Assembly and Healing: Capacitive and Conductive Plasmonic Interfacing via a Unified and Clean Wet Chemistry Route.

Solution-based nanoparticle assembly represents a highly promising way to build functional metastructures based on a wealth of synthetic nanomaterial building blocks with well-controlled morphology and crystallinity. In particular, the involvement of DNA molecular programming in these bottom-up processes gradually helps the ambitious goal of customizable chemical nanofabrication. However, a fundamental challenge is to realize strong interunit coupling in an assembly toward emerging functions and applications. Herein, we present a unified and clean strategy to address this critical issue based on a H2O2-redox-driven "assembly and healing" process. This facile solution route is able to realize both capacitively coupled and conductively bridged colloidal boundaries, simply switchable by the reaction temperature, toward bottom-up nanoplasmonic engineering. In particular, such a "green" process does not cause surface contamination of nanoparticles by exogenous active metal ions or strongly passivating ligands, which, if it occurs, could obscure the intrinsic properties of as-formed structures. Accordingly, previously raised questions regarding the activities of strongly coupled plasmonic structures are clarified. The reported process is adaptable to DNA nanotechnology, offering molecular programmability of interparticle charge conductance. This work represents a new generation of methods to make strongly coupled nanoassemblies, offering great opportunities for functional colloidal technology and even metal self-healing.

DNA-Condensed Plasmonic Supraballs Transparent to Molecules.

DNA nanotechnology offers an unrivaled programmability of plasmonic nanoassemblies based on encodable Watson-Crick basepairing. However, it is very challenging to build rigidified three-dimensional supracolloidal assemblies with strong electromagnetic coupling and a self-confined exterior shape. We herein report an alternative strategy based on a DNA condensation reaction to make such structures. Using DNA-grafted gold nanoparticles as building blocks and metal ions with suitable phosphate affinities as abiological DNA-bonding agents, a seedless growth of spheroidal supraparticles is realized via metal-ion-induced DNA condensation. Some governing rules are disclosed in this process, including kinetic and thermodynamic effects stemming from electrostatic and coordinative forces with different interaction ranges. The supraballs are tailorable by adjusting the volumetric ratio between DNA grafts and gold cores and by overgrowing extra gold layers toward tunable plasmon coupling. Various appealing and highly desirable properties are achieved for the resulting metaballs, including (i) chemical reversibility and fixation ability, (ii) stability against denaturant, salt, and molecular adsorbates, (iii) enriched and continuously tunable plasmonic hotspots, (iv) permeability to small guest molecules and antifoulingness against protein contaminates, and (v) Raman-enhancing and photocatalytic activities. Innovative applications are thus foreseeable for this emerging class of meta-assemblies in contrast to what is achieved by DNA-basepaired ones.

Decoupled Roles of DNA-Surfactant Interactions: Instant Charge Inversion, Enhanced Colloidal and Chemical Stabilities, and Fully Tunable DNA Conjugation of Shaped Plasmonic Nanocrystals.

Surfactant-dictated syntheses of nanomaterials with well-defined shapes offer an extra dimension of control beyond nanoparticle size and chemical composition on the properties and self-assembly behaviors of colloidal materials. However, the surfactant bilayers on nanocrystals often cause great difficulty toward DNA grafting due to their unfavorable electrostatic charges and dense surface packing. Herein a revisit to this dilemma unveils a rapid charge inversion and enhanced colloidal/chemical stabilities of cationic-bilayer-covered nanocrystals upon DNA adsorption. Decoupling this hidden scenario provides a rationale to significantly improve DNA functionalization of surfactant-capped nanocrystals. Accordingly, fully tunable DNA conjugation (via Au-S bonding) on up to seven classes of surfactant-coated metal nanounits is easily and consistently achievable. The DNA-nanocrystal complexes featuring a continuously variable DNA density function well in DNA-guided nanoassembly. Our method opens the door to a wealth of material building blocks derived by surfactant-directed nanosyntheses toward DNA-programmable, extremely diversified, and highly complicated structures and functions.

Steering DNA Condensation on Engineered Nanointerfaces.

DNA has received increasing attention in nanotechnology due to its ability to fold into prescribed structures. Different from the commonly adopted base-pairing strategy, an emerging class of amorphous DNA materials are formed by DNA's abiological interactions. Despite the great successes, a lack of nanoscale nucleation/growth control disables more advanced considerations. This work aims at harnessing the heterogeneous nucleation of metal-ion-glued DNA condensates on nanointerfaces. Upon unveiling key orthogonal factors including solution pH, ionic cross-linkers, and surface functionalities, chemically programmable DNA condensation on nanoparticle seeds is achieved, resembling a famous Stöber process for silica coating. The nucleation rules discovered on individual nanoseeds can be passed on to their dimeric assemblies, where broken spherical symmetry and the existence of interparticle gaps help a regiospecific DNA gelation. The steerable DNA condensation, and the multifunctions from DNA, metal ions, and nanocores, hold a great promise in noncanonical DNA nanotechnology toward novel applications.

Evaporative Drying: A General and Readily Scalable Route to Spherical Nucleic Acids with Quantitative, Fully Tunable, and Record-High DNA Loading.

Nanoparticles (NPs) grafted with highly dense DNA strands are termed as spherical nucleic acids (SNAs), which have important applications benefiting from various unique properties unpossessed by naturally occurring nucleic acids. To overcome existing challenges toward an ideal SNA synthesis, herein, a very simple, while highly effective evaporative drying strategy featuring various long-desired advantages, is reported. This includes record-high DNA loading, generality for more NP materials, fully and quantitatively tunable DNA density, and readiness toward bulk production. The process requires almost zero care and the solid products are especially suitable for a long-time storage without quality degradation. The research reveals a quick and highly efficient packing of thiol-tagged DNA on the NP surface at the critical moment of drying, which refreshes previous knowledge on DNA conjugation chemistry. Based on this advancement, practical applications of SNAs in various fields may become possible.

DNA-Programmable AgAuS-Primed Conductive Nanowelding Wires-Up Wet Colloids.

Self-assembly of nanomaterials, directed by molecular or supramolecular interactions, is a powerful strategy to build nanoscale devices. Despite many advantages of such solution-based processes, a big challenge is to realize interparticle ohmic contacts toward facilitated charge transport over a long distance. We report a new concept of primed nanowelding to thread solution-borne nanoparticles in prescribed assemblies. The process starts with a gap-specific deposition of Ag2 E (E=S, Se) materials in pre-assembled gold structures, which spontaneously transform into AgAuE semiconductors via directional gold diffusion. Treatment with tributylphosphine generates alloyed Au/Ag welding spots that conductively wire-up nanoparticles into discrete "molecules" and micron-long "polymers". This method is compatible with DNA programming and delivers a possible way to solve the problem of the carrier-transport dilemma in solution-processed nanostructures for better-functioning nanodevices.

Flash Synthesis of Spherical Nucleic Acids with Record DNA Density.

Nanoparticles (NPs) decorated with a high density of DNA strands, also known as spherical nucleic acids (SNAs), are widely used in DNA-programmable assembly, sensing, imaging, and therapeutics. A regular SNA synthesis is very time-consuming, which requires great caution to avoid NP aggregation. Herein we report an extremely simple, efficient, and scalable process to realize instant (in seconds) synthesis of SNAs with record-high DNA density. Our method relies on a rapid water removal from a DNA/NP mixture in contact with a butanol phase. This process generates a dehydrated "solid solution" that greatly accelerates DNA anchorage on NPs via Au-S bonding. Compared to a state-of-the-art DNA conjugation strategy in the literature, up to 3-time increase of DNA density is achieved by the instant dehydration in butanol (INDEBT). The ultradense DNA grafting is accomplished in a few seconds, which is highly hybridizable to form core-satellite assemblies. Our work turns SNA synthesis into an easy job, and enables future explorations of physical, chemical, and biological effects of SNAs with ultrahigh DNA density.

Antibody responses to SARS-CoV-2 in healthy individuals returning to Shenzhen.

To verify reliability of antibody detection and investigate population immunity to severe acute respiratory syndrome-related coronavirus 2 (SARS-CoV-2) in the local Chinese population. A cross-sectional study was conducted in Shenzhen to detect anti-coronavirus antibodies including, immunoglobulin G (IgG), immunoglobulin M (IgM), and immunoglobulin A (IgA). In the COVID-19 group, nine patients were enrolled after diagnosis. In the control group, 1589 individuals without clinical symptoms (cough, fever, and fatigue) and returning from outside Shenzhen were enrolled. The first study enrollment occurred at the end of February 2020; the final study visit was 18 March 2020. In the COVID-19 group, the seven of nine patients were positive for IgM, IgG, and IgA. Meanwhile, six of the 1589 healthy individuals were found to be weakly positive for IgG. According to SARS-CoV-2 nucleic acid tests, the six individuals were all negative. Strong supplemental support for clinical information can be provided by antibody detection, especially for IgA. According to comparison with overseas reports, the infection rate of the Chinese population outside Shenzhen, China, is significantly low, so most of the population in China is still susceptible. Hence, social distancing measures are still inevitable until a vaccine is developed successfully.

Ag Ion Soldering: An Emerging Tool for Sub-nanomeric Plasmon Coupling and Beyond.

Self-assembly represents probably the most flexible way to construct metastructured materials and devices from a wealth of colloidal building blocks with synthetically controllable sizes, shapes, and elemental compositions. In principle, surface capping is unavoidable during the synthesis of nanomaterials with well-defined geometry and stability. The ligand layer also endows inorganic building blocks with molecular recognition ability responsible for their assembly into desired structures. In the case of plasmonic nanounits, precise positioning of them in a nanomolecule or an ordered nanoarray provides a chance to shape their electrodynamic behaviors and thereby assists experimental demonstration of modern nanoplasmonics toward practical uses. Despite previous achievements in bottom-up nanofabrication, a big challenge exists toward strong coupling and facile charge transfer between adjacent nanounits in an assembly. This difficulty has impeded a functional development of plasmonic nanoassemblies. The weakened interparticle coupling originates from the electrostatic and steric barriers of ionic/molecular adsorbates to guarantee a good colloidal stability. Such a dilemma is rooted in fundamental colloidal science, which lacks an effective solution. During the past several years, a chemical tool termed Ag ion soldering (AIS) has been developed to overcome the above situation toward functional colloidal nanotechnology. In particular, a dimeric assembly of plasmonic nanoparticles has been taken as an ideal model to study plasmonic coupling and interparticle charge transfer. This Account starts with a demonstration of the chemical mechanism of AIS, followed by a verification of its workability in various self-assembly systems. A further use of AIS to realize postsynthetic coupling of DNA-directed nanoparticle clusters evidences its compatibility with DNA nanotechnology. Benefiting from the sub-nanometer interparticle gap achieved by AIS, a conductive pathway is established between two nanoparticles in an assembly. Accordingly, light-driven charge transfer between the conductively bridged plasmonic units is realized with highly tunable resonance frequencies. These situations have been demonstrated by thermal/photothermal sintering of silica-isolated nanoparticle dimers as well as gap-specific electroless gold/silver deposition. The regioselective silver deposition is then combined with galvanic replacement to obtain catalytically active nanofoci (plasmonic nanogaps). The resulting structures are useful for real time and on-site Raman spectroscopic tracking of chemical reactions in the plasmonic hotspots (nanogaps) as well as for study of plasmon-mediated/field-enhanced catalysis. The Account is concluded by a deeper insight into the chemical mechanism of AIS and its adaption to conformation-rich structures. Finally, AIS-enabled functional pursuits are suggested for self-assembled materials with strongly coupled and easily reshapable physicochemical properties.

Base-Sequence-Independent Efficient Redox Switching of Self-Assembled DNA Nanocages.

Stimuli responsivity has been extensively pursued in dynamic DNA nanotechnology, due to its incredible application potentials. Among diverse dynamic systems, redox-responsive DNA assembly holds great promise for broad applications, especially considering that redox processes widely exist in various physiological environments. However, only a few studies have been reported on redox-sensitive dynamic DNA assembly. Albeit ingenious, most of these studies are either dependent on the DNA sequence or involve chemical modification. Herein, a facile and universal mechanism to realize redox-responsive self-assembly of DNA nanocages (tetrahedron and cube) driven by the interconversion between cystamine and cysteamine toward dynamic DNA nanotechnology is reported.

Stimuli-Responsive DNA Self-Assembly: From Principles to Applications.

Stimuli-responsive DNA self-assembly shares the advantages of both designed stimuli-responsiveness and the molecular programmability of DNA structures, offering great opportunities for basic and applied research in dynamic DNA nanotechnology. In this minireview, we summarize the most recent progress in this rapidly developing field. The trigger mechanisms of the responsive DNA systems are first divided into six categories, which are then explained with illustrative examples following this classification. Subsequently, proof-of-concept applications in terms of biosensing, in vivo pH-mapping, drug delivery, and therapy are discussed. Finally, we provide some remarks on the challenges and opportunities of this highly promising research direction in DNA nanotechnology.

Nanosecond-Laser-Based Charge Transfer Plasmon Engineering of Solution-Assembled Nanodimers.

The ability to re-engineer self-assembled functional structures with nanometer accuracy through solution-processing techniques represents a big challenge in nanotechnology. Herein we demonstrate that Ag+-soldered nanodimers with a steric confinement coating of silica can be harnessed to realize an in-solution nanosecond laser reshaping to form interparticle conductive pathway with finely controlled conductance. The high structural purity of the nanodimers, the rigid silica coating, and the uniform (but still adjustable) sub-1-nm interparticle gap together determine the success of the laser reshaping process. This method is applicable to DNA-assembled nanodimers, and thus promises DNA-based programming toward higher structural complexity. The resulting structures exhibit highly tunable charge transfer plasmons at visible and near-infrared frequencies dictated by the fluence of the laser pulses. Our work provides an in-solution, rapid, and nonperturbative route to realize charge transfer plasmonic coupling along prescribed paths defined by self-assembly, conferring great opportunities for functional metamaterials in the context of chemical, biological, and nanophotonic applications. The ability to continuously control a subnm interparticle gap and the nanomeric width of a conductive junction also provides a platform to investigate modern plasmonic theories involving quantum and nonlocal effects.

Freeze the Moment: High Speed Capturing of Weakly Bonded Dynamic Nanoparticle Assemblies in Solution by Ag Ion Soldering.

Despite the versatile forms of colloidal aggregates, these spontaneously formed structures are often hard to find a suitable application in nanotechnology and materials science. A determinate reason is the lack of a suitable method to capture the transiently formed and quickly evolving colloidal structures in solution. To address this challenge, a simple but highly efficient strategy is herein reported to capture the dynamic and metastable colloidal assemblies formed in an aqueous or nonaqueous solution. This process takes advantage of a recently developed Ag ion soldering reaction to realize a rapid fixation of as-formed metastable assemblies. This method works efficiently for both solid (3D) nanoparticle aggregates and weakly bonded fractal nanoparticle chains (1D). In both cases, very high capturing speed and close to 100% efficiency are achieved to fully retain a quickly growing structure. The soldered nanochains further enable a fabrication of discrete, uniform, and functionalizable nanoparticle clusters with enriched linear conformation by mechanical shearing, which would otherwise be difficult to make. The captured products are water dispersible and mechanically robust, favoring an exploration of their properties toward possible applications. The work paves a way to previously untouched aspects of colloidal science and thus would create new chances in nanotechnology.

Universal pH-Responsive and Metal-Ion-Free Self-Assembly of DNA Nanostructures.

pH-responsiveness has been widely pursued in dynamic DNA nanotechnology, owing to its potential in biosensing, controlled release, and nanomachinery. pH-triggering systems mostly depend on specific designs of DNA sequences. However, sequence-independent regulation could provide a more general tool to achieve pH-responsive DNA assembly, which has yet to be developed. Herein, we propose a mechanism for dynamic DNA assembly by utilizing ethylenediamine (EN) as a reversibly chargeable (via protonation) molecule to overcome electrostatic repulsions. This strategy provides a universal pH-responsivity for DNA assembly since the regulation originates from externally co-existing EN rather than specific DNA sequences. Furthermore, it endows structural DNA nanotechnology with the benefits of a metal-ion-free environment including nuclease resistance. The concept could in principle be expanded to other organic molecules which may bring unique controls to dynamic DNA assembly.

Uncoordinated Amine Groups of Metal-Organic Frameworks to Anchor Single Ru Sites as Chemoselective Catalysts toward the Hydrogenation of Quinoline.

Here we report a precise control of isolated single ruthenium site supported on nitrogen-doped porous carbon (Ru SAs/N-C) through a coordination-assisted strategy. This synthesis is based on the utilization of strong coordination between Ru3+ and the free amine groups (-NH2) at the skeleton of a metal-organic framework, which plays a critical role to access the atomically isolated dispersion of Ru sites. Without the assistance of the amino groups, the Ru precursor is prone to aggregation during the pyrolysis process, resulting in the formation of Ru clusters. The atomic dispersion of Ru on N-doped carbon can be verified by the spherical aberration correction electron microscopy and X-ray absorption fine structure measurements. Most importantly, this single Ru sites with single-mind N coordination can serve as a semihomogeneous catalyst to catalyze effectively chemoselective hydrogenation of functionalized quinolones.

Optimal design for the support structure of a cavity mirror in a chemical oxygen iodine laser resonator.

The dynamic characteristics of the cavity mirror support structure strongly influence the quality of the output beam. However, the contradiction between excellent dynamic performance and light weight make the design process challenging. To cope with the problems encountered in the original design of a chemical oxygen iodine laser system, this paper presents a two-dimensional adjustable support structure based on spherical constraints with large specific stiffness in the initial design phase. Subsequently, a two-level optimization strategy containing a macro design and a detailed design is adopted to optimize the initial structure. At the macro design stage, a two-step topology optimization procedure is introduced, in which the scale of the optimization model is dramatically reduced using the independent continuous mapping algorithm to improve the calculation speed in the first step, and the gray elements are eliminated using the bi-directional evolutionary structural optimization method to clearly obtain the optimal topology in the second step. This method is verified to overcome the defect of low efficiency, while still eliminating gray elements. At the detailed design stage, an adaptive surrogate model and the multi-objective design optimization method are employed to seek the best compromise between the lower weight and higher dynamic performance. The results from the application to the example of the cavity mirror support structure show that the mass is reduced by 41.8%, and the dynamic performance requirement is fulfilled.

Graphene Oxide Attenuates the Cytotoxicity and Mutagenicity of PCB 52 via Activation of Genuine Autophagy.

Graphene oxide (GO), owing to its large surface area and abundance of oxygen-containing functional groups, is emerging as a potential adsorbent for polychlorinated biphenyls (PCBs), which accumulate over time and are harmful to both natural ecosystems and human health. However, the effect of GO against PCB-induced toxicity remains largely unexplored. The present study aimed to investigate the protective effect of GO against PCB 52 induced cytotoxic and genotoxic response in mammalian cells at various exposure conditions and clarify the protective role of autophagy. Pretreatment with GO dramatically decreased PCB 52 induced cytotoxicity and CD59 gene mutation in human-hamster hybrid (AL) cells. The toxic response in cells either pretreated with PCB 52 and then treated with GO or concurrently treated with GO and PCB 52 did not differ significantly from the toxic response in the cells treated with PCB 52 alone. Using autophagy inhibitors (3-methyladenine and wortmannin) and inducers (trehalose and rapamycin), we found that genuine autophagy induced by GO was involved in decreasing PCB 52 induced toxicity. These findings suggested that GO has an antagonistic effect against the toxicity of PCB 52 mainly by triggering a genuine autophagic process, which might provide new insights into the potential application of GO in PCB disposal and environmental and health risk assessment.

Dry Sintering Meets Wet Silver-Ion "Soldering": Charge-Transfer Plasmon Engineering of Solution-Assembled Gold Nanodimers From Visible to Near-Infrared†I and II†Regions.

Achieving highly tunable and localized surface plasmon resonance up to near infrared (NIR) regions is a key target in nanoplasmonics. In particular, a self-assembly process capable of producing highly uniform and solution-processable nanomaterials with tailor-made plasmonic properties is lacking. We herein address this problem through a conjunctive use of wet Ag+ soldering and dry thermal sintering to produce nanodimer-derived structures with precisely engineered charge-transfer plasmon (CTP). The sintered dimers are water soluble, featuring gradually shifted CTP spanning an 800 nm wavelength range (up to NIR II). Upon silica removal, the products are grafted by DNA to offer surface functionality. This process is also adaptable to DNA-linked AuNP dimers toward plasmonic meta-materials via DNA-guided soldering and sintering.

Single Cobalt Atoms with Precise N-Coordination as Superior Oxygen Reduction Reaction Catalysts.

A new strategy for achieving stable Co single atoms (SAs) on nitrogen-doped porous carbon with high metal loading over 4 wt % is reported. The strategy is based on a pyrolysis process of predesigned bimetallic Zn/Co metal-organic frameworks, during which Co can be reduced by carbonization of the organic linker and Zn is selectively evaporated away at high temperatures above 800 °C. The spherical aberration correction electron microscopy and extended X-ray absorption fine structure measurements both confirm the atomic dispersion of Co atoms stabilized by as-generated N-doped porous carbon. Surprisingly, the obtained Co-Nx single sites exhibit superior ORR performance with a half-wave potential (0.881 V) that is more positive than commercial Pt/C (0.811 V) and most reported non-precious metal catalysts. Durability tests revealed that the Co single atoms exhibit outstanding chemical stability during electrocatalysis and thermal stability that resists sintering at 900 °C. Our findings open up a new routine for general and practical synthesis of a variety of materials bearing single atoms, which could facilitate new discoveries at the atomic scale in condensed materials.

Ordered Porous Pd Octahedra Covered with Monolayer Ru Atoms.

Monolayer Ru atoms covered highly ordered porous Pd octahedra have been synthesized via the underpotential deposition and thermodynamic control. Shape evolution from concave nanocube to octahedron with six hollow cavities was observed. Using aberration-corrected high-resolution transmission electron microscopy and X-ray photoelectron spectroscopy, we provide quantitative evidence to prove that only a monolayer of Ru atoms was deposited on the surface of porous Pd octahedra. The as-prepared monolayer Ru atoms covered Pd nanostructures exhibited excellent catalytic property in terms of semihydrogenation of alkynes.