Biocompatibility of Amine‐Functionalized Silica Nanoparticles: The Role of Surface Coverage

Here, amorphous silica nanoparticles (NPs), one of the most abundant nanomaterials, are used as an example to illustrate the utmost importance of surface coverage by functional groups which critically determines biocompatibility. Silica NPs are functionalized with increasing amounts of amino groups, and the number of surface exposed groups is quantified and characterized by detailed NMR and fluorescamine binding studies. Subsequent biocompatibility studies in the absence of serum demonstrate that, irrespective of surface modification, both plain and amine‐modified silica NPs trigger cell death in RAW 264.7 macrophages. The in vitro results can be confirmed in vivo and are predictive for the inflammatory potential in murine lungs. In the presence of serum proteins, on the other hand, a replacement of only 10% of surface‐active silanol groups by amines is sufficient to suppress cytotoxicity, emphasizing the relevance of exposure conditions. Mechanistic investigations identify a key role of lysosomal injury for cytotoxicity only in the presence, but not in the absence, of serum proteins. In conclusion, this work shows the critical need to rigorously characterize the surface coverage of NPs by their constituent functional groups, as well as the impact of serum, to reliably establish quantitative nanostructure activity relationships and develop safe nanomaterials.     

Highly Ordered Arrays of Particle-in-Bowl Plasmonic Nanostructures for Surface-Enhanced Raman Scattering

A highly ordered particle-in-bowl (PIB) nanostructure array is designed and fabricated to achieve large field enhancement for the surface-enhanced Raman scattering (SERS) application. This new type of PIB structure is composed of an Ag particle located at the bottom of an Au bowl, and the two are separated by a precisely controlled nanoscale dielectric layer. The fabrication of the PIB structure is based on the self-assembly of polystyrene spheres and atomic layer deposition (ALD), which allows good control of the metal particle size and gap distance, as well as large-scale ordering. Numerical simulation reveals a high enhancement of the local field at the nanogaps. The SERS performance of the PIB arrays, and the effects of the Ag particle size and the ALD dielectric layer thickness are characterized, results of which are in reasonable agreement with simulation. With Rhodmaine 6G as the probe molecule, the spatially averaged SERS enhancement factor is on the order of 3.8 × 10(7) and the local field enhancement from simulation can be up to 10(8) .     

Plasmon‐Enhanced Spectroscopies with Shell‐Isolated Nanoparticles

Shell‐isolated nanoparticle‐enhanced Raman spectroscopy (SHINERS), due to its versatility, has been able to break the long‐term limitations of the material‐ and substrate‐specific generalities in the traditional field of surface‐enhanced Raman spectroscopy. With a shell‐isolated work principle, this method provides an opportunity to investigate successfully in surface, biological systems, energetic materials, and environmental sciences. Both the shell material and core morphology are being improved continuously to meet the requirements in diverse systems, such as the electrochemical studies at single crystal electrode surfaces, in situ monitoring of photoinduced reaction processes, practical applications in energy conversion and storage, inspections in food safety, and the surface‐enhanced fluorescence. Predictably, the concept of shell‐isolated nanoparticle‐enhancement could be expanded to the wider range for the performance of plasmon‐enhanced spectral modifications.     

Highly-ordered, 3D petal-like array for surface-enhanced Raman scattering

Despite the great potential of the application of surface-enhanced Raman scattering (SERS), the difficulty in fabricating suitable SERS substrates is still a problem. Based on the self-assembly of silica nanoparticles, a simple method is here proposed to fabricate a highly-ordered, 3D, petal-like arrayed structure (3D PLAS) that serves as a promising SERS substrate for both its high reproducibility and enormous SERS enhancement. Such a novel structure is easily achieved by anisotropically etching a self-assembly bilayer of silica nanoparticles, followed by metal deposition. The SERS performance of the 3D PLAS and its relationship with the main parameters, including the etching time, the diameter of silica nanoparticles, and the deposited metal film, are characterized using 632.8 nm incident light. With Rhodamine 6G as a probe molecule, the spatially averaged SERS enhancement factor is on the order of 5 × 10(7) and the local enhancement factor is much higher, both of which can be improved further by optimizing the parameters.     

Designing Lubricant‐Impregnated Textured Surfaces to Resist Scale Formation

Scale formation is a widespread problem in industries and households—from scaling of cooking pots in ancient times to the plugging of pipelines in the modern age. Developing surfaces that have a low affinity to scale has been an area of great interest in the last decade. In this work, we demonstrate the anti‐scaling properties of textured surfaces impregnated with a lubricant. Since scale deposition can be reduced by lowering the nucleation rate, which depends on the properties of the substrate, we optimize the design of the lubricant‐impregnated surfaces (LIS) based on the surface tension of the lubricant and its spreading coefficient on the solid. Scale deposition experiments show that the nucleation rate on optimized LIS is reduced owing to their low surface energy and low density of nucleation sites. Mass gain measurements indicate that the optimized LIS perform 10 times better than uncoated smooth surfaces. This idea is extended to an engineering material like stainless steel and, along with low scale deposition, low adhesion of scale to LIS is also achieved.     

Nanostructured surfaces and assemblies as SERS media

Metallic nanostructures attract much interest as an efficient media for surface-enhanced Raman scattering (SERS). Significant progress has been made on the synthesis of metal nanoparticles with various shapes, composition, and controlled plasmonic properties, all critical for an efficient SERS response. For practical applications, efficient strategies of assembling metal nanoparticles into organized nanostructures are paramount for the fabrication of reproducible, stable, and highly active SERS substrates. Recent progress in the synthesis of novel plasmonic nanoparticles, fabrication of highly ordered one-, two-, and three-dimensional SERS substrates, and some applications of corresponding SERS effects are discussed.     

M‐shaped Grating by Nanoimprinting: A Replicable,Large‐Area,Highly Active Plasmonic Surface‐Enhanced Raman Scattering Substrate with Nanogaps

Plasmonic nanostructures separated by nanogaps enable strong electromagnetic‐field confinement on the nanoscale for enhancing light‐matter interactions, which are in great demand in many applications such as surface‐enhanced Raman scattering (SERS). A simple M‐shaped nanograting with narrow V‐shaped grooves is proposed. Both theoretical and experimental studies reveal that the electromagnetic field on the surface of the M grating can be pronouncedly enhanced over that of a grating without such grooves, due to field localization in the nanogaps formed by the narrow V grooves. A technique based on room‐temperature nanoimprinting lithography and anisotropic reactive‐ion etching is developed to fabricate this device, which is cost‐effective, reliable, and suitable for fabricating large‐area nanostructures. As a demonstration of the potential application of this device, the M grating is used as a SERS substrate for probing Rhodamine 6G molecules. Experimentally, an average SERS enhancement factor as high as 5×10⁸ has been achieved, which verifies the greatly enhanced light–matter interaction on the surface of the M grating over that of traditional SERS surfaces.     

Bioinspired Surfaces with Superwettability for Anti‐Icing and Ice‐Phobic Application: Concept,Mechanism, and Design

Ice accumulation poses a series of severe issues in daily life. Inspired by the nature, superwettability surfaces have attracted great interests from fundamental research to anti‐icing and ice‐phobic applications. Here, recently published literature about the mechanism of ice prevention is reviewed, with a focus on the anti‐icing and ice‐phobic mechanisms, encompassing the behavior of condensate microdrops on the surface, wetting, ice nucleation, and freezing. Then, a detailed account of the innovative fabrication and fundamental research of anti‐icing materials with special wettability is summarized with a focus on recent progresses including low‐surface energy coatings and liquid‐infused layered coatings. Finally, special attention is paid to a discussion about advantages and disadvantages of the technologies, as well as factors that affect the anti‐icing and ice‐phobic efficiency. Outlooks and the challenges for future development of the anti‐icing and ice‐phobic technology are presented and discussed.     

Design of Magnetic‐Plasmonic Nanoparticle Assemblies via Interface Engineering of Plasmonic Shells for Targeted Cancer Cell Imaging and Separation

Magnetic‐plasmonic nanoparticles have received considerable attention for widespread applications. These nanoparticles (NPs) exhibiting surface‐enhanced Raman scattering (SERS) activities are developed due to their potential in bio‐sensing applicable in non‐destructive and sensitive analysis with target‐specific separation. However, it is challenging to synthesize these NPs that simultaneously exhibit low remanence, maximized magnetic content, plasmonic coverage with abundant hotspots, and structural uniformity. Here, a method that involves the conjugation of a magnetic template with gold seeds via chemical binding and seed‐mediated growth is proposed, with the objective of obtaining plasmonic nanostructures with abundant hotspots on a magnetic template. To obtain a clean surface for directly functionalizing ligands and enhancing the Raman intensity, an additional growth step of gold (Au) and/or silver (Ag) atoms is proposed after modifying the Raman molecules on the as‐prepared magnetic‐plasmonic nanoparticles. Importantly, one‐sided silver growth occurred in an environment where gold facets are blocked by Raman molecules; otherwise, the gold growth is layer‐by‐layer. Moreover, simultaneous reduction by gold and silver ions allowed for the formation of a uniform bimetallic layer. The enhancement factor of the nanoparticles with a bimetallic layer is approximately 10⁷. The SERS probes functionalized cyclic peptides are employed for targeted cancer‐cell imaging and separation.     

Functional Femtoliter Droplets for Ultrafast Nanoextraction and Supersensitive Online Microanalysis

A universal femtoliter surface droplet‐based platform for direct quantification of trace of hydrophobic compounds in aqueous solutions is presented. Formation and functionalization of femtoliter droplets, concentrating the analyte in the solution, are integrated into a simple fluidic chamber, taking advantage of the long‐term stability, large surface‐to‐volume ratio, and tunable chemical composition of these droplets. In situ quantification of the extracted analytes is achieved by surface‐enhanced Raman scattering (SERS) spectroscopy by nanoparticles on the functionalized droplets. Optimized extraction efficiency and SERS enhancement by tuning droplet composition enable quantitative determination of hydrophobic model compounds of rhodamine 6G, methylene blue, and malachite green with the detection limit of 10^?9 to 10^?11 m and a large linear range of SERS signal from 10^?9 to 10^?6 m of the analytes. The approach addresses the current challenges of reproducibility and the lifetime of the substrate in SERS measurements. This novel surface droplet platform combines liquid–liquid extraction and highly sensitive and reproducible SERS detection, providing a promising technique in current chemical analysis related to environment monitoring, biomedical diagnosis, and national security monitoring.     

Controlled Assembly of Highly Raman‐Enhancing Silver Nanocap Arrays Templated by Porous Anodic Alumina Membranes

A convenient nanoscale technique is reported for the fabrication of highly ordered hemispherical silver nanocap arrays templated by porous anodic alumina (PAA) membranes as robust and cost‐efficient surface‐enhanced Raman scattering (SERS) substrates. This geometry produces a high Raman signal due to its periodic hexagonal arrangements and control of the gap between the nanostructures in the sub‐10‐nm regime. The surface structure can be tuned further to optimize the enhancement factor according to optional PAA fabrication and silver deposition parameters. Finite‐difference time‐domain calculations indicate that the structure may possess excellent SERS characteristics due to the high density and abundance of hot spots.