led to surface-enhanced Raman spectroscopy (SERS)-based sensing applications. However, the study of nanoassembly in microdroplets has previously been hindered by the lack of on-chip characterization tools, particularly at early timescales. Enabled by a refractive index matching microdroplet formulation, dark-field spectroscopy is exploited to directly track the formation of nanometer-spaced gold nanoparticle assemblies in microdroplets. Measurements in flow provide millisecond time resolution through the assembly process, allowing identification of a regime where dimer formation dominates the dark-field scattering and SERS. Furthermore, it is shown that small numbers of nanoparticles can be isolated in microdroplets, paving the way for simple high-yield assembly, isolation, and sorting of few nanoparticle structures.

Microcapsule Buckling Triggered by Compression-Induced Interfacial Phase Change

There is an emerging trend toward the fabrication of microcapsules at liquid interfaces. In order to control the parameters of such capsules, the interfacial processes governing their formation must be understood. Here, poly(vinyl alcohol) films are assembled at the interface of water-in-oil microfluidic droplets. The polymer is cross-linked using cucurbit[8]uril ternary supramolecular complexes. It is shown that compression-induced phase change causes the onset of buckling in the interfacial film. On evaporative compression, the interfacial film both increases in density and thickens, until it reaches a critical density and a phase change occurs. We show that this increase in density can be simply related to the film Poisson ratio and area compression. This description captures fundamentals of many compressive interfacial phase changes and can also explain the observation of a fixed thickness-to-radius ratio at buckling, [Formula: see text].

Controlling Nanowire Growth by Light.

Individual Au catalyst nanoparticles are used for selective laser-induced chemical vapor deposition of single germanium nanowires. Dark-field scattering reveals in real time the optical signatures of all key constituent growth processes. Growth is initially triggered by plasmonic absorption in the Au catalyst, while once nucleated the growing Ge nanowire supports magnetic and electric resonances that then dominate the laser interactions. This spectroscopic understanding allows real-time laser feedback that is crucial toward realizing the full potential of controlling nanomaterial growth by light.

Rapid microcantilever-thickness determination by optical interferometry

Silicon microcantilevers are widely used in scanning-probe microscopy and in cantilever-sensing applications. However, the cantilever thickness is not well controlled in conventional lithography and, since it is also difficult to measure, it is the most important undefined factor in mechanical variability. An accurate method to measure this parameter is thus essential. We demonstrate the capability to measure microcantilever thicknesses rapidly (>1 Hz) and accurately (±2 nm) by optical interferometry. This is achieved with standard microscopy equipment and so can be implemented as a standard technique in both research and in batch control for commercial microfabrication. In addition, we show how spatial variations in the thickness of individual microcantilevers can be mapped, which has applications in the precise mechanical calibration of cantilevers for force spectroscopy.

Research data supporting "Microcapsule Buckling Triggered by Compression-Induced Interfacial Phase Change"

Numerical data from each graph are provided in tab-delimited text format. Uncropped versions of each image used are provided in png format. AFM data are enclosed in a zip folder containing mi format files. mi files can be opened with Gwyddion software which is freely available online. The files are labelled according to the relevant figure number. Refer to the manuscript and ESI for a description of the data.