Device-quality, reconfigurable metamaterials from shape-directed nanocrystal assembly.

Anchoring nanoscale building blocks, regardless of their shape, into specific arrangements on surfaces presents a significant challenge for the fabrication of next-generation chip-based nanophotonic devices. Current methods to prepare nanocrystal arrays lack the precision, generalizability, and postsynthetic robustness required for the fabrication of device-quality, nanocrystal-based metamaterials [Q. Y. Lin et al. Nano Lett. 15, 4699-4703 (2015); V. Flauraud et al., Nat. Nanotechnol. 12, 73-80 (2017)]. To address this challenge, we have developed a synthetic strategy to precisely arrange any anisotropic colloidal nanoparticle onto a substrate using a shallow-template-assisted, DNA-mediated assembly approach. We show that anisotropic nanoparticles of virtually any shape can be anchored onto surfaces in any desired arrangement, with precise positional and orientational control. Importantly, the technique allows nanoparticles to be patterned over a large surface area, with interparticle distances as small as 4 nm, providing the opportunity to exploit light-matter interactions in an unprecedented manner. As a proof-of-concept, we have synthesized a nanocrystal-based, dynamically tunable metasurface (an anomalous reflector), demonstrating the potential of this nanoparticle-based metamaterial synthesis platform.

DNA-Mediated Size-Selective Nanoparticle Assembly for Multiplexed Surface Encoding.

Multiplexed surface encoding is achieved by positioning two different sizes of gold nanocubes on gold surfaces with precisely defined locations for each particle via template-confined, DNA-mediated nanoparticle assembly. As a proof-of-concept demonstration, cubes with 86 and 63 nm edge lengths are assembled into arrangements that physically and spectrally encrypt two sets of patterns in the same location. These patterns can be decrypted by mapping the absorption intensity of the substrate at λ = 773 and 687 nm, respectively. This multiplexed encoding platform dramatically increases the sophistication and density of codes that can be written using colloidal nanoparticles, which may enable high-security, high-resolution encoding applications.

Design Rules for Template-Confined DNA-Mediated Nanoparticle Assembly.

Template-based strategies are becoming increasingly important for controlling the position of nanoparticle-based (NP-based) structures on surfaces for a wide variety of encoding and device fabrication strategies. Thus, there is an increasing need to understand the behavior of NPs in confined spaces. Herein, a systematic investigation of the diffusion and adsorption properties of DNA-modified NPs is presented in lithographically defined, high-aspect-ratio pores using a template-confined, DNA-mediated assembly. Leveraging the sequence-specific binding affinity of DNA, it is discovered that although NP adsorption in deep polymer pores follows a traditional Langmuir adsorption model when under thermodynamic control, such NPs kinetically follow Fick's classical law of diffusion. Importantly, these observations allow one to establish design rules for template-confined, DNA-mediated NP assembly on substrates based on pore dimensions, NP size and shape, NP concentration, temperature, and time. As a proof-of-concept example, these design rules are used to engineer a vertical, four-layer assembly consisting of individual octahedral NPs stacked on top of one another, with in-plane positioning defined by pores generated by e-beam lithography.

Contraction and Expansion of Stimuli-Responsive DNA Bonds in Flexible Colloidal Crystals.

DNA surface ligands can be used as programmable "bonds" to control the arrangement of nanoparticles into crystalline superlattices. Here, we study the intrinsic responsiveness of these DNA bonds to changes in local dielectric constant (εr) as a new approach to dynamically modulate superlattice structure. Remarkably, ethanol (EtOH) addition can be used to controllably tune DNA bond length from 16 to 3 nm and to increase bond stability by >40 °C, while retaining long-range order and crystal habit. Interestingly, we find that these structural changes, which involve the expansion and contraction of crystals by up to 75% in volume, occur in a cooperative fashion once a critical percentage of EtOH is reached. These results provide a facile and robust approach to create stimuli-responsive lattices, to access high volume fractions, and to improve thermal stability.

Strong Coupling between Plasmonic Gap Modes and Photonic Lattice Modes in DNA-Assembled Gold Nanocube Arrays.

Control of both photonic and plasmonic coupling in a single optical device represents a challenge due to the distinct length scales that must be manipulated. Here, we show that optical metasurfaces with such control can be constructed using an approach that combines top-down and bottom-up processes, wherein gold nanocubes are assembled into ordered arrays via DNA hybridization events onto a gold film decorated with DNA-binding regions defined using electron beam lithography. This approach enables one to systematically tune three critical architectural parameters: (1) anisotropic metal nanoparticle shape and size, (2) the distance between nanoparticles and a metal surface, and (3) the symmetry and spacing of particles. Importantly, these parameters allow for the independent control of two distinct optical modes, a gap mode between the particle and the surface and a lattice mode that originates from cooperative scattering of many particles in an array. Through reflectivity spectroscopy and finite-difference time-domain simulation, we find that these modes can be brought into resonance and coupled strongly. The high degree of synthetic control enables the systematic study of this coupling with respect to geometry, lattice symmetry, and particle shape, which together serve as a compelling example of how nanoparticle-based optics can be useful to realize advanced nanophotonic structures that hold implications for sensing, quantum plasmonics, and tunable absorbers.

Tip-Directed Synthesis of Multimetallic Nanoparticles.

Alloy nanoparticles are important in many fields, including catalysis, plasmonics, and electronics, due to the chemical and physical properties that arise from the interactions between their components. Typically, alloy nanoparticles are made by solution-based synthesis; however, scanning-probe-based methods offer the ability to make and position such structures on surfaces with nanometer-scale resolution. In particular, scanning probe block copolymer lithography (SPBCL), which combines elements of block copolymer lithography with scanning probe techniques, allows one to synthesize nanoparticles with control over particle diameter in the 2-50 nm range. Thus far, single-element structures have been studied in detail, but, in principle, one could make a wide variety of multicomponent systems by controlling the composition of the polymer ink, polymer feature size, and metal precursor concentrations. Indeed, it is possible to use this approach to synthesize alloy nanoparticles comprised of combinations of Au, Ag, Pd, Ni, Co, and Pt. Here, such structures have been made with diameters deliberately tailored in the 10-20 nm range and characterized by STEM and EDS for structural and elemental composition. The catalytic activity of one class of AuPd alloy nanoparticles made via this method was evaluated with respect to the reduction of 4-nitrophenol with NaBH4. In addition to being the first catalytic studies of particles made by SPBCL, these proof-of-concept experiments demonstrate the potential for SPBCL as a new method for studying the fundamental science and potential applications of alloy nanoparticles in areas such as heterogeneous catalysis.

Apertureless cantilever-free pen arrays for scanning photochemical printing.

A novel, apertureless, cantilever-free pen array can be used for dual scanning photochemical and molecular printing. Serial writing with light is enabled by combining self-focusing pyramidal pens with an opaque backing between pens. The elastomeric pens also afford force-tuned illumination and simultaneous delivery of materials and optical energy. These attributes make the technique a promising candidate for maskless high-resolution photopatterning and combinatorial chemistry.

The sources, properties, extraction, biosynthesis, pharmacology, and application of lycopene.

Lycopene is an important pigment with an alkene skeleton from Lycopersicon esculentum, which is also obtained from some red fruits and vegetables. Lycopene is used in the food field with rich functions and serves in the medical field with multiple clinical values because it has dual functions of both medicine and food. It was found that lycopene was mainly isolated by solvent extraction, ultrasonic-assisted extraction, supercritical fluid extraction, high-intensity pulsed electric field-assisted extraction, enzymatic-assisted extraction, and microwave-assisted extraction. Meanwhile, it was also obtained via 2 synthetic pathways: chemical synthesis and biosynthesis. Pharmacological studies revealed that lycopene has anti-oxidant, hypolipidemic, anti-cancer, immunity-enhancing, hepatoprotective, hypoglycemic, cardiovascular-protective, anti-inflammatory, neuroprotective, and osteoporosis-inhibiting effects. The application of lycopene mainly includes food processing, animal breeding, and medical cosmetology fields. It is hoped that this review will provide some useful information and guidance for future study and exploitation of lycopene.

Building superlattices from individual nanoparticles via template-confined DNA-mediated assembly.

DNA programmable assembly has been combined with top-down lithography to construct superlattices of discrete, reconfigurable nanoparticle architectures on a gold surface over large areas. Specifically, the assembly of individual colloidal plasmonic nanoparticles with different shapes and sizes is controlled by oligonucleotides containing "locked" nucleic acids and confined environments provided by polymer pores to yield oriented architectures that feature tunable arrangements and independently controllable distances at both nanometer- and micrometer-length scales. These structures, which would be difficult to construct by other common assembly methods, provide a platform to systematically study and control light-matter interactions in nanoparticle-based optical materials. The generality and potential of this approach are explored by identifying a broadband absorber with a solvent polarity response that allows dynamic tuning of visible light absorption.

Solution-Phase Photochemical Nanopatterning Enabled by High-Refractive-Index Beam Pen Arrays.

A high-throughput, solution-based, scanning-probe photochemical nanopatterning approach, which does not require the use of probes with subwavelength apertures, is reported. Specifically, pyramid arrays made from high-refractive-index polymeric materials were constructed and studied as patterning tools in a conventional liquid-phase beam pen lithography experiment. Two versions of the arrays were explored with either metal-coated or metal-free tips. Importantly, light can be channeled through both types of tips and the appropriate solution phase (e.g., H2O or CH3OH) and focused on subwavelength regions of a substrate to effect a photoreaction in solution that results in localized patterning of a self-assembled monolayer (SAM)-coated Au thin film substrate. Arrays with as many as 4500 pyramid-shaped probes were used to simultaneously initiate thousands of localized free-radical photoreactions (decomposition of a lithium acylphosphinate photoinitiator in an aqueous solution) that result in oxidative removal of the SAM. The technique is attractive since it allows one to rapidly generate features less than 200 nm in diameter, and the metal-free tips afford more than 10-fold higher intensity than the tips with nanoapertures over a micrometer propagation length. In principle, this mask-free method can be utilized as a versatile tool for performing a wide variety of photochemistries across multiple scales that may be important in high-throughput combinatorial screening applications related to chemistry, biology, and materials science.

Size-Selective Nanoparticle Assembly on Substrates by DNA Density Patterning.

The vision of nanoscale self-assembly research is the programmable synthesis of macroscale structures with controlled long and short-range order that exhibit a desired set of properties and functionality. However, strategies to reliably isolate and manipulate the nanoscale building blocks based on their size, shape, or chemistry are still in their infancy. Among the promising candidates, DNA-mediated self-assembly has enabled the programmable assembly of nanoparticles into complex architectures. In particular, two-dimensional assembly on substrates has potential for the development of integrated functional devices and analytical systems. Here, we combine the high-resolution patterning capabilities afforded by electron-beam lithography with the DNA-mediated assembly process to enable direct-write grayscale DNA density patterning. This method allows modulation of the functionally active DNA surface density to control the thermodynamics of interactions between nanoparticles and the substrate. We demonstrate that size-selective directed assembly of nanoparticle films from solutions containing a bimodal distribution of particles can be realized by exploiting the cooperativity of DNA binding in this system. To support this result, we study the temperature-dependence of nanoparticle assembly, analyze the DNA damage by X-ray photoelectron spectroscopy and fluorescence microscopy, and employ molecular dynamics simulations to explore the size-selection behavior.

Polyelemental nanoparticle libraries.

Multimetallic nanoparticles are useful in many fields, yet there are no effective strategies for synthesizing libraries of such structures, in which architectures can be explored in a systematic and site-specific manner. The absence of these capabilities precludes the possibility of comprehensively exploring such systems. We present systematic studies of individual polyelemental particle systems, in which composition and size can be independently controlled and structure formation (alloy versus phase-separated state) can be understood. We made libraries consisting of every combination of five metallic elements (Au, Ag, Co, Cu, and Ni) through polymer nanoreactor-mediated synthesis. Important insight into the factors that lead to alloy formation and phase segregation at the nanoscale were obtained, and routes to libraries of nanostructures that cannot be made by conventional methods were developed.

Step-by-step fracture of two-layer stacked graphene membranes.

Layer-by-layer assembly of graphene has been proven to be an effective way to improve its mechanical properties, but its fracture mechanism, which is crucial for practical device applications, is still not clear and has not been fully studied yet. By consecutive stacking of two graphene monolayers, we fabricate two-layer stacked graphene membranes with a clean interface between the two layers. Fracture behavior of the two-layer stacked graphene membranes is studied using nanoindentation performed by atomic force microscopy. It is found that the fracture force distribution of stacked graphene is very different from that of monolayer graphene. Weibull statistics of fracture forces show that after layer-by-layer stacking of graphene, the membrane becomes less sensitive to the defects during nanoindentation, improving the overall performance of the graphene membranes. Interestingly, a third of our tested membranes show a stepwise fracture, which could serve as a warning message for the mechanical failure of multilayer graphene devices. Our study provides insight into the fracture mechanism of multilayer graphene membranes.

Stretch-induced stiffness enhancement of graphene grown by chemical vapor deposition.

The mechanical properties of ultrathin membranes have attracted considerable attention recently. Nanoindentation based on atomic force microscopy is commonly employed to study mechanical properties. We find that the data processing procedures in previous studies are nice approximations, but it is difficult for them to illustrate the mechanical properties precisely. Accordingly, we develop a revised numerical method to describe the force curve properly, by which the intrinsic mechanical properties of these membranes can be acquired. Combining the nanoindentation measurements with the revised numerical method, we demonstrate that loading-unloading cycles under large load can lead to a pronounced improvement in stiffness of graphene grown by chemical vapor deposition (CVD). The Young's moduli of the stretched CVD graphene membranes can be improved to ∼1 TPa, closing to the value of the pristine graphene. Our findings demonstrate a possible way to recover the exceptional elastic properties of CVD graphene from the softened stiffness caused by wrinkles.

Effect of cilostazol on cerebral arteries in secondary prevention of ischemic stroke.

OBJECTIVE: To compare the effects of cilostazol on cerebral arteries and cerebrovascular blood flow in secondary prevention of ischemic stroke, with those of aspirin. METHODS: Sixty-eight patients who had ischemic stroke during the recent 1-6 months were recruited and randomized into cilostazol or aspirin group. Cerebrovascular condition was assessed by magnetic resonance angiography (MRA) and transcranial doppler ultrasonography (TCD) at the beginning of the study and after 12-month medication. RESULTS: During the clinical follow-up, ischemic stroke recurred in 2 patients in cilostazol group, while in aspirin group, one case of ischemic stroke recurrence and one case of acute myocardial infarction were found. MRA revealed that in aspirin group, the percentages of patients experiencing aggravation and attenuation of cerebrovascular condition were 3.3% and 6.7%, respectively, while in aspirin group, they were 3.3% and 10%, respectively. Moreover, TCD revealed that 26.9% of the patients in aspirin group and 14.3% of the patients in cilostazol group experienced aggravation of cerebrovascular condition. However, the systolic peak flow velocity of the previously abnormal arteries increased by 42.9% after 12-month medication of cilostazol, which was significantly higher than that after aspirin medication (27.5%) (P = 0.04). Furthermore, as a major side effect of antiplatelet therapy, the frequency of bleeding was much less in cilostazol group (0 case in cilostazol group vs 5 in aspirin, P< 0.05). CONCLUSION: Cilostazol is as effective as aspirin in preventing the aggravation of cerebral arteries in secondary prevention of ischemic stroke. Besides, it is more safe. Cilostazol can increase the systolic peak flow velocity of cerebral arteries, which may improve the blood supply of focal ischemia.