ACS Nano最新文献

The vast extensional planes of two-dimensional (2D) nanomaterials are recognized as desirable ground for electrocatalytic reactions. However, they tend to exhibit catalytic inertia due to their surface-ordered coordination configurations. Herein, an in situ autoxidation strategy enables high-density grafting of ultrafine CeO₂ nanoclusters on 2D Co(OH)₂. Affluent active units were activated at the inert interface of Co(OH)₂ via the formation of Co-O-Ce units. The optimized catalyst exhibits oxygen evolution reaction activity with an overpotential of 83 mV lower than that of Co(OH)₂ at 10 mA cm^-2. The cascade orbital coupling between Co (3d) and Ce (4f) in Co-O-Ce units drives electron transfer by unlocking a "d-f electron ladder". Meanwhile, the bond-order theorem analyses and the d-band center show that the occupancy of Co-3d-e_g is optimized to balance the adsorption-desorption process of active sites to the key reaction intermediate *OOH, thereby making it easier to release oxygen. This work will drive the development of wider area electron modulation methods and provide guidance for the surface engineering of 2D nanomaterials.

Transmetalation represents an appealing strategy toward fabricating and tuning functional metal-organic polymers and frameworks for diverse applications. In particular, building two-dimensional metal-organic and organometallic networks affords versatile nanoarchitectures of potential interest for nanodevices and quantum technology. The controlled replacement of embedded metal centers holds promise for exploring versatile material varieties by serial modification and different functionalization. Herein, we introduce a protocol for the modification of a single-layer carbon-metal-based organometallic network via transmetalation. By integrating external Cu atoms into the alkynyl-Ag organometallic network constructed with 1,3,5-triethynylbenzene precursors, we successfully realized in situ its highly regular alkynyl-Cu counterpart on the Ag(111) surface. While maintaining a similar lattice periodicity and pore morphology to the original alkynyl-Ag sheet, the Cu-based network exhibits increased thermal stability, guaranteeing improved robustness for practical implementation.

Intraperitoneal co-delivery of chemotherapeutic drugs (CDs) and immune checkpoint inhibitors (ICIs) brings hope to improve treatment outcomes in patients with peritoneal metastasis from ovarian cancer (OC). However, current intraperitoneal drug delivery systems face issues such as rapid drug clearance from lymphatic drainage, heterogeneous drug distribution, and uncontrolled release of therapeutic agents into the peritoneal cavity. Herein, we developed an injectable nanohydrogel by combining carboxymethyl chitosan (CMCS) with bioadhesive nanoparticles (BNPs) based on polylactic acid-hyperbranched polyglycerol. This system enables the codelivery of CD and ICI into the intraperitoneal space to extend drug retention. The nanohydrogel is formed by cross-linking of aldehyde groups on BNPs with amine groups on CMCS via reversible Schiff base bonds, with CD and ICI loaded separately into BNPs and CMCS network. BNP/CMCS nanohydrogel maintained the activity of the biomolecules and released drugs in a sustained manner over a 7 day period. The adhesive property, through the formation of Schiff bases with peritoneal tissues, confers BNPs with an extended residence time in the peritoneal cavity after being released from the nanohydrogel. In a mouse model, BNP/CMCS nanohydrogel loaded with paclitaxel (PTX) and anti-PD-1 antibodies (αPD-1) significantly suppressed peritoneal metastasis of OC compared to all other tested groups. In addition, no systemic toxicity of nanohydrogel-loaded PTX and αPD-1 was observed during the treatment, which supports potential translational applications of this delivery system.

Lead chalcogenide colloidal quantum dots are one of the most promising materials to revolutionize the field of short-wavelength infrared optoelectronics due to their bandgap tunability and strong absorption. By self-assembling these quantum dots into ordered superlattices, mobilities approaching those of the bulk counterparts can be achieved while still retaining their original optical properties. The recent literature focused mostly on PbSe-based superlattices, but PbS quantum dots have several advantages, including higher stability. In this work, we demonstrate highly ordered 3D superlattices of PbS quantum dots with tunable thickness up to 200 nm and high coherent ordering, both in-plane and along the thickness. We show that we can successfully exchange the ligands throughout the film without compromising the ordering. The superlattices as the active material of an ion gel-gated field-effect transistor achieve electron mobilities up to 220 cm² V^-1 s^-1. To further improve the device performance, we performed a postdeposition passivation with PbI₂, which noticeably reduced the subthreshold swing making it reach the Boltzmann limit. We believe this is an important proof of concept showing that it is possible to overcome the problem of high trap densities in quantum dot superlattices enabling their application in optoelectronic devices.

The Stöber method for forming spherical silica colloids is well-established as one of the pillars of colloidal synthesis. In a modified form, it has been extensively used to deposit both porous and protective shells over metal nanomaterials. Current best-practice techniques require that the vitreophobic surface of metal nanoparticles be primed with a surface ligand to promote silica deposition. Although such techniques have proved highly successful in forming core-shell configurations, the site-selective deposition of silica onto preselected areas of faceted metal nanostructures has proved far more challenging. Herein, a primer-free TEOS-based synthesis is demonstrated that is capable of forming architecturally complex nanoframes and nanocages on the pristine surfaces of faceted gold nanostructures. The devised synthesis overcomes vitreophobicity using elevated TEOS concentrations that trigger silica nucleation along the low-coordination sites where gold facets meet. Continued deposition sees the emergence of a well-connected frame followed by the lateral infilling of the openings formed over gold facets. With growth readily terminated at any point in this sequence, the synthesis distinguishes itself in being able to achieve patterned and tunable silica depositions expressing interfaces that are uncorrupted by primers. The so-formed structures are demonstrated as template materials capable of asserting high-level control over synthesis and assembly processes by using the deposited silica as a mask that deactivates selected areas against these processes while allowing them to proceed elsewhere. The work, hence, extends the capabilities and versatility of TEOS-based syntheses and provides pathways for forming multicomponent nanostructures and nanoassemblies with structurally engineered properties.

The band gap constraint of the photocatalyst for overall water splitting limits the utilization of solar energy. A strategy to broaden the range of light absorption is employing a two-dimensional (2D) polar material as photocatalyst, benefiting from the deflection of the energy level due to their intrinsic internal electric field. Here, by using first-principles computational screening, we search for 2D polar semiconductors for photocatalytic water splitting from both ground- and excited-state perspectives. Applying a unique electronic structure model of polar materials, there are 13 photocatalyst candidates for the hydrogen evolution reaction (HER) and 8 candidates for the oxygen evolution reaction (OER) without barrier energies from the perspective of the ground-state free energy variation calculation. In particular, Cu₂As₄Cl₂S₃ and Cu₂As₄Br₂S₃ can catalyze HER and OER simultaneously, becoming promising photocatalysts for overall water splitting. Furthermore, by combining ground-state band structure calculations with excited-state charge distribution and transfer calculated by linear-response time-dependent density functional theory (LR-TDDFT) and time-dependent ab initio nonadiabatic molecular dynamics (NAMD), respectively, the rationality of the 2D polar material model has been manifested. The intrinsic built-in electric field promotes the separation of charge carriers while suppressing their recombination. Therefore, our computational work provides a high-throughput method to design high-performance photocatalysts for water splitting.

Recent advances enable the creation of nanoscale building blocks with complex geometries and interaction specificities for self-assembly. This nearly boundless design space necessitates design principles for defining the mutual interactions between multiple particle species to target a user-specified complex structure or pattern. In this article, we develop a symmetry-based method to generate the interaction matrices that specify the assembly of two-dimensional tilings, which we illustrate using equilateral triangles. By exploiting the allowed 2D symmetries, we develop an algorithmic approach by which any periodic 2D tiling can be generated from an arbitrarily large number of subunit species, notably addressing an unmet challenge of engineering 2D crystals with periodicities that can be arbitrarily larger than the subunit size. To demonstrate the utility of our design approach, we encode specific interactions between triangular subunits synthesized by DNA origami and show that we can guide their self-assembly into tilings with a wide variety of symmetries, using up to 12 unique species of triangles. By conjugating specific triangles with gold nanoparticles, we fabricate gold-nanoparticle supracrystals whose lattice parameter spans up to 300 nm. Finally, to generate economical design rules, we compare the design economy of various tilings. In particular, we show that (1) higher symmetries allow assembly of larger unit cells with fewer subunits and (2) linear supracrystals can be designed more economically using linear primitive unit cells. This work provides a simple algorithmic approach to designing periodic assemblies, aiding in the multiscale assembly of supracrystals of nanostructured "meta-atoms" with engineered plasmonic functions.

Protein nanoparticles are effective platforms for antigen presentation and targeting effector immune cells in vaccine development. Encapsulins are a class of protein-based microbial nanocompartments that self-assemble into icosahedral structures with external diameters ranging from 24 to 42 nm. Encapsulins from Myxococcus xanthus were designed to package bacterial RNA when produced in E. coli and were shown to have immunogenic and self-adjuvanting properties enhanced by this RNA. We genetically incorporated a 20-mer peptide derived from a mutant strain of the SARS-CoV-2 receptor binding domain (RBD) into the encapsulin protomeric coat protein for presentation on the exterior surface of the particle, inducing the formation of several nonicosahedral structures that were characterized by cryogenic electron microscopy. This immunogen elicited conformationally relevant humoral responses to the SARS-CoV-2 RBD. Immunological recognition was enhanced when the same peptide was presented in a heterologous prime/boost vaccination strategy using the engineered encapsulin and a previously reported variant of the PP7 virus-like particle, leading to the development of a selective antibody response against a SARS-CoV-2 RBD point mutant. While generating epitope-focused antibody responses is an interplay between inherent vaccine properties and B/T cells, here we demonstrate the use of orthogonal nanoparticles to fine-tune the control of epitope focusing.