Homologous pairing in short double-stranded DNA-grafted colloidal microspheres.

Homologous pairing (HP), i.e., the pairing of similar or identical double-stranded DNA, is an insufficiently understood fundamental biological process. HP is now understood to also occur without protein mediation, but crucial mechanistic details remain poorly established. Unfortunately, systematic studies of sequence dependence are not practical due to the enormous number of nucleotide permutations and multiple possible conformations involved in existing biophysical strategies even when using as few as 150 basepairs. Here, we show that HP can occur in DNA as short as 18 basepairs in a colloidal microparticle-based system. Exemplary systematic studies include resolving opposing reports of the impact of % AT composition, validating the impact of nucleotide order and triplet framework and revealing isotropic bendability to be crucial for HP. These studies are enabled by statistical analysis of crystal size and fraction within coexisting fluid-crystal phases of double-stranded DNA-grafted colloidal microspheres, where crystallization is predicated by HP.

Effect of Chemical Microenvironment in Spirothiopyran Monolayer Direct-Write Photoresists.

We study the effect of the microenvironment on writing chemical patterns into spirothiopyran monolayers over large areas in a single step with light. Surfaces functionalized with photoresponsive spirothiopyran are fabricated by chemically modifying amine-terminated monolayers. The merocyanine isomer selectively participates in a thiol-Michael addition reaction with maleimide-functionalized molecules, rendering these surfaces ideal for fast, mask-less direct writing. The local microenvironment of spirothiopyran is found to strongly influence the kinetics of photoswitching. The quantum yield of ring opening is found to be 17 times faster for spirothiopyran surrounded by a locally charged environment rich in guanidinium diluent molecules as compared to a closed-packed monolayer without diluents. Hydrophilic environments are also found to improve the kinetics of ring closing. Optimization of the diluent concentration leads to dramatic improvements in both contrast and yield of direct writing. This enables the monolayer to be used for maskless two-color photopatterning in which spatial control over patterning is obtained by varying the relative intensity of incident UV and green light. These experiments demonstrate the capacity of spirothiopyran monolayers to serve as a versatile toolbox for rapid, large-area surface functionalization.

Quantification of functional crosslinker reaction kinetics via super-resolution microscopy of swollen microgels.

Super resolution microscopy (SRM) brings the advantages of optical microscopy to the imaging of nanostructured soft matter, and in colloidal microgels, promises to quantify variations of crosslink densities at unprecedented length scales. However, the distribution of all crosslinks does not coincide with that of dye-tagged crosslinks, and density quantification in SRM is not guaranteed due to over/under-counting dye molecules. Here we demonstrate that SRM images of microgels encode reaction rate constants of functional cross linkers, which hold the key to correlating these distributions. Combined with evolution of microgel particle radii, the functional cross linker distributions predict consumption versus time with high fidelity. Using a Bayesian regression approach, we extract reaction rate constants for homo and cross propagation of the functional crosslinker, which should be widely useful for predicting spatial variations in crosslink density of gels.

Size effects in plasma-enhanced nano-transfer adhesion.

Plasma bonding and layer-by-layer transfer molding have co-existed for decades, and here we offer a combination of the two that drives both techniques to the nanoscale. Using fluorinated elastomeric stamps, lines of plasma-treated poly(dimethylsiloxane) (PDMS) were stacked into multi-layer woodpile structures via transfer molding, and we observe a pronounced size effect wherein nanoscale lines (≤280 nm period) require ultra-low plasma dose (<20 J) and fail to bond at the much higher range of plasma dose (600 J to 900 J) recommended in the PDMS plasma bonding literature. The size effect appears to be related to the thickness of the oxide film that develops on the PDMS surface during treatment, and we employ an empirical relationship, , to estimate the thickness of this film in the low plasma dose (<100 J) regime. The empirical relationship shows good agreement with existing studies on plasma-treated PDMS oxide film thickness, and the transition between successful transfer and delamination coincides well with a critical value of the oxide thickness relative to the thickness of the transferred layer. Through peel testing, we identified a transition in failure mode of flat plasma-bonded PDMS consistent with the optimal plasma dose in previous literature but otherwise observed strong, irreversible adhesion even at ultra-low plasma dose. By demonstrating the importance of low plasma dose for plasma-enhanced nano-transfer adhesion, these results advance our understanding of irreversible adhesion of soft materials at the nanoscale and open up new opportunities within the relatively unstudied ultra-low dose plasma treatment regime.

Dynamic imaging of colloidal-crystal nanostructures at 200 frames per second.

The dynamic noninvasive imaging of colloidal nanostructures has been precluded by the diffraction-limited resolution of (confocal) light microscopy. Using Fast Stimulated Emission Depletion (STED) microscopy, we demonstrate the ability to resolve the formation of a colloidal crystal (monolayer) from particles of 200 nm size, where the voids in the crystal are as small as 30 nm. With a temporal resolution of 5 ms, we exemplify the technique by visualizing the annealing of potential point defects during the formation of the colloidal crystal.

Block copolymer nanostructures mapped by far-field optics.

We demonstrate stimulated emission depletion microscopy using opposing objective lenses to noninvasively reveal the nanoscale morphology of block copolymers in three dimensions with focused light. This is exemplified in a poly(styrene-block-2-vinylpyridine) model system in which contrast is achieved by specifically staining the vinylpyridine phase with a fluorescent dye. We image swelling induced mesopores and other convoluted structures within the bulk of samples, at scales that have so far required electron and scanning probe microscopes.

Coupled Electromagnetic and Reaction Kinetics Simulation of Super-Resolution Interference Lithography.

Inspired by the ability of super-resolved fluorescence microscopy to circumvent the diffraction barrier, two-color super-resolution interference lithography exploits nonequilibrium kinetics in materials to achieve large-area nanopatterning while using visible light. Periodic patterns with super-resolved features down to tens of nanometers have been demonstrated in thin films and monolayers. Extending these advances to the bulk nanopatterning of thick films requires a quantitative understanding of the time-dependent interactions of optical dynamics, including absorption, diffraction, and intensity modulation at two wavelengths, with the photoactivated and inhibited reaction kinetics. Here, we develop an efficient electromagnetic (EM) perturbation theory approach that facilitates for the first time fully coupled simulations of EM and chemical kinetics in two-color interference lithography. Applied to a spirothiopyran-functionalized photoresist system, these simulations show that diffraction and absorption effects are negligible (<0.1%) for depths up to 10 µm, and that tuning exposure time and intensities can lead to concentration contrast up to 80%. We investigate multiple exposure strategies to reduce the pitch of the line pattern including sequential exposures with different times to achieve uniform lines and multiplexed exposures with equal periods. This capability to rapidly and accurately predict the coupled optical and chemical dynamics facilitates the computational design of high-precision patterns in two-color interference lithography.

One-pot surfactant-free modulation of size and functional group distribution in thermoresponsive microgels.

Control over the size and functional group distribution of soft responsive hydrogel particles is essential for applications such as drug delivery, catalysis and chemical sensing. Traditionally, targeted functional group distributions are achieved with semi-batch techniques which require specialized equipment, while the preparation of size-tailored particles typically involves the use of surfactants. Herein, we present a simple and robust surfactant-free method for the modulation of size and carboxylic acid functional group distribution in poly(N-isopropylacrylamide) thermoresponsive microgels, employing reaction pH as the single experimental parameter. The varying distributions of carboxylic acid residues arise due to differences in kinetic reactivity, which are a function of the degree of dissociation of methacrylic acid, and thus of reaction pH. Incorporated charged residues induce a surfactant-like action during the particle nucleation stage, and impact the final particle size. Characterization with dynamic light scattering, and electron microscopy consistently supports the pH-tailored morphology of the microgels. A mathematical model which accounts for particle deformation on the imaging substrate also shows excellent agreement with the experimental results.

Super-resolution interference lithography enabled by non-equilibrium kinetics of photochromic monolayers.

Highly parallelized optical super-resolution lithography techniques are key for realizing bulk volume nanopatterning in materials. The majority of demonstrated STED-inspired lithography schemes are serial writing techniques. Here we use a recently developed model spirothiopyran monolayer photoresist to study the non-equilibrium kinetics of STED-inspired lithography systems to achieve large area interference lithography with super-resolved feature dimensions. The linewidth is predicted to increase with exposure time and the contrast is predicted to go through a maximum, resulting in a narrow window of optimum exposure. Experimental results are found to match with high quantitative accuracy. The low photoinhibition saturation threshold of the spirothiopyran renders it especially conducive for parallelized large area nanopatterning. Lines with 56 and 92 nm FWHM were obtained using serial and parallel patterning, respectively. Functionalization of surfaces with heterobifunctional PEGs enables diverse patterning of any desired chemical functionality on these monolayers. These results provide important insight prior to realizing a highly parallelized volume nanofabrication technique.

Dye doped concentric shell nanoparticles for enhanced photophysical performance of downconverting light emitting diodes.

In this study, we examined the potential for perylene dye doped nanoparticles to enhance Light Emitting Diodes (LED) efficacy by minimizing π-π intermolecular aggregation, and enhancing photoluminescence and photostability of the dye molecules in the solid state. Towards this end, we encapsulated perylene dyes, suitably modified with a reactive silica precursor, into silica nanoparticles within a silica-dye-silica concentric layered shell. We found that the fluorescent yield was higher when the dye was embedded in a buried concentric shell within the silica nanoparticles (NPs) compared to an undoped shell/dye doped core nanoparticle morphology or unencapsulated dye with the same net dye concentration in solution. A strong dependence of relative quantum yield on dye doping concentration in the silica-dye-silica nanoparticles was observed. The uniform ∼ 100 nm large silica-dye-silica layered nanoparticles were used to prepare transparent dye doped silica nanoparticle/silicone nanocomposites. Dye doped silica nanoparticle/silicone nanocomposites exhibited higher photostability than the unencapsulated dye samples during long time aging tests under a blue LED with a wavelength of 455 nm at 300 ±â€¯3% mA for 24 h. Novel dye doped layered silica NPs and their nanocomposites offer scope for developing organic luminescent materials into efficient and color-tunable light emitters for low-cost display, lighting, and optical communication applications.

Resolution scaling in STED microscopy.

We undertake a comprehensive study of the inverse square root dependence of spatial resolution on the saturation factor in stimulated emission depletion (STED) microscopy and generalize it to account for various focal depletion patterns. We used an experimental platform featuring a high quality depletion pattern which results in operation close to the optimal optical performance. Its superior image brightness and uniform effective resolution <25 nm are evidenced by imaging both isolated and self-organized convectively assembled fluorescent beads. For relevant saturation values, the generalized square-root law is shown to predict the practical resolution with high accuracy.

3D mapping of nanoscale crosslink heterogeneities in microgels.

The majority of swollen polymer networks exhibit spatial variations in crosslink density. These spatial heterogeneities are particularly important in colloidal gel particles, or microgels, where they manifest themselves on the nanoscale and impact mechanical and transport properties. Despite their importance, the real space nanostructure of these heterogeneities at the individual particle level has remained elusive. Using state of the art super-resolution microscopy known as Whole cell 4Pi Single Molecule Switching Nanoscopy (W-4PiSMSN) we demonstrate 3D nanoscale mapping of spatial crosslink heterogeneities in a model system of poly(N-isopropylacrylamide) colloidal gel particles containing a novel fluorophore tagged crosslinker. We reveal the presence of higher crosslink density clusters embedded in a lower crosslink density matrix within the core of individual microgel particles, a phenomenon that has been predicted, but never been observed before in real space. The morphology of the clusters provides insight into the kinetics of microgel formation. This study also provides proof-of-concept 3D super-resolution imaging of spatial heterogeneities in bulk hydrogels.

Wetting Regimes for Residual-Layer-Free Transfer Molding at Micro- and Nanoscales.

Transfer molding offers a low-cost approach to large-area fabrication of isolated structures in a variety of materials when recessed features of the open-faced mold are filled without leaving a residual layer on the plateaus of the mold. Considering both macroscale dewetting and microscale capillary flow, a proposed map of wetting regimes for blade meniscus coating provides a guide for achieving discontinuous dewetting at maximum throughput. Dependence of meniscus morphology on the azimuthal orientation of the stamp provides insight into the dominant mechanisms for discontinuous dewetting of one-dimensional (1-D) patterns. Critical meniscus velocity is measured and residual-layer-free filling is demonstrated for 1-D patterned soft molds (stamps) with periods ranging from 140 nm to 6 µm. Transfer of isolated lines, and multilayer woodpile structures were achieved through plasma bonding. These results are relevant to other roll-to-roll compatible processes for scalable production of high-resolution structures across large areas.

Three-dimensional nanoscopy of colloidal crystals.

We demonstrate the direct three-dimensional imaging of densely packed colloidal nanostructures using stimulated emission depletion microscopy. A combination of two de-excitation patterns yields a resolution of 43 nm in the lateral and 125 nm in the axial direction and an effective focal volume that is by 126-fold smaller than that of a corresponding confocal microscope. The mapping of a model system of spheres organized by confined convective assembly unambiguously identified face-centered cubic, hexagonal close-packed, random hexagonal close-packed, and body-centered cubic structures.

Shape control of multivalent 3D colloidal particles via interference lithography.

We present a new route for the fabrication of highly nonspherical complex multivalent submicron particles. This technique exploits the ability of holographic interference lithography to control geometrical elements such as symmetry and volume fraction in 3D lattices on the submicron scale. Colloidal particles with prescribed complex concave shapes are obtained by cleaving low volume fraction connected structures fabricated by interference lithography. Controlling which Wyckoff sites in the space group of the parent structure are connected assures specific "valencies" of the particles. Two types of particles, 2D "4-valent" and 3D "6-valent" particles are fabricated via this technique. In addition to being able to control multivalent particle shape, this technique has the potential to provide tight control over size, yield, and dispersity.

Mechanically tunable three-dimensional elastomeric network/air structures via interference lithography.

We show how to employ an interference lithographic template (ILT) as a facile mold for fabricating three-dimensional bicontinuous PDMS (poly(dimethylsiloxane)) elastomeric structures and demonstrate the use of such a structure as a mechanically tunable PDMS/air phononic crystal. A positive photoresist was used to make the ILT, and after infiltration with PDMS, the resist was removed in a water-based basic solution which avoided PDMS swelling or pattern collapse occurring during the ILT removal process. Since the period of the structure is approximately 1 microm, the density of states of gigahertz phonons are altered by the phononic PDMS/air crystal. Brillouin light scattering (BLS) was employed to measure phononic modes of the structure as a function of mechanical strain. The results demonstrate that the phononic band diagram of such structures can be tuned mechanically.

Exploring for 3D photonic bandgap structures in the 11 f.c.c. space groups.

The promise of photonic crystals and their potential applications has attracted considerable attention towards the establishment of periodic dielectric structures that in addition to possessing robust complete bandgaps, can be easily fabricated with current techniques. A number of theoretical structures have been proposed. To date, the best complete photonic bandgap structure is that of diamond networks having Fd3m symmetry (2-3 gap). The only other known complete bandgap in a face-centred-cubic (f.c.c.) lattice structure is that of air spheres in a dielectric matrix (8-9 gap; the so called 'inverse-opal' structure). Importantly, there is no systematic approach to discovering champion photonic crystal structures. Here we propose a level-set approach based on crystallography to systematically examine for photonic bandgap structures and illustrate this approach by applying it to the 11 f.c.c. groups. This approach gives us an insight into the effects of symmetry and connectivity. We classify the F-space groups into four fundamental geometries on the basis of the connectivity of high-symmetry Wyckoff sites. Three of the fundamental geometries studied display complete bandgaps--including two: the F-RD structure with Fm3m symmetry and a group 216 structure with F43m symmetry that have not been reported previously. By using this systematic approach we were able to open gaps between the 2-3, 5-6 and 8-9 bands in the f.c.c. systems.

Triply periodic bicontinuous structures through interference lithography: a level-set approach.

Interference lithography holds the promise of fabricating large-area, defect-free photonic structures on the sub-micrometer scale both rapidly and cheaply. There is a need for a procedure to establish a connection between the structures that are formed and the parameters of the interfering beams. There is also a need to produce self-supporting three-dimensional bicontinuous structures. A generic technique correlating parameters of the interfering beams with the symmetry elements present in the resultant structures by a level-set approach is developed. A particular space group is ensured by equating terms of the intensity equation to a representative level surface of the desired space group. Single- and multiple-exposure techniques are discussed. The beam parameters for certain cubic bicontinuous structures relevant to photonic crystals, viz.,the diamond(D), the simple cubic (P), and the chiral gyroid (G) are derived by utilizing either linear or elliptically polarized light.