Plasmonic catalysis provides a possible means for driving chemical reactions under relatively mild conditions. Rational design of these systems is impeded by the difficulty in understanding the electron dynamics and their interplay with reactions. Real-time, time-dependent density functional theory (RT-TDDFT) can provide dynamic information on excited states in plasmonic systems, including those relevant to plasmonic catalysis, at time scales and length scales that are otherwise out of reach of many experimental techniques. Here, we discuss previous RT-TDDFT studies of plasmonic systems, focusing on recent work that gains insight into plasmonic catalysis. These studies provide insight into plasmon dynamics, including size effects and the role of specific electronic states. Further, these studies provide significant insight into mechanisms underlying plasmonic catalysis, showing the importance of charge transfer between metal and adsorbate states, as well as local field enhancement, in different systems.

Molybdenum blues (MBs) are a distinct class of polyoxometalates, exhibiting versatile/impressive architectures and high structural flexibility. In acidified and reduced aqueous environments, isopolymolybdates generate precisely organizable building blocks, which enable unique nanoscopic molecular systems (MBs) to be constructed and further fine-tuned by hetero elements such as lanthanide (Ln) ions. This Review discusses wheel-shaped MB-based structure types with strong emphasis on the ∼30 Ln-containing MBs as of August 2021, which include both organically hybridized and nonhybridized structures synthesized to date. The spotlight is thereby put on the lanthanide ions and ligand types, which are crucial for the resulting Ln-patterns and alterations in the gigantic structures. Several critical steps and reaction conditions in their synthesis are highlighted, as well as appropriate methods to investigate them both in solid state and in solution. The final section addresses the homogeneous/heterogeneous catalytic, molecular recognition and separation properties of wheel-shaped Ln-MBs, emphasizing their inimitable behavior and encouraging their application in these areas.

Solid-state nanopores have been widely employed in the detection of biomolecules, but low signal-to-noise ratios still represent a major obstacle in the discrimination of nucleic acid and protein sequences substantially smaller than the nanopore diameter. The addition of 50% poly(ethylene) glycol (PEG) to the external solution is a simple way to enhance the detection of such biomolecules. Here, we demonstrate with finite-element modeling and experiments that the addition of PEG to the external solution introduces a strong imbalance in the transport properties of cations and anions, drastically affecting the current response of the nanopore. We further show that the strong asymmetric current response is due to a polarity-dependent ion distribution and transport at the nanopipette tip region, leading to either ion depletion or enrichment for few tens of nanometers across its aperture. We provide evidence that a combination of the decreased/increased diffusion coefficients of cations/anions in the bath outside the nanopore and the interaction between a translocating molecule and the nanopore–bath interface is responsible for the increase in the translocation signals. We expect this new mechanism to contribute to further developments in nanopore sensing by suggesting that tuning the diffusion coefficients of ions could enhance the sensitivity of the system.

Nanoparticle-based drug delivery systems have the potential for increasing the efficiency of chemotherapeutics by enhancing the drug accumulation at specific target sites, thereby reducing adverse side effects and mitigating patient acquired resistance. In particular, photo-responsive nanomaterials have attracted much interest due to their ability to release molecular cargos on demand upon light irradiation. In some settings, they can also provide complementary information by optical imaging on the (sub)cellular scale. We herein present a system based on lithium niobate harmonic nanoparticles (LNO HNPs) for the decoupled multi-harmonic cell imaging and near-infrared light-triggered delivery of an erlotinib derivative (ELA) for the treatment of epidermal growth factor receptor (EGFR)-overexpressing carcinomas. The ELA cargo was covalently conjugated to the surface of silica-coated LNO HNPs through a coumarinyl photo-cleavable linker, achieving a surface loading of the active molecule of 27 nmol/mg NPs. The resulting nanoconjugates (LNO-CM-ELA NPs) were successfully imaged upon pulsed laser excitation at 1250 nm in EGFR-overexpressing human prostate cancer cells DU145 by detecting the second harmonic emission at 625 nm, in the tissue transparency window. Tuning the laser at 790 nm resulted in the uncaging of the ELA cargo as a result of the second harmonic emission of the inorganic HNP core at 395 nm. This protocol induced a significant growth inhibition in DU145 cells, which was only observed upon specific irradiation at 790 nm, highlighting the promising capabilities of LNO-CM-ELA NPs for theranostic applications.

Understanding the polydispersity of nanoparticles is crucial for establishing the efficacy and safety of their role as drug delivery carriers in biomedical applications. Detonation nanodiamonds (DNDs), 3–5 nm diamond nanoparticles synthesized through detonation process, have attracted great interest for drug delivery due to their colloidal stability in water and their biocompatibility. More recent studies have challenged the consensus that DNDs are monodispersed after their fabrication, with their aggregate formation poorly understood. Here, we present a novel characterization method of combining machine learning with direct cryo-transmission electron microscopy imaging to characterize the unique colloidal behavior of DNDs. Together with small-angle X-ray scattering and mesoscale simulations we show and explain the clear differences in the aggregation behavior between positively and negatively charged DNDs. Our new method can be applied to other complex particle systems, which builds essential knowledge for the safe implementation of nanoparticles in drug delivery.

Nanoparticles based on biodegradable polymers have been shown to be excellent herbicide carriers, improving weed control and protecting the active ingredient in the crop fields. Metribuzin is often found in natural waters, which raises environmental concerns. Nanoencapsulation of this herbicide could be an alternative to reduce its losses to the environment and improve gains in its efficiency. However, there is a paucity of information about the behavior of nanoformulations of herbicides in environmental matrices. In this study, the stability of nanoencapsulated metribuzin in polymeric nanoparticles (nanoMTZ) was verified over time, as well as its dissipation in different soils, followed by the effects on soil enzymatic activity. The physiological parameters and control effects of nanoMTZ on Ipomoea grandifolia plants were investigated. No differences were verified in the half-life of nanoencapsulated metribuzin compared to a commercial formulation of the herbicide. Moreover, no suppressive effects on soil enzymatic activities were observed. The retention of nanoMTZ in the tested soils was lower compared to its commercial analogue. However, the mobility of nanoencapsulated metribuzin was not greatly increased, reflecting a low risk of groundwater contamination. Weed control was effective even at the lowest dose of nanoMTZ (48 g a.i. ha–1), which was consistent with the higher efficiency of nanoMTZ compared to the conventional herbicide in inhibiting PSII activity and decreasing pigment levels. Overall, we verified that nanoMTZ presented a low environmental risk, with increased weed control.

Corticosteroids are widely used as an anti-inflammatory treatment for eye inflammation, but the current methods used in clinical practice for delivery are in the form of eye drops which is usually complicated for patients or ineffective. This results in an increase in the risk of detrimental side effects. In this study, we demonstrated proof-of-concept research for the development of a contact lens-based delivery system. The sandwich hydrogel contact lens consists of a polymer microchamber film made via soft lithography with an encapsulated corticosteroid, in this case, dexamethasone, located inside the contact lens. The developed delivery system showed sustained and controlled release of the drug. The central visual part of the lenses was cleared from the polylactic acid microchamber in order to maintain a clean central aperture similar to the cosmetic-colored hydrogel contact lenses.

Electron transfer at a donor–acceptor quantum dot–metal oxide interface is a process fundamentally relevant to solar energy conversion architectures as, e.g., sensitized solar cells and solar fuels schemes. As kinetic competition at these technologically relevant interfaces largely determines device performance, this Review surveys several aspects linking electron transfer dynamics and device efficiency; this correlation is done for systems aiming for efficiencies up to and above the ∼33% efficiency limit set by Shockley and Queisser for single gap devices. Furthermore, we critically comment on common pitfalls associated with the interpretation of kinetic data obtained from current methodologies and experimental approaches, and finally, we highlight works that, to our judgment, have contributed to a better understanding of the fundamentals governing electron transfer at quantum dot–metal oxide interfaces.

The band structure and electronic properties of a material are defined by the sort of elements, the atomic registry in the crystal, the dimensions, the presence of spin–orbit coupling, and the electronic interactions. In natural crystals, the interplay of these factors is difficult to unravel, since it is usually not possible to vary one of these factors in an independent way, keeping the others constant. In other words, a complete understanding of complex electronic materials remains challenging to date. The geometry of two- and one-dimensional crystals can be mimicked in artificial lattices. Moreover, geometries that do not exist in nature can be created for the sake of further insight. Such engineered artificial lattices can be better controlled and fine-tuned than natural crystals. This makes it easier to vary the lattice geometry, dimensions, spin–orbit coupling, and interactions independently from each other. Thus, engineering and characterization of artificial lattices can provide unique insights. In this Review, we focus on artificial lattices that are built atom-by-atom on atomically flat metals, using atomic manipulation in a scanning tunneling microscope. Cryogenic scanning tunneling microscopy allows for consecutive creation, microscopic characterization, and band-structure analysis by tunneling spectroscopy, amounting in the analogue quantum simulation of a given lattice type. We first review the physical elements of this method. We then discuss the creation and characterization of artificial atoms and molecules. For the lattices, we review works on honeycomb and Lieb lattices and lattices that result in crystalline topological insulators, such as the Kekulé and “breathing” kagome lattice. Geometric but nonperiodic structures such as electronic quasi-crystals and fractals are discussed as well. Finally, we consider the option to transfer the knowledge gained back to real materials, engineered by geometric patterning of semiconductor quantum wells.

Thienothiophene thienoisoindigo (ttTII)-based covalent organic frameworks (COFs) have been shown to offer low band gaps and intriguing optical and electrochromic properties. So far, only one tetragonal thienothiophene thienoisoindigo-based COF has been reported showing stable and fast electrochromism and good coloration efficiencies. We have developed two novel COFs using this versatile and nearly linear ttTII building block in a tetragonal and a hexagonal framework geometry to demonstrate their attractive features for optoelectronic applications of thienoisoindigo-based COFs. Both COFs exhibit good electrical conductivities, show promising optical absorption features, are redox-active, and exhibit a strong electrochromic behavior when applying an external electrical stimulus, shifting the optical absorption even farther into the NIR region of the electromagnetic spectrum and achieving absorbance changes of up to 2.5 OD. Cycle-stable cyclic voltammograms with distinct oxidation and reduction waves reveal excellent reversibility and electrochromic switching over 200 cycles and confirm the high stability of the frameworks. Furthermore, high coloration efficiencies in the NIR region and fast switching speeds for coloration/decoloration as fast as 0.75 s/0.37 s for the Cz-ttTII COF and 0.61 s/0.29 s for the TAPB-ttTII COF at 550 nm excitation were observed, outperforming many known electrochromic materials, and offering options for a great variety of applications, such as stimuli-responsive coatings, optical information processing, or thermal control.

Optimizing the synthesis of atomically precise metal nanoclusters by virtue of molecular tools is highly desirable but quite challenging. Herein we report how 19F NMR spectroscopy can be used to guide the high-yield synthesis of N-heterocyclic carbene (NHC)-stabilized gold nanoclusters. In spite of little difference, 19F NMR signals of fluoro-incorporated NHCs (FNHC) are highly sensitive to the tiny change in their surrounding chemical environments with different N-substituents, metals, or anions, thus providing a convenient strategy to discriminate species in reaction mixtures. By using 19F NMR, we first disclosed that the one-pot reduction of FNHC-Au-X (X is halide) yields multiple compounds, including cluster compounds and also a large amount of highly stable [Au(FNHC)2]+ byproduct. The detailed quantitative 19F NMR analyses over the reductive synthesis of NHC-stabilized Au nanoclusters reveal that the formation of the di-NHC complex is deleterious to the high-yield synthesis of NHC-stabilized Au nanoclusters. With the understanding, the reaction kinetic was then slowed by controlling the reduction rate to achieve the high yield of a [Au24(FNHC)14X2H3]3+ nanocluster with a unique structure. The strategy demonstrated in this work is expected to provide an effective tool to guide the high-yield synthesis of organic ligand-stabilized metal nanoclusters.

We are thrilled to feature a set of outstanding papers in the first issue of Volume 2 of ACS Nanoscience Au! As was also the case in our first issue (DOI: 10.1021/acsnanoscienceau.1c00051), these papers showcase the breadth of the field. When I read this collection, I was struck by the common theme of “design” that was integral throughout the wide range of topics. All of these papers present new knowledge that improves and expands our ability to design nanostructures with precise features, which directly correlate with their functions. A Perspective by Jia Guo, Ting Cheng, and Yan Li from Peking University and Rong Xiang and Shigeo Maruyama from the University of Tokyo discusses one-dimensional (1D) van der Waals (vdW) heterostructures, which offer distinct properties and applications relative to 2D vdW materials that have been extensively studied. The authors emphasize the building-block nature of 1D vdW nanostructures and pathways for synthesizing them, ultimately showcasing a strategy for designing and synthesizing high-quality 1D vdW heterostructures. A Review by Renyun Zhang and Håkan Olin from Mid Sweden University highlights how many different types of inorganic nanomaterials can be used to produce triboelectric nanogenerators that convert mechanical energy to electricity. Zhang and Olin discuss the types and compositions of inorganic nanomaterials that are used in triboelectric nanogenerators, as well as their roles. This comprehensive overview provides design guidelines for how inorganic nanomaterials can be incorporated into triboelectric nanogenerators to achieve unique properties. An Article by Zehua Li, Lei Kang, Robert Lord, Raymond Schaak, Douglas Werner, and Kenneth Knappenberger Jr. from Penn State University and Kyoungweon Park, Andrew Gillman, and Richard Vaia from the Air Force Research Laboratory demonstrates that chiroptical signals can arise from achiral objects due to subtle morphological effects, including atomic-level faceting and asymmetric rounding at nanorod tips. These insights provide new guidelines for designing chiral nanostructures, and I am honored to be a coauthor on this work. An Article by Qing Tang and Fuhua Li from Chongqing University and De-en Jiang from the University of California, Riverside, shows how the structure, bonding, and properties of an atomically precise gold nanocluster evolve with pressure. This computational study provides guidelines for designing cluster-based crystals that have new structures and properties and motivates future experimental studies. An Article by Marcus Tornberg, Robin Sjökvist, Krishna Kumar, Carina Maliakkal, Daniel Jacobsson, and Kimberly Dick from Lund University and Christopher Andersen from Lund University and the Technical University of Denmark provides direct microscopic visualization of twin formation during growth of GaAs nanowires. (The videos provided as Supporting Information are definitely worth viewing! See video 1, video 2, and video 3.) Thermodynamic modeling complements the in situ microscopy to provide new insights and guidelines that will help to enable atomic-level precision during semiconductor nanowire growth. Finally, an Article by Yusuke Sakai, Gerrit Wilkens, Karol Wolski, Szczepan Zapotoczny, and Jonathan Heddle from Jagiellonian University, which is featured on the front cover, reports a general method for producing topologically linked DNA origami. The authors show that catenated single-stranded DNA circles serve as a universal scaffold for catenated DNA origami structures of any design. This approach provides a simple strategy for designing and synthesizing “topogami” DNA nanostructures that are typically challenging to prepare. The research in the second issue of ACS Nanoscience Au provides the nanoscience and nanotechnology communities with knowledge and insights that will be useful for designing new nanostructures with unique features and functions. We are excited about these papers and look forward to seeing more contributions in these and other areas of research! Other research that is available online, which will feature in future issues of ACS Nanoscience Au, describes finite-size effects on energy transfer in nanocrystalline phosphors, photoluminescent lead-free halide perovskite nanocrystals, quantum-confined nanoparticles for photocatalysis, metal-oxide nanomaterials for flexible and wearable sensors, single-molecule sensing of miniproteins with nanopores, and an in vivo imaging platform based on chemically modifiable nanoemulsions. These ASAP publications also highlight the broad topical diversity that defines nanoscience and nanotechnology, and we look forward to featuring these topics, and many others, in future issues! This article has not yet been cited by other publications.

MXenes are a growing family of 2D transition-metal carbides and nitrides, which display excellent performance in myriad of applications. Theoretical calculations suggest that manipulation of the MXene surface termination (such as ═O or −F) could strongly alter their functional properties; however, experimental control of the MXene surface termination is still in the developmental stage. Here, we demonstrate that annealing MXenes in an Ar + O2 low-power plasma results in increased ═O functionalization with minimal formation of secondary phases. We apply this method to two MXenes, Ti2CTx and Mo2TiC2Tx (Tx represents the mixed surface termination), and show that in both cases, the increased ═O content increases the electrical resistance and decreases the surface transition-metal’s electron count. For Mo2TiC2Ox, we show that the O content can be reversibly altered through successive vacuum and plasma annealing. This work provides an effective way to tune MXene surface functionalization, which may unlock exciting surface-dependent properties.

Cation exchange is becoming extensively used for nanocrystal (NC) doping in order to produce NCs with unique optical and electronic properties. However, despite its ever-increasing use, the relationships between the cation exchange process, its doped NC products, and the resulting NC photophysics are not well characterized. For example, similar doping procedures on NCs with the same chemical compositions have resulted in quite different photophysics. Through a detailed single molecule investigation of a postsynthesis Ag+ doping of CdSe NCs, a number of species were identified within a single doped NC sample, suggesting the differences in the optical properties of the various synthesis methods are due to the varied contributions of each species. Electrostatic force microscopy (EFM), electron energy loss spectroscopy (EELS) mapping, and single molecule photoluminescence (PL) studies were used to identify four possible species resulting from the Ag+-CdSe cation exchange doping process. The heterogeneity of these samples shows the difficulty in controlling a postsynthesis cation exchange method to produce homogeneous samples needed for use in any potential application. Additionally, the heterogeneity in the doped samples demonstrates that significant care must be taken in describing the ensemble or average characteristics of the sample.

The electronic properties of electrode materials play a crucial role in defining their electrochemical behavior in energy conversion and storage devices. The assembly of van der Waals heterostructures and fabrication into mesoscopic devices enable the dependence of an electrochemical response on electronic properties to be systematically interrogated. Here, we evaluate the effect of charge carrier concentration on heterogeneous electron transfer at few-layer MoS2 electrodes by combining spatially resolved electrochemical measurements with field-effect electrostatic manipulation of band alignment. Steady-state cyclic voltammograms and finite-element simulations reveal a strong modulation of the measured electrochemical response for outer-sphere charge transfer at the electrostatic gate voltage. In addition, spatially resolved voltammetric responses, obtained at a series of locations at the surface of few-layer MoS2, reveal the governing role of in-plane charge transport on the electrochemical behavior of 2D electrodes, especially under conditions of low carrier densities.

Information processing by traditional, serial electronic processors consumes an ever-increasing part of the global electricity supply. An alternative, highly energy efficient, parallel computing paradigm is network-based biocomputation (NBC). In NBC a given combinatorial problem is encoded into a nanofabricated, modular network. Parallel exploration of the network by a very large number of independent molecular-motor-propelled protein filaments solves the encoded problem. Here we demonstrate a significant scale-up of this technology by solving four instances of Exact Cover, a nondeterministic polynomial time (NP) complete problem with applications in resource scheduling. The difficulty of the largest instances solved here is 128 times greater in comparison to the current state of the art for NBC.

Controlling the flow of broadband electromagnetic energy at the nanoscale remains a critical challenge in optoelectronics. Surface plasmon polaritons (or plasmons) provide subwavelength localization of light but are affected by significant losses. On the contrary, dielectrics lack a sufficiently robust response in the visible to trap photons similar to metallic structures. Overcoming these limitations appears elusive. Here we demonstrate that addressing this problem is possible if we employ a novel approach based on suitably deformed reflective metaphotonic structures. The complex geometrical shape engineered in these reflectors emulates nondispersive index responses, which can be inverse-designed following arbitrary form factors. We discuss the realization of essential components such as resonators with an ultrahigh refractive index of n = 100 in diverse profiles. These structures support the localization of light in the form of bound states in the continuum (BIC), fully localized in air, in a platform in which all refractive index regions are physically accessible. We discuss our approach to sensing applications, designing a class of sensors where the analyte directly contacts areas of ultrahigh refractive index. Leveraging this feature, we report an optical sensor with sensitivity two times higher than the closest competitor with a similar micrometer footprint. Inversely designed reflective metaphotonics offers a flexible technology for controlling broadband light, supporting optoelectronics’ integration with large bandwidths in circuitry with miniaturized footprints.

Vanadium dioxide (VO2) can adopt many different crystal structures at ambient temperature and pressure, each with different, and often desirable, electronic, optical, and chemical properties. Understanding how to control which crystal phase forms under various reaction conditions is therefore crucial to developing VO2 for various applications. This paper describes the impact of ligand acidity on the formation of VO2 nanocrystals from the solvothermal reaction of vanadyl acetylacetonate (VO(acac)2) with stoichiometric amounts of water. Carboxylic acids examined herein favor the formation of the monoclinic VO2(B) phase over the tetragonal VO2(A) phase as the concentration of water in the reaction increases. However, the threshold concentration of water required to obtain phase-pure VO2(B) nanocrystals increases as the pKa of the carboxylic acid decreases. We also observe that increasing the concentration of VO(acac)2 or the concentration of acid while keeping the concentration of water constant favors the formation of VO2(A). Single-crystal electron diffraction measurements enable the identification of vanadyl carboxylate species formed in reactions that do not contain enough water to promote the formation of VO2. Increasing the length of the carbon chain on aliphatic carboxylic acids did not impact the phase of VO2 nanocrystals obtained but did result in a change from nanorod to nanoplatelet morphology. These results suggest that inhibiting the rate of hydrolysis of the VO(acac)2 precursor either by decreasing the ratio of water to VO(acac)2 or by increasing the fraction of water molecules that are protonated favors the formation of VO2(A) over VO2(B).

Developing new techniques to prepare free-standing tubular scaffolds has always been a challenge in the field of regenerative medicine. Here, we report a new and simple way to prepare free-standing collagen constructs with rolled-up architecture by self-assembling nanofibers on porous alumina (Al2O3) textiles modified with different silanes, carbon or gold. Following self-assembly and cross-linking with glutaraldehyde, collagen nanofibers spontaneously rolled up on the modified Al2O3 textiles and detached. The resulting collagen constructs had an inner diameter of approximately 2 to 4 mm in a rolled-up state and could be easily detached from the underlying textiles. Mechanical testing of wet collagen scaffolds following detachment yielded mean values of 3.5 ± 1.9 MPa for the tensile strength, 41.0 ± 20.8 MPa for the Young’s modulus and 8.1 ± 3.7% for the elongation at break. No roll-up was observed on Al2O3 textiles without any modification, where collagen did not assemble into fibers, either. Blends of collagen and chitosan were also found to roll into fibrous constructs on silanized Al2O3 textiles, while fibrinogen nanofibers or blends of collagen and elastin did not yield such structures. Based on these differences, we hypothesize that textile surface charge and protein charge, in combination with the porous architecture of protein nanofibers and differences in mechanical strain, are key factors in inducing a scaffold roll-up. Further studies are required to develop the observed roll-up effect into a reproducible biofabrication process that can enable the controlled production of free-standing collagen-based tubes for soft tissue engineering.

Recently, the advent of health risks due to the cytotoxicity of fine particulate matter (FPM) is concerning. Numerous studies have reported abundant data elucidating the FPM-induced cell death pathways. However, several challenges and knowledge gaps are still confronted nowadays. On one hand, the undefined components of FPM (such as heavy metals, polycyclic aromatic hydrocarbons, and pathogens) are all responsible for detrimental effects, thus rendering it difficult to delineate the specific roles of these copollutants. On the other hand, owing to the crosstalk and interplay among different cell death signaling pathways, precisely determining the threats and risks posed by FPM is difficult. Herein, we recapitulate the current knowledge gaps present in the recent studies regarding FPM-induced cell death, and propose future research directions for policy-making to prevent FPM-induced diseases and improve knowledge concerning the adverse outcome pathways and public health risks of FPM.