Protocol for preparing patterned superlattice structures by printing assembly technology for multi-channel detection.

The transformation of superlattice structures into functional devices requires high-quality preparation. Inkjet printing is potentially a cutting-edge technology for nanofabrication. Here, we present a protocol to prepare inks for constructing patterned superlattice structures using print assembly techniques. We describe steps for preparing oleophobic substrates, optimizing ink parameters, and preparing the patterned superlattice array. We then detail procedures for preparing a multichannel surface-enhanced Raman scattering sensor and evaluating its performance. This protocol can potentially facilitate the commercialization of superlattice-related devices. For complete details regarding the use and execution of this protocol, please refer to Zhao et al.1.

Colorimetric Aerogel Gas Sensor with High Sensitivity and Stability.

The detection of formic acid vapor in the usage environment is extremely important for human health and safety. The utilization of metal-organic frameworks (MOFs) for the detection of gaseous molecules is an attractive strategy. However, the rational design and construction of MOF-based gas sensors with high sensitivity and mechanical stability remain a significant challenge. In this study, a simple approach is reported to fabricate colorimetric aerogel sensors assembled from MOF particles via ice template-assisted methods. As the aerogel sensor with staggered lamellae structures significantly provides a high air-volume intake of flowing gas, it generates a sufficient probability of contact reactions for highly mobile target molecules. Additionally, it enhances the mechanical stability by providing stress resistance between the staggered lamellae structures. Compared to conventional film sensors for the detection of formic acid molecules, aerogel sensors exhibit an 8-fold lower limit of detection, 15-fold better sensitivity at low concentrations, 34-fold faster response time, and higher stability. This approach shows great potential for rapid and real-time detection of target molecules as well as superior performance in the structural construction of various gas-sensitive materials.

Printable assemblies of perovskite nanocubes on meter-scale panel.

Hierarchical assemblies of functional nanoparticles can have applications exceeding those of individual constituents. Arranging components in a certain order, even at the atomic scale, can result in emergent effects. We demonstrate that printed atomic ordering is achieved in multiscale hierarchical structures, including nanoparticles, superlattices, and macroarrays. The CsPbBr3 perovskite nanocubes self-assemble into superlattices in ordered arrays controlled across 10 scales. These structures behave as single nanoparticles, with diffraction patterns similar to those of single crystals. The assemblies repeat as two-dimensional planar unit cells, forming crystalline superlattice arrays. The fluorescence intensity of these arrays is 5.2 times higher than those of random aggregate arrays. The multiscale coherent states can be printed on a meter-scale panel as a micropixel light-producing layer of primary-color photon emitters. These hierarchical assemblies can boost the performance of optoelectronic devices and enable the development of high-efficiency, directional quantum light sources.

A point-of-care biosensor for rapid and ultra-sensitive detection of SARS-CoV-2.

In a recent study in Nature Biomedical Engineering, Wei's group constructed a field-effect transistor (FET) based on the "molecular electromechanical system" (MolEMS). MolEMS enabled FETs to specifically capture viral nucleic acids and efficiently transduce signals, achieving a rapid and ultra-sensitive detection of SARS-CoV-2.

Gold Nanoparticle-Bridge Array to Improve DNA Hybridization Efficiency of SERS Sensors.

The interfacial mass transfer rate of a target has a significant impact on the sensing performance. The surface reaction forms a concentration gradient perpendicular to the surface, wherein a slow mass transfer process decreases the interfacial reaction rate. In this work, we self-assembled gold nanoparticles (AuNPs) in the gap of a SiO2 opal array to form a AuNP-bridge array. The diffusion paths of vertical permeability and a microvortex effect provided by the AuNP-bridge array synergistically improved the target mass transfer efficiency. As a proof of concept, we used DNA hybridization efficiency as a research model, and the surface-enhanced Raman spectroscopy (SERS) signal acted as a readout index. The experimental verification and theoretical simulation show that the AuNP-bridge array exhibited rapid mass transfer and high sensitivity. The DNA hybridization efficiency of the AuNP-bridge array was 15-fold higher than that of the AuNP-planar array. We believe that AuNP-bridge arrays can be potentially applied for screening drug candidates, genetic variations, and disease biomarkers.

Influence of Elasticity of Hydrogel Nanoparticles on Their Tumor Delivery.

Polymeric nanocarriers have a broad range of clinical applications in recent years, but an inefficient delivery of polymeric nanocarriers to target tissues has always been a challenge. These results show that tuning the elasticity of hydrogel nanoparticles (HNPs) improves their delivery efficiency to tumors. Herein, a microfluidic system is constructed to evaluate cellular uptake of HNPs of different elasticity under flow conditions. It is found that soft HNPs are more efficiently taken up by cells than hard HNPs under flow conditions, owing to the greater adhesion between soft HNPs and cells. Furthermore, in vivo imaging reveals that soft HNPs have a more efficient tumor delivery than hard HNPs, and the greater targeting potential of soft HNPs is associated with both prolonged blood circulation and a high extent of cellular adhesion.

A Separation-Sensing Platform Performing Accurate Diagnosis of Jaundice in Complex Biological Tear Fluids.

The detection of biomarkers in tears has aroused great interest owing to the advantages of non-invasive and rapid collection. The combination of ultrasensitivity and label-free detection of surface-enhanced Raman spectroscopy (SERS) sensors is expected to achieve real-time diagnosis in home medical care. However, the surface of SERS sensors is susceptible to biofouling and inactivation by biological impurities in tears, resulting in rapid degradation of sensitivity, limiting the commercialization of point-of-care devices. Herein, a binary nanosphere array with dual properties is constructed as a separation-sensing platform for the diagnosis of target molecules in tears. The upper part of the structure is composed of Au nanoparticles (AuNPs) and a sputtering Au layer, which can bind the target molecules that interact with Au and provide high-strength and high-density SERS hotspots. The lower half is an inactive SiO2 nanosphere array with periodic large pores that allows biological impurities to penetrate the lower part and be separated from the target analyte. Furthermore, this substrate was integrated into homemade tear kits, enabling simultaneous tear collection, pre-separation, and detection. Combined with the Raman spectra of tears and LDA analysis, we successfully identified patients with jaundice in clinics. This platform is expected to provide an opportunity for early disease screening based on biological fluids.

Spatial Confinement Tunes Cleavage and Re-Formation of C=N Bonds in Fluorescent Molecules.

Molecules in confined spaces exhibit unusual behaviors that are not typically observed in bulk systems. Such behavior can provide alternative strategies for exploring new reaction pathways. Cleavage of the C=N bond of Nile red (NR) in solution is an irreversible reaction. Here, we used spatial confinement within a cationic micelle-confined system to convert this reaction to a reversible process. The fluorescence of NR shifted between red and green for nine cycles. The new chemical pathway based on spatial confinement can be attributed to two factors: increasing the local concentration of reactants and reducing the reaction energy barrier. This effect is supported by both experimental evidence and theoretical calculations. The cross-linked silica shell comprising the confinement chamber stabilizes the enclosed molecules. This reduces fluorophore leakage and maintains fluorescence intensity in most environments, including in solution, on paper, and in hydrogel films, and expands practical applications in encrypted information and multi-informational displays.

Nanoassembled Interface for Dynamics Tailoring.

The properties and performance of solid nanomaterials in heterogeneous chemical reactions are significantly influenced by the interface between the nanomaterial and environment. Oriented tailoring of interfacial dynamics, that is, modifying the shared boundary for mass and energy exchange has become a common goal for scientists. Although researchers have designed and constructed an abundance of nanomaterials with excellent performances for the tailoring of reaction dynamics, a complete understanding of the mechanism of nanomaterial-environment interfacial interaction still remains elusive. To predictively understand the nanomaterial-environment relationship over a wide range of time scale, a deep and dynamic insight is required urgently. In this Account, our recent works including advances in the design and construction of nanoassembled interfaces and understanding the dynamic interaction mechanisms between different combinations of nanoparticle (NP) assembly environment interfaces for tailoring the reaction dynamics.NP assemblies with well-defined structures and compositions are inherently suitable for replacing bulk-type nanomaterials for the research on interfaces. We primarily introduced two most relevant nanoassembled surfaces that were fabricated in our laboratory, namely, ordered self-assembly interface and animate nanoassembled interface. The disordered nanoparticles can be arranged into an ordered superlattice based on the self-assembly method and patterned-assembly method. In addition, we used NPs with flexible properties to construct three-dimensional (3D) animate assemblies. On the basis of a thorough understanding of the structure-property correlation, a series of nanoassembled interfaces with various structures have been developed for practice. In comparison with traditional nanomaterial-environment interfaces, the nanoassembled interfaces can change the mode of contact between the nanomaterial and environment, thereby maximizing the number of active sites and driving interferent/product off the nanoassembled interface. The geometry, porosity, and deformable/motional properties in the nanoassembled interface can be applied to enhance the mass transfer dynamics in the chemical reaction. Moreover, the nanoassembled interface can be used to strengthen the affinity between the NP assemblies and targets, thereby enhancing the adsorption efficiency. As shown in these examples, the nanoassembled interface can effectively change the speed, intensity, and mode of interactions between the NP assemblies and environment in spatiotemporal scales.The overall performance of the interfacial dynamics can be improved by the nanoassembled interface, thereby facilitating practical application in flowing systems. We have extended the applications of nanoassembled interfaces from simple adsorption to complex reactions in flowing systems, including in vivo magnetic resonance imaging, electrocatalytic gas evolution reaction, bacterial capture, sensing of exhaled volatile organic compounds, and heterogeneous catalysis. Our current endeavors to explore the applicability of animate nanoassembled interfaces for dynamic tailoring have widened the scope of research, and attempts to construct intelligent interfaces for applications are underway.

Mechanical penetration of ß-lactam-resistant Gram-negative bacteria by programmable nanowires.

ß-Lactam-resistant (BLR) Gram-negative bacteria that are difficult or impossible to treat are causing a global health threat. However, the development of effective nanoantibiotics is limited by the poor understanding of changes in the physical nature of BLR Gram-negative bacteria. Here, we systematically explored the nanomechanical properties of a range of Gram-negative bacteria (Salmonella, Escherichia coli, Pseudomonas aeruginosa, and Klebsiella pneumoniae) with different degrees of ß-lactam resistance. Our observations indicated that the BLR bacteria had cell stiffness values almost 10× lower than that of ß-lactam-susceptible bacteria, caused by reduced peptidoglycan biosynthesis. With the aid of numerical modeling and experimental measurements, we demonstrated that these stiffness findings can be used to develop programmable, stiffness-mediated antimicrobial nanowires that mechanically penetrate the BLR bacterial cell envelope. We anticipate that these stiffness-related findings will aid in the discovery and development of novel treatment strategies for BLR Gram-negative bacterial infections.

Mechanical and Tribological Performances Enhanced by Self-Assembled Structures.

Taking inspiration from natural materials, composite materials can be reinforced by creating matrix architectures that can better accommodate and control internal stresses. Despite the recent success in the synthesis of artificial assemblies for local reinforcement through the introduction of oriented fibers and plates into host multilayered composites, there is a lack of fundamental understanding of the factors that determine mechanical properties. Moreover, designing building blocks and interfaces that facilitate higher resistance and energy dissipation is highly challenging. When the intrinsic material is fixed, the mechanical and tribological properties can be further adjusted. In this study, europium oxide nanosheets are arranged in interlocked-junction superstructures that resist sliding at junction points, thereby enhancing the mechanical properties of the nanosheet assemblies compared to those of the conventional face-to-face superstructures formed by parallel nanosheets. Furthermore, the crystalline origin of building blocks is revealed by demonstrating that faulty crystal nanosheets adopting an amorphous structure are different from single-crystal nanosheets, with the former exhibiting superior mechanical reinforcement and improved abrasive resistance.

Universal Strategy for Improving the Sensitivity of Detecting Volatile Organic Compounds by Patterned Arrays.

The diffusion of target analytes is a determining factor for the sensitivity of a given gas sensor. Surface adsorption results in a low-concentration region near the sensor surface, producing a concentration gradient perpendicular to the surface, and drives a net flux of molecules toward solid reactive reagents on the sensor surface, that is, vertical diffusion. Here, organic semiconductor supramolecules were patterned into micromeshed arrays to integrate vertical and horizontal diffusion pathways. When used as a gas sensor, these arrays have an order of magnitude higher sensitivity than traditional film-based sensors. The sensor sensitivity ramp down with the increase in coverage density of reactive reagents, yielding two linear regions demarcated by 0.3 coverage, which are identified by the experimental results and simulations. The universal nature of template-assisted patterning allows adjustments in the composition, size, and shape of the constituent material, including nanofibers, nanoparticles, and molecules, and thus serves to improve the sensitivity of gas sensors for detecting various volatile organic compounds.

Effect of structure: A new insight into nanoparticle assemblies from inanimate to animate.

Nanoparticle (NP) assemblies are among the foremost achievements of nanoscience and nanotechnology because their interparticle interactions overcome the weaknesses displayed by individual NPs. However, previous studies have considered NP assemblies as inanimate, which had led to their dynamic properties being overlooked. Animate properties, i.e., those mimicking biological properties, endow NP ensembles with unique and unexpected functionalities for practical applications. In this critical review, we highlight recent advances in our understanding of the properties of NP assemblies, particularly their animate properties. Key examples are used to illustrate critical concepts, and special emphasis is placed on animate property-dependent applications. Last, we discuss the barriers to further advances in this field.

A Metal-Organic Framework Nanosheet-Assembled Frame Film with High Permeability and Stability.

The engineering of metal-organic frameworks (MOFs) into membranes and films is being investigated, to transform laboratory-synthesized MOFs into industrially viable products for a range of attractive applications. However, rational design and construction of highly permeable MOF thin films, without trade-offs in terms of structural mechanical stability, remains a significant challenge. Herein, a simple, general strategy is reported to prepare thin MOF nanosheet (NS)-assembled frame film via heteroepitaxial growth from metal hydroxide film. As the thin MOF NS-assembled film significantly enhances the permeability of mass though the film, the resultant gold nanoparticle (Au NP)@MOF film exhibits much higher catalytic efficiency than the Au NP@MOF bulk film. Meanwhile, the unique framework of the MOF NS-assembled film resists torsion and collapse, so the composite catalyst exhibits long-term stability.

Deformable Metal-Organic Framework Nanosheets for Heterogeneous Catalytic Reactions.

The dynamic status near the surface of a catalyst can significantly affect the catalytic process, because the overall reaction rate depends on the mass velocity of product attachment and reactant detachment. As a dominant diffusion mechanism, molecular diffusion is known as a slow process that inhibits the fast contact between the reactants and the heterogeneous catalyst, which depresses catalytic conversion efficiency. Herein, we report a strategy that can break such a stagnant layer to facilitate the mass transport toward the catalyst surface, wherein Pd nanocubes (NCs) encapsulated in soft metal-organic framework (MOF) nanosheets are used as catalysts for the hydrogenation reactions. The soft MOF supports render deformable features to enhance mass transport across the Pd NCs, which is vital to enhance the catalyst performance. In combination with numerical simulations, we identify the deformable MOF driven by the shear force of flowing fluid to increase dye adsorption and catalytic conversion by 5- and 3-fold, respectively, as compared to a counterpart system containing nondeformable MOFs. The catalytic efficiency presents a volcano-type trend with the length-to-spacing ratio of MOF nanosheet being designed and reaches the maximum with a length-to-spacing ratio of 2:1. This technique provides unique opportunities to design a proof-of-concept self-propelled catalysis on the basis of a greater mechanistic understanding of heterogeneous catalytic reactions.

Nanomaterial-based gas sensors used for breath diagnosis.

Gas-sensing applications commonly use nanomaterials (NMs) because of their unique physicochemical properties, including a high surface-to-volume ratio, enormous number of active sites, controllable morphology, and potential for miniaturisation. NM-based gas sensors, as a noninvasive, real-time technique, are a promising candidate for monitoring human breath. This review focuses on NM-based gas sensors used for breath diagnosis. First we describe some representative biomarkers of diseases that are detectable in breath and requirements for breath sensors. Then we review electrical, optical and mass-sensitive gas sensors in terms of these performance requirements, together with describing the detection capability of these sensors for trace concentrations of biomarkers and their initial attempts to diagnose disease. Moreover, we discuss breath sensor platforms with a multivariable sensing system, wireless communication and breath sampling, essential for predictive, preventive, personalised, and participatory ("P4") medicine. Finally, we conclude with problems and challenges associated with the selectivity, humidity and validation of breath sensors. We hope that this article will inspire the development of high-performance gas sensors based on novel NMs.

General Strategy to Optimize Gas Evolution Reaction via Assembled Striped-Pattern Superlattices.

Redesigning heterogeneous catalysts so that they can simultaneously integrate the efficiency and durability under reaction environments with respect to gas fuel production, such as hydrogen (H2), oxygen (O2), or carbon monoxide (CO), has proven challenging. In this work, we report the successful template-assisted printing-based assembly of platinum (Pt) nanoparticles (NPs) into striped-pattern (SP) superlattices to produce H2. In comparison to drop-casting flat Pt NPs films, SP superlattices lead to higher mass transference and smaller bubble stretch force, representing a general strategy to improve the efficiency and durability of pre-existed Pt catalysts for the hydrogen evolution reaction (HER), as well as higher current densities than commercial Pt/C, Pt NP films, and many of the other Pt-based or non-Pt-based HER catalysts reported in the literature. The generic nature of template-assisted printing leads to flexibility in the composition, size, and shape of the constituent NPs or molecules, and thus extends such an accelerated technique for producing the oxygen evolution reaction and electrochemical reduction of CO2 to CO.

Coordination mode engineering in stacked-nanosheet metal-organic frameworks to enhance catalytic reactivity and structural robustness.

Optimising the supported modes of atom or ion dispersal onto substrates, to synchronously integrate high reactivity and robust stability in catalytic conversion, is an important yet challenging area of research. Here, theoretical calculations first show that three-coordinated copper (Cu) sites have higher activity than four-, two- and one-coordinated sites. A site-selective etching method is then introduced to prepare a stacked-nanosheet metal-organic framework (MOF, CASFZU-1)-based catalyst with precisely controlled coordination number sites on its surface. The turnover frequency value of CASFZU-1 with three-coordinated Cu sites, for cycloaddition reaction of CO2 with epoxides, greatly exceed those of other catalysts reported to date. Five successive catalytic cycles reveal the superior stability of CASFZU-1 in the stacked-nanosheet structure. This study could form a basis for the rational design and construction of highly efficient and robust catalysts in the field of single-atom or ion catalysis.

Survey on the Mechanical Properties of Lamellar Ag-MXA Supercluster Architectures.

Lamellar nanomaterials with specific architectures and novel properties have received increasing attention from both scientific and technological fields in recent years because of their potential applications in catalysis, energy conversion, and storage devices. Bulk supercluster pellets with well-defined lamellar structures were fabricated by assembling silver clusters and mercaptoalkyl acids (MXA) to investigate the mechanical properties. The relationship between the assembled structure and pressure resistance was surveyed for the first time. The enhanced interlayer interactions were found to increase the elastic modulus of the Ag-MXA supercluster architectures.

Ruthenium@N-doped graphite carbon derived from carbon foam for efficient hydrogen evolution reaction.

Ru nanoparticles doped in carbon foam were encapsulated in nitrogen-doped graphite carbon materials (Ru-NGC). The resultant Ru-NGC possesses superior hydrogen evolution activity with a small onset potential of 9.5 mV and excellent durability due to the optimized Ru electronic state in nitrogen-doped graphite.