Evolution of Anisotropic Arrow Nanostructures during Controlled Overgrowth

Anisotropic metal nanoparticles (NPs), such as high-aspect-ratio Au nanorods (NRs), play an important role for applications in photocatalysis, sensing, and drug delivery because of their adjustable plasmon resonances. Their performance for these applications can be further improved by fine-tuning their morphologies. Achieving desired NP architectures requires insight into their formation mechanisms. Here, liquid-phase transmission electron microscopy is used to directly follow the overgrowth of Au NR seeds into nanoarrows (NAs) with fourfold symmetric wings along the sides. Adding thiol molecules like L-cysteine to the growth solution can lead to the formation of NAs with periodic prismatic teeth instead of the straight side wings. These observations suggest that this transition is controlled by binding of L-cysteine to the NR surface, which in turn, slows down the metal deposition rate, switching the overgrowth from the kinetically to thermodynamically controlled process. Furthermore, simulations demonstrate that these prismatic teeth enhance the NPs’ plasmonic properties. The study describes how thiol additives control the morphological evolution of metal NPs, which is important for the fabrication of NPs with tailored shapes for a broad range of applications.     

Ultrasensitive Plasmonic Response of Bimetallic Au/Pd Nanostructures to Hydrogen

Hydrogen detection is crucial for the safety of all hydrogen‐related applications. Compared to electrical hydrogen sensors, which usually suffer from possible electric sparks, optical hydrogen sensors offer advantages of remote and contact‐free readout and therefore the avoidance of spark generation. Herein, bimetallic Au/Pd nanostructure monolayers that exhibit ultrasensitive plasmonic response to hydrogen are reported. Bimetallic Au/Pd nanostructures with continuous and discontinuous Pd shells are prepared. The plasmonic response to hydrogen is monitored by measuring the extinction spectra of the ensemble Au/Pd nanostructures deposited on glass slides. Introduction of hydrogen induces red plasmon shifts, which become larger for the nanostructures with thicker Pd shells. For the nanostructures with continuous Pd shell, the plasmon shift can reach 56 nm at the hydrogen volume concentration below the explosion limit. The plasmon resonance wavelength displays an excellent linear dependence on the hydrogen volume concentration below 1%. The detection limit in the experiments reaches 0.2%. The nanostructures with discontinuous Pd shell show smaller plasmon shifts than those with continuous Pd shell. The extinction measurements on the ensemble nanostructures supported on transparent substrates and the unprecedentedly large plasmon shifts and sensitivity make the results very promising for the development of practical optical hydrogen sensors.     

Topographically Flat Substrates with Embedded Nanoplasmonic Devices for Biosensing

The ability to precisely control the topography, roughness, and chemical properties of metallic nanostructures is crucial for applications in plasmonics, nanofluidics, electronics, and biosensing. Here a simple method to produce embedded nanoplasmonic devices that can generate tunable plasmonic fields on ultraflat surfaces is demonstrated. Using a template‐stripping technique, isolated metallic nanodisks and wires are embedded in optical epoxy, which is capped with a thin silica overlayer using atomic layer deposition. The top silica surface is topographically flat and laterally homogeneous, providing a uniform, high‐quality biocompatible substrate, while the nanoplasmonic architecture hidden underneath creates a tunable plasmonic landscape for optical imaging and sensing. The localized surface plasmon resonance of gold nanodisks embedded underneath flat silica films is used for real‐time kinetic sensing of the formation of a supported lipid bilayer and subsequent receptor‐ligand binding. Gold nanodisks can also be embedded in elastomeric materials, which can be peeled off the substrate to create flexible plasmonic membranes that conform to non‐planar surfaces.     

Near‐Infrared SERS Nanoprobes with Plasmonic Au/Ag Hollow‐Shell Assemblies for In Vivo Multiplex Detection

For the effective application of surface‐enhanced Raman scattering (SERS) nanoprobes for in vivo targeting, the tissue transparency of the probe signals should be as high as it can be in order to increase detection sensitivity and signal reproducibility. Here, near‐infrared (NIR)‐sensitive SERS nanoprobes (NIR SERS dots) are demonstrated for in vivo multiplex detection. The NIR SERS dots consist of plasmonic Au/Ag hollow‐shell (HS) assemblies on the surface of silica nanospheres and simple aromatic Raman labels. The diameter of the HS interior is adjusted from 3 to 11 nm by varying the amount of Au³⁺ added, which results in a red‐shift of the plasmonic extinction of the Au/Ag nanoparticles toward the NIR (700–900 nm). The red‐shifted plasmonic extinction of NIR SERS dots causes enhanced SERS signals in the NIR optical window where endogenous tissue absorption coefficients are more than two orders of magnitude lower than those for ultraviolet and visible light. The signals from NIR SERS dots are detectable from 8‐mm deep in animal tissues. Three kinds of NIR SERS dots, which are injected into live animal tissues, produce strong SERS signals from deep tissues without spectral overlap, demonstrating their potential for in vivo multiplex detection of specific target molecules.     

Au/AgI Dimeric Nanoparticles for Highly Selective and Sensitive Colorimetric Detection of Hydrogen Sulfide

The development of Au/AgI dimeric nanoparticles (NPs) is reported for highly selective colorimetric detection of hydrogen sulfide (H₂S). The detection mechanism is designed by taking advantage of the chemical transformation of AgI to Ag₂S upon reacting with sulfide, which leads to a shift in the plasmonic band of the attached Au NPs. The plasmonic shift is accompanied by a color change of the solution from purplish red to blue and finally to light green depending on the concentration of sulfide, thus enables a naked‐eye readout and UV–vis quantitation of the sulfide exposure. The Au/AgI dimeric NPs are further immobilized in agarose gels to produce test strips, which can be used for both naked‐eye readout and quantitative detection of sulfide using UV–vis spectroscopy thanks to its transparency in the visible region. Compared to commercial Pb(Ac)₂ test papers, the agarose gel strip has superior performance for detecting sulfide in terms of sensitivity, selectivity, stability, and fidelity. The agarose gel is also capable of detecting gaseous H₂S at important concentration thresholds, suggesting its practicability in real life applications. The potential of agarose gels is further highlighted by its ability in the enrichment and colorimetric detection of gaseous H₂S released during cell cultivation.     

Large‐Area Fabrication of Periodic Arrays of Nanoholes in Metal Films and Their Application in Biosensing and Plasmonic‐Enhanced Photovoltaics

Plasmonics is a fast developing research area with a great potential for practical applications. However, the implementation of plasmonic devices requires low cost methodologies for the fabrication of organized metallic nanostructures that covers a relative large area (～1 cm²). Here the patterning of periodic arrays of nanoholes (PANHs) in gold films by using a combination of interference lithography, metal deposition, and lift off is reported. The setup allows the fabrication of periodic nanostructures with hole diameters ranging from 110 to 1000 nm, for 450 and 1800 nm of periodicity, respectively. The large areas plasmonic substrates consist of 2 cm × 2 cm gold films homogeneously covered by nanoholes and gold films patterned with a regular microarray of 200 μm diameter circular patches of PANHs. The microarray format is used for surface plasmon resonance (SPR) imaging and its potential for applications in multiplex biosensing is demonstrated. The gold films homogeneously covered by nanoholes are useful as electrodes in a thin layer organic photovoltaic. This is first example of a large area plasmonic solar cell with organized nanostructures. The fabrication approach reported here is a good candidate for the industrial‐scale production of metallic substrates for plasmonic applications in photovoltaics and biosensing.     

High‐Temperature Large‐Scale Self‐Assembly of Highly Faceted Monocrystalline Au Metasurfaces

Localized surface plasmon resonance (LSPR) devices based on resonant metallic metasurfaces have shown disruptive potential for many applications including biosensing and photocatalysis. Despite significant progress, highly performing Au plasmonic nanotextures often suffer of suboptimal electric field enhancement, due to damping effects in multicrystalline domains. Fabricating well‐defined Au nanocrystals over large surfaces is very challenging, and usually requires time‐intensive multi‐step processes. Here, presented are first insights on the large‐scale self‐assembly of monocrystalline Au nano‐islands with tunable size and separation, and their application as efficient LSPR surfaces. Highly homogeneous centimeter‐sized Au metasurfaces are fabricated by one‐step deposition and in situ coalescence of hot nanoparticle aerosols into a discontinuous monolayer of highly faceted monocrystals. First insights on the mechanisms driving the high‐temperature synthesis of these highly faceted Au nanotextures are obtained by molecular dynamic and detailed experimental investigation of their growth kinetics. Notably, these metasurfaces demonstrat high‐quality and tunable LSPR, enabling the fabrication of highly performing optical gas molecule sensors detecting down to 3 × 10^?6 variations in refractive index at room temperature. It is believed that these findings provide a rapid, low‐cost nanofabrication tool for the engineering of highly homogenous Au metasurfaces for large‐scale LSPR devices with application ranging from ultrasensitive optical gas sensors to photocatalytic macroreactors.     

Gold Coating of Silver Nanoprisms

Core–shell Ag@Au nanoprisms are prepared through a surfactant‐free seed‐mediated approach by taking advantage of the anisotropic structure of silver nanoprisms as seeds. The gold coating on the silver nanoprism surface is achieved by using hydroxylamine as a mild reducing agent, and the final fully gold‐coated prism structures are confirmed by microscopic and spectroscopic characterization. The resulting Ag@Au core–shell structure preserves the optical signatures of nanoprisms and offers versatile functionality and particularly better stability against oxidation than the bare silver nanoprism. The surface plasmon resonances of the core–shell Ag@Au nanoprisms can be tuned throughout the visible and near‐IR range as a function of the Au shell thickness. Such tailorable optical features and surfactant‐free gold shells have great potential applications in biosensing and bioimaging.     

Detection of Glioma‐Derived Exosomes with the Biotinylated Antibody‐Functionalized Titanium Nitride Plasmonic Biosensor

Titanium nitride (TiN), as an excellent alternative plasmonic supporting material compared to gold and silver, exhibits tunable plasmonic properties in the visible and near‐infrared spectra. However, label‐free surface plasmon resonance biosensing with TiN is seldom reported due to lack of proper surface functionalization protocols. Herein, this study reports biotinylated antibody‐functionalized TiN (BAF‐TiN) for high‐performance label‐free biosensing applications. The BAF‐TiN biosensor can quantitatively detect exosomes of 30–200 nm extracellular vesicles, isolated from a human glioma cell line. The limit of detection for an exosomal membrane protein with the BAF‐TiN biosensor is found to be 4.29 × 10^?3µg mL^?1 for CD63, an exosome marker, and 2.75 × 10^?3µg mL^?1 for epidermal growth factor receptor variant‐III, a glioma specific mutant protein, respectively. In conclusion, combining the biocompatibility, high stability, and excellent label‐free sensing performance of TiN, the BAF‐TiN biosensor could have great potential for the detection of cancer biomarkers, including exosomal surface proteins.     

Emerging Plasmonic Assemblies Triggered by DNA for Biomedical Applications

Plasmonic gold nanocrystal represents plasmonic metal nanomaterials, and has a variety of unique and beneficial properties, such as optical signal enhancement, catalytic activity, and photothermal properties tuned by local temperature, which are useful in physical, chemical, and biological applications. In addition, the inherent properties of predictable programmability, sequence specificity, and structural plasticity provide DNA nanostructures with precise controllability, spatial addressability, and targeting recognition, serving as ideal ligands to link or position building blocks during the self-assembly process. Self-assembly is a common technique for the organization of prefabricated and discrete nanoparticle blocks for the construction of extremely sophisticated nanocomposites. To this end, the integration of DNA nanotechnology with Au nanomaterials, followed by assembly of DNA-functionalized Au nanomaterials can form novel functional Au nanomaterials that are difficult to obtain through conventional methods. Here, recent progress in DNA-assembled Au nanostructures of various shapes is summarized, and their functions are discussed. The fabrication strategies that employ DNA for the self-assembly of Au nanostructures, including dimers, tetramers, satellites, nanochains, and other nanostructures with more complex geometric configurations are first described. Then, the characteristic optical properties and applications of biosensing, bioimaging, drug delivery, and therapy are discussed. Finally, the remaining challenges and prospects are elucidated.     

Plasmon‐Induced Hot Carrier Separation across Dual Interface in Gold–Nickel Phosphide Heterojunction for Photocatalytic Water Splitting

Precise control of the topology of metal nanocrystals and appropriate modulation of the metal–semiconductor heterostructure is an important way to understand the relationship between structure and material properties for plasmon‐induced solar‐to‐chemical energy conversion. Here, a bottom‐up wet chemical approach to synthesize Au/Ni₂P heterostructures via Pt‐catalyzed quasi‐epitaxial overgrowth of Ni on Au nanorods (NR) is presented. The structural motif of the Ni₂P is controlled using the aspect ratio of the Au NR and the effective micelle concentration of the C₁₆TAB capping agent. Highly ordered Au/Pt/Ni₂P nanostructures are employed as the photoelectrocatalytic anode system for water splitting. Electrochemical and ultrafast absorption spectroscopy characterization indicates that the structural motif of the Ni₂P (controlled by the outer‐shell deposition of Ni) helps to manipulate hot electron transfer during surface plasmon decay. With optimized Ni₂P thickness, Pt‐tipped Au NR with an aspect ratio of 5.2 exhibits a geometric current density of 10 mA cm^?2 with an overpotential of 140 mV. The photoanode displays unprecedented long‐term stability with continuous chronoamperometric performance of 50 h at an input potential of 1.5 V with over 30 days. This work provides definitive guidance for designing plasmonic–catalytic nanomaterials for enhanced solar‐to‐chemical energy conversion.     

Aptamer‐Conjugated Nanoparticles Efficiently Control the Activity of Thrombin

Thrombin‐binding aptamer‐conjugated gold nanoparticles (TBA‐Au NPs) for highly effective control of thrombin activity towards fibrinogen are demonstrated. While a 29‐base long oligonucleotide (TBA₂₉) has known no enzymatic inhibitory functions for thrombin‐mediated coagulation, the ultrahigh anticoagulant potency of TBA₂₉‐Au NPs can be demonstrated via the steric blocking effect, at two orders of magnitude higher than that of free TBA₂₉. The surface aptamer density on the Au NPs is important in determining their enzymatic inhibition of thrombin and their stability in the presence of nuclease. The practicality of 100TBA₂₉‐Au NPs (100 TBA₂₉ molecules per Au NP) for controlling thrombin‐mediated coagulation in plasma is found, and the 100TBA₂₉‐Au NPs has an ultra binding affinity towards thrombin (K_d = 2.7 × 10^?11M ) due to their high ligand density. The anticoagulant activity of TBA₂₉‐Au NPs is found to be suppressed by TBA₂₉ complementary sequence (cTBA₂₉) modified Au NPs (cTBA₂₉‐Au NPs), with a suppression rate 4.6‐fold higher than that of cTBA₂₉. The easily prepared and low‐cost TBA₂₉‐Au NPs and cTBA₂₉‐Au NPs show their potential in biomedical applications for treating various diseases related to blood clotting disorders. In principle, this study opens the possibility of regulation of molecule binding, protein recognizing, and enzyme activity by using aptamer‐functionalized nanomaterials.     

Shell-Isolated Plasmonic Nanostructures for Biosensing,Catalysis, and Advanced Nanoelectronics

Shell-isolated nanostructures, consisting of an inert shell and a plasmonic core, have recently been intensively explored for biosensing, catalysis, and nanoelectronics applications owing to their functional shells and unique plasmonic properties. Such designer shell-isolated plasmonic nanostructures possess the potential to improve the detectability of biosensors and provide powerful platforms to explore in-depth plasmon enhancement principles and finally boost significantly their photo(electro)catalytic efficiency. In addition, such structural optimization and interface nanoengineering promote solid developments of advanced nanoelectronics toward real applications, revealing new electron transport mechanisms and enabling exploration of new functional and integrated optoelectronic devices. In this overview, the state-of-the-art progresses of shell-isolated plasmonic nanostructures (SHIPNSs) in the field of biosensing, photo(electro)catalysis, and nanoelectronics is summarized, focusing on the superiority of the core–shell materials in exploration of biosensing, catalytic enhancement mechanisms, and electron transport principles. A brief overview of synthetic methods is introduced, and then the significant importance of shell-isolated nanomaterials in fabrication and promising direction for future development and challenges are discussed.     

磷酰化芳香族氨基酸的激光诱导荧光光谱

利用Ｎｄ：ＹＡＧ激光器的四倍频输出２６６ｎｍ近紫外光激发固体纯磷酰化芳香族氨基酸样品，获得可见光波段的荧光发射，其光谱结构分别为芳香环和磷酰基的发射，结果发现取代基的导入使芳香环荧光峰红移，而对磷酰基的荧光峰的影响则为紫移。     

傅里叶红外光谱研究光敏剂5-氨基酮戊酸的光动力作用机制

本文测定了光敏剂5-氨基酮戊酸对人宫颈癌细胞HeLa光敏作用后的傅里叶红外光谱。结果显示：光敏作用后,HeLa细胞磷酸二酯基团的对称伸缩振动峰1085cm。和不对称伸缩振动峰1246cm。蓝移,强度下降;蛋白质酰胺Ⅰ带1656cm。发生蓝移,酰胺Ⅱ带1546cm^-1出现红移;CH2对称伸缩振动峰2858cm^-1,峰位蓝移2cm^-1,峰值明显减弱。结果表明：DNA、蛋白质和磷脂是5-氨墓酮戊酸光敏作用的主要靶分子。     

Gold Nanobipyramid‐Supported Silver Nanostructures with Narrow Plasmon Linewidths and Improved Chemical Stability

Silver nanostructures with narrow plasmon linewidths and good chemical stability are strongly desired for plasmonic applications. Herein, a facile method is discussed for the preparation of Ag nanostructures with narrow plasmon linewidths and improved chemical stability through Ag overgrowth on monodispersed Au nanobipyramids. Structural evolution from bipyramid through rice to rod is observed, indicating that Ag atoms are preferentially deposited on the side surfaces of Au nanobipyramids. The resultant (Au nanobipyramid)@Ag nanostructures possess high size and shape uniformities, and much narrower plasmon linewidths than other Ag nanostructures. The spectral evolution of the supported Ag nanostructures is ascertained by both ensemble and single‐particle characterizations, together with electrodynamic simulations. Systematic measurements of the refractive index sensing characteristics indicate that Ag nanostructures in this study possess high index sensitivities and figure of merit (sensitivity divided by linewidth) values. Moreover, Ag nanostructures in this study exhibit greatly improved chemical stability. The superior sensing capability of Ag nanostructures in this study is further demonstrated by the detection of sulfide ions at a relatively low detection limit. Taken together, results of this study show that the Au‐nano­bipyramid‐supported Ag nanostructures will be an outstanding candidate for the design of ultrasensitive plasmonic sensing devices as well as for the development of other plasmon‐enabled technological applications.     

Bioinspired Trans‐Scale Functional Interface for Enhanced Enzymatic Dynamics and Ultrasensitive Detection of microRNA

Protein interactions with specific nucleic acid sequences are crucial in cell growth. Inspired by such binding events that often occur at nanoscale biointerface, here a trans‐scale functional interface capable of considerably enhancing in vitro DNA‐enzyme interaction is reported. Using a screen‐printed electrode with nanoroughened carbon surface, the high‐curvature gold nanostructures in a single electrodeposition step can be programmed. In this process, a synergistic effect is found between nanoroughened carbon and polyelectrolyte multilayer enabling the formation of high‐stability and high‐curvature nanostructures. More importantly, these fractal nanostructures effectively overcome neighboring probes aggregation at high density and allow the probes to be more freely accessed by target molecules. As compared to its planar counterparts, this nanostructuring interface demonstrates faster enzymatic dynamics that enables ultrasensitive detection of microRNA with a detection limit of 35 × 10⁻¹⁸ m . Such an efficient trans‐scale biosensing interface has also accurately differentiated the patients with rheumatic arthritis from the health ones, signifying its great potential in precision medicine.     

Fabrication of Low‐Threshold 3D Void Structures inside a Polymer Matrix Doped with Gold Nanorods

We report on a low‐threshold three‐dimensional (3D) void generation inside a polyvinyl‐alcohol (PVA) polymer matrix doped with gold nanorods (NRs) by near infra red femtosecond laser pulses. By matching the laser wavelength to the surface plasmon resonance band of the embedded gold NRs, the void generation threshold could be reduced by one order of magnitude lower than undoped matrix. We discuss physical mechanisms involved in the void generation, where distinction between the decomposition of gold NR or PVA is drawn in single pulse and multiple pulse irradiations. We also demonstrate 3D void recording for applications in 3D optical data storage.     

DNA Origami‐Guided Assembly of the Roundest 60–100 nm Gold Nanospheres into Plasmonic Metamolecules

DNA origami can provide programmed information to guide the self‐assembly of gold nanospheres (Au NSs) into higher‐order supracolloids. Molecularly precise and truly 2D/3D integration of Au NSs is possible using DNA origami‐enabled assembly, and the resulting assemblies have potential applications in plasmonics and metamaterials. However, the relatively small size (<60 nm) and randomly faceted Au NSs that have been used thus far in DNA origami‐enabled assembly have limited their nanophotonic applications. Here, the robust self‐assembly of the 60–100 nm roundest Au NSs into metamolecular assemblies using 3D DNA origami is described. These Au NSs are successfully conjugated with DNA oligonucleotides and are therefore stable at high salt concentrations even without backfilling using organic ligands. The roundest Au NSs are successfully assembled into supracolloidal metamolecules and chains via 3D DNA origami. These plasmonic metamolecules and chains display strong electric and unnatural magnetic resonances that can be deterministically controlled.     

Plasmomechanical Systems: Principles and Applications

Extreme confinement of electromagnetic waves and mechanical displacement fields to nanometer dimensions through plasmonic nanostructures offers unprecedented opportunities for greatly enhanced interaction strength, increased bandwidth, lower power consumption, chip-scale fabrication, and efficient actuation of mechanical systems at the nanoscale. Conversely, coupling mechanical oscillators to plasmonic nanostructures introduces mechanical degrees of freedom to otherwise static plasmonic structures thus giving rise to the generation of extremely large resonance shifts even for minor position changes. This nanoscale marriage of plasmonics and mechanics has led to the emergence of a new field of study called plasmomechanics that explores the fundamental principles underneath the coupling between light and plasmomechanical nanoresonators. In this review, both the fundamental concepts and applications of plasmomechanics as an emerging field of study are discussed. After an overview of the basic principles of plasmomechanics, the active tuning mechanisms of plasmonic nano-mechanical systems are extensively analyzed. Moreover, the recent developments on the practical implications of plasmomechanic systems for such applications as biosensing and infrared detection are highlighted. Finally, an outlook on the implications of the plasmomechanical nanosystems for development of point-of-care diagnostic devices that can help early and rapid detection of fatal diseases are forwarded.