Facile preparation of a metal-phenolic network-based lymph node targeting nanovaccine for antitumor immunotherapy.

Cancer vaccines are being explored for enhanced cancer immunotherapy and prophylaxis. Some of their prevailing weaknesses, however, such as complicated preparation, poor biocompatibility, and failure to elicit strong cellular immune responses, have limited their further clinical applications. Here, we reported a multifunctional nanovaccine that was prepared in a quick and simple way. During the self-assembly of metal-phenolic networks (MPNs), the antigen ovalbumin (OVA) and immunoreactive chlorogenic acid (CHA) were simultaneously loaded. Owing to its dual pH and reduction sensitivities, the nanovaccine could deliver antigens into the cytoplasm of dendritic cells (DCs) and facilitate the cross-presentation of antigens. Moreover, the results of in vivo immunization assays demonstrated that the nanovaccine significantly excited the antigen presentation of DCs and provoked a robust cellular immune response with the restrained activation of regulatory T cells (Tregs), by targeting lymph nodes and executing the function of CHA. In vivo antitumor assays indicated that the nanovaccine with good biocompatibility afforded conspicuous cancer treatment and prevention effects. Overall, the nanovaccine presented in this study shows a promise for potentiating cancer immunotherapy by the lymph node-targeted delivery. STATEMENT OF SIGNIFICANCE: Cancer nanovaccines can be used for cancer immunotherapy. However, some existing shortcomings, such as cumbersome preparation, poor biocompatibility, and failure to elicit strong immune responses, limit the clinical application of cancer nanovaccines. This study developed a multifunctional nanovaccine that was readily prepared through the self-assembly of metal-phenolic networks. The nanovaccine with dual pH and reduction sensitivities could efficiently promote the antigen lysosome escape and cross-presentation. In vivo, it efficiently delivered antigen into lymph nodes and provoked strong cellular immune responses, and thus it showed significant cancer immunotherapy and prevention effect.

Template-Assisted Direct Growth of 1 Td/in(2) Bit Patterned Media.

We present a method for growing bit patterned magnetic recording media using directed growth of sputtered granular perpendicular magnetic recording media. The grain nucleation is templated using an epitaxial seed layer, which contains Pt pillars separated by amorphous metal oxide. The scheme enables the creation of both templated data and servo regions suitable for high density hard disk drive operation. We illustrate the importance of using a process that is both topographically and chemically driven to achieve high quality media.

Low-temperature plasma etching of high aspect-ratio densely packed 15 to sub-10 nm silicon features derived from PS-PDMS block copolymer patterns.

The combination of block copolymer (BCP) lithography and plasma etching offers a gateway to densely packed sub-10 nm features for advanced nanotechnology. Despite the advances in BCP lithography, plasma pattern transfer remains a major challenge. We use controlled and low substrate temperatures during plasma etching of a chromium hard mask and then the underlying substrate as a route to high aspect ratio sub-10 nm silicon features derived from BCP lithography. Siloxane masks were fabricated using poly(styrene-b-siloxane) (PS-PDMS) BCP to create either line-type masks or, with the addition of low molecular weight PS-OH homopolymer, dot-type masks. Temperature control was essential for preventing mask migration and controlling the etched feature's shape. Vertical silicon wire features (15 nm with feature-to-feature spacing of 26 nm) were etched with aspect ratios up to 17 : 1; higher aspect ratios were limited by the collapse of nanoscale silicon structures. Sub-10 nm fin structures were etched with aspect ratios greater than 10 : 1. Transmission electron microscopy images of the wires reveal a crystalline silicon core with an amorphous surface layer, just slightly thicker than a native oxide.

Super-selective cryogenic etching for sub-10 nm features.

Plasma etching is a powerful technique for transferring high-resolution lithographic masks into functional materials. Significant challenges arise with shrinking feature sizes, such as etching with thin masks. Traditionally this has been addressed with hard masks and consequently additional costly steps. Here we present a pathway to high selectivity soft mask pattern transfer using cryogenic plasma etching towards low-cost high throughput sub-10 nm nanofabrication. Cryogenic SF(6)/O(2) gas chemistry is studied for high fidelity, high selectivity inductively coupled plasma etching of silicon. Selectivity was maximized on large features (400 nm-1.5 µm) with a focus on minimizing photoresist etch rates. An overall anisotropic profile with selectivity around 140:1 with a photoresist mask for feature size 1.5 µm was realized with this clean, low damage process. At the deep nanoscale, selectivity is reduced by an order of magnitude. Despite these limits, high selectivity is achieved for anisotropic high aspect ratio 10 nm scale etching with thin polymeric masks. Gentler ion bombardment resulted in planar-dependent etching and produced faceted sub-100 nm features.

High aspect ratio sub-15 nm silicon trenches from block copolymer templates.

High-aspect-ratio sub-15-nm silicon trenches are fabricated directly from plasma etching of a block copolymer mask. A novel method that combines a block copolymer reconstruction process and reactive ion etching is used to make the polymer mask. Silicon trenches are characterized by various methods and used as a master for subsequent imprinting of different materials. Silicon nanoholes are generated from a block copolymer with cylindrical microdomains oriented normal to the surface.

Thermal emission spectra from individual suspended carbon nanotubes.

We study the thermal emission spectra of individual suspended carbon nanotubes induced by electrical heating. Semiconducting and metallic devices exhibit different spectra, based on their distinctive band structures. These spectra are compared with the ideal blackbody emission spectrum. In the visible wavelength range, the thermal emission spectra of semiconducting devices agree well with Planck's law, while the spectra of metallic devices show an additional peak between 1.5 and 1.9 eV. In the near-infrared wavelength range, the semiconducting nanotubes exhibit a peak around 1 eV. These additional peaks are attributed to the E11M and E22SC transitions that are thermally driven under these high applied bias voltages. These peaks show a strong polarization dependence, while the blackbody tail is unpolarized, which provides further evidence for electron-hole recombination in thermal emission. For semiconducting devices, the temperature of the nanotube is fit to Planck's law and compared with the temperatures obtained from the G band and 2D band Raman downshifts, as well as the anti-Stokes/Stokes intensity ratio. For devices showing thermal non-equilibrium, the electron temperature agrees well with G+ downshift but deviates from G_ downshift.

Plasmon resonant enhancement of photocatalytic water splitting under visible illumination.

We demonstrate plasmonic enhancement of photocatalytic water splitting under visible illumination by integrating strongly plasmonic Au nanoparticles with strongly catalytic TiO2. Under visible illumination, we observe enhancements of up to 66× in the photocatalytic splitting of water in TiO2 with the addition of Au nanoparticles. Above the plasmon resonance, under ultraviolet radiation we observe a 4-fold reduction in the photocatalytic activity. Electromagnetic simulations indicate that the improvement of photocatalytic activity in the visible range is caused by the local electric field enhancement near the TiO2 surface, rather than by the direct transfer of charge between the two materials. Here, the near-field optical enhancement increases the electron-hole pair generation rate at the surface of the TiO2, thus increasing the amount of photogenerated charge contributing to catalysis. This mechanism of enhancement is particularly effective because of the relatively short exciton diffusion length (or minority carrier diffusion length), which otherwise limits the photocatalytic performance. Our results suggest that enhancement factors many times larger than this are possible if this mechanism can be optimized.

Optical manipulation of plasmonic nanoparticles, bubble formation and patterning of SERS aggregates.

We present an optical method for patterning SERS (surface-enhanced Raman spectroscopy)--enhancing aggregates of gold nanoparticles, using a focused laser beam to optically trap the nanoparticles in suspension. At high laser powers, heat generated from the plasmonic excitation causes boiling of the aqueous suspension and the formation of gaseous bubbles of water vapor. By measuring the Raman peak of the hydroxyl bond of water, the temperature in the laser spot during the aggregation can be determined in situ. The hydrophilic nanoparticles are found to aggregate at the liquid-vapor interface. By allowing the suspension to dry, a ring of gold nanoparticles is deposited on the substrate, producing a highly SERS-active region. These aggregates are studied using optical microscopy, scanning electron microscopy and micro-Raman spectroscopy.