Reliable detection of malachite green by self-assembled SERS substrates based on gold-silicon heterogeneous nano pineapple structures.

Morphology regulation of heterodimer nanoparticles and the use of their asymmetric features for further practical applications are crucial because of the rich optical properties and various combinations of heterodimers. This work used silicon to asymmetrically wrap half of a gold sphere and grew gold branches on the bare gold surface to form heterogeneous nano pineapples (NPPs) which can effectively improve Surface-enhanced Raman scattering (SERS) properties through chemical enhancement and lightning-rod effect respectively. The asymmetric structures of NPPs enabled them to self-assemble into the monolayer membrane with consistent branch orientation. The prepared substrate had high homogeneity and better SERS ability than disorganized substrates, and achieved reliable detection of malachite green (MG) in clams with a detection limit of 7.8 × 10-11 M. This work provided a guide to further revise the morphology of heterodimers and a new idea for the use of asymmetric dimers for practically photochemical and biomedical sensing.

Morphology and optical properties of Au-Ag hybrid nanoparticles regulation and its ultra-sensitive SERS immunoassay detection in carbohydrate antigen 19-9.

The development of an ultra-sensitive detection method for carbohydrate antigen 19-9 (CA19-9) is very important for the early diagnosis of pancreatic cancer. In this work, we developed a new strategy to achieve a variety of Au-Ag hybrid nanoparticles from janus to core-satellite which is controlled by the volume of AgNO3 and the concentration of benzimidazolecarboxylic acid (MBIA). With the volume of AgNO3 increased, Au-Ag hybrid nanoparticles changed from janus to core-satellite and the characteristic absorption peak showed two opposite trends. The size and number of Ag islands were determined by the concentration of MBIA. Au-Ag core-satellites nanoparticles with a large number of small-sized Ag have the highest SERS intensity. Then we used them as SERS nanotags and Au-Polystyrene nanospheres modified by captured anti-CA19-9 antibody as solid substrates to realize the ultra-sensitive detection of CA19-9 with a low limit of detection of 1.25 × 10-6 IU/mL and a wide linear range of 1.00 × 10-5 -1.00 × 104 IU/mL. This work not only demonstrates that MBIA and AgNO3 were the key factors in the growth of Au-Ag hybrid nanoparticles from 2D to 3D structure but also supplies an ultra-sensitive detection method for CA19-9 which has a potential practicability in the clinical early diagnoses of pancreatic cancer.

Exclusive Core-Janus Satellite Assembly Based on Au-Ag Janus Self-Aligned Distributions with Abundant Hotspots for Ultrasensitive Detection of CA19-9.

The development of surface-enhanced Raman scattering (SERS) probes with high sensitivity and stability is imminent to improve the accuracy of cancer diagnosis. Here, an exclusive core-Janus satellite (CJS) assembly was constructed by a hierarchical assembly strategy in which the Au-Ag Janus satellite is vertically self-aligned on the core surface. In the process, a silica shell template was ingeniously employed to asymmetrically mask the presatellites for the in situ formation of the Janus structure, and a series of Janus satellites with different morphologies were developed by regulating the encapsulated area of the presatellites. The ordered-oriented arrangement of Au-Ag Janus and unique heterojunction morphology permit CJS assemblies, featuring two types of plasmonic nanogaps, including intrananocrevices for individual Janus and internanogaps between neighboring Janus, thereby multiplying the "hotspots" compared to conventional core-monotonous satellites, which contributes to superior SERS activity. As anticipated, the enhancement factor of CJS assemblies was as high as 3.8 × 108. Moreover, it is intriguing that the directional distribution and head physically immobilized by Janus provided uniform and stable SERS signals. The SERS probe based on the CJS assembly for the detection of carbohydrate antigen 19-9 resulted in an ultrahigh sensitivity with a limit of detection of 3.7 × 10-5 IU·mL-1, which is nearly 10 times lower than other SERS probes, and a wide detection range of 3 × 10-5 to 1 × 104 IU·mL-1. The CJS assembly with excellent SERS performance is promising to advance further development of the early diagnosis of pancreatic cancer.

Application of nanotechnology in bladder cancer diagnosis and therapeutic drug delivery.

Bladder cancer (BC) is one of the most common malignant tumors in the urinary system, and its high recurrence rate is a great economic burden to patients. Traditional diagnosis and treatment methods have the disadvantages of insufficient targeting, obvious side effects and low sensitivity, which seriously limit the accurate diagnosis and efficient treatment of BC. Due to their small size, easy surface modification, optical properties such as plasmon resonance, and surface enhanced Raman scattering, good electrical conductivity and photothermal conversion properties, nanomaterials have great potential application value in the realization of specific diagnosis and targeted therapy of BC. At present, the application of nanomaterials in the diagnosis and treatment of BC is attracting great attention and achieving rich research results. Therefore, this paper summarizes the recent research on nanomaterials in the diagnosis and treatment of BC, clarifies the existing advantages and disadvantages, and provides theoretical guidance for promoting the accurate diagnosis and efficient treatment of BC.

An anisotropic nanobox based core-shell-satellite nanoassembly of multiple SERS enhancement with heterogeneous interface for stroke marker determination.

Herein, A novel gold-silver alloy nanobox (AuAgNB)@SiO2-gold nanosphere (AuNP) nanoassembly based on core-shell-satellite structure is fabricated and applied to the surface-enhanced Raman scattering (SERS) detection of S100 calcium-binding protein B protein (S100B). It contains an anisotropic hollow porous AuAgNB core with rough surface, an ultrathin silica interlayer labeled with reporter molecules, and AuNP satellites. The nanoassemblies were systematically optimized by tuning the reporter molecules concentration, silica layer thickness, AuAgNB size, and the size and number of AuNP satellite size. Remarkably, AuNP satellites are adjacent to AuAgNB@SiO2, developing AuAg-SiO2-Au heterogeneous interface. With the strong plasmon coupling between AuAgNB and AuNP satellites, chemical enhancement from heterogeneous interface, and the tip "hot spots" of AuAgNB, the SERS activity of the nanoassemblies was multiply enhanced. Additionally, the stability of nanostructure and Raman signal was significantly improved by the silica interlayer and AuNP satellites. Eventually, the nanoassemblies were applied for S100B detection. It demonstrated satisfactory sensitivity and reproducibility with a wide detection range of 10 fg/mL-10 ng/mL and a limit of detection (LOD) of 1.7 fg/mL. This work based on the AuAgNB@SiO2-AuNP nanoassemblies with multiple SERS enhancements and favorable stability demonstrates the promising application in stroke diagnosis.

Site-selective growth and plasmonic spectral properties of L-shaped Janus Au-Ag gold nanodumbbells for surface-enhanced Raman scattering.

Ligand-mediated interface control has been broadly applied as a powerful tool in constructing asymmetric multicomponent nanoparticles (AMNP), and induces the anisotropic growth with fine-tuning morphology, composition, plasmonic property and functionality. As a new kind of AMNP, the synthesis of Janus Au-Ag nanoparticles with tunable negative surface curvature is still a challenge. Here, we demonstrate that the synergistic surface energy effects between gold nanodumbbells (Au NDs) with a negative surface curvature and 4-mercaptobenzoic acid (4-MBA) can direct the site-selective growth of anisotropic silver domains on gold nanodumbbells (Au NDs@Ag NPs). By adjusting the 4-MBA concentration-dependent interfacial energy, the Au NDs@Ag NPs could be continuously tuned from dumbbell-like core-shell structures, to L-shaped Janus, and then rod-like core-shell structures with directional and asymmetric spatial distributions of resizable Ag domains by site-selective growth. Based on the calculation results of discrete dipole approximation (DDA) method, it has been found that the Au NDs@Ag L-shaped Janus NPs with Ag island domains created polarization orientation-dependent plasmonic extinction spectra and hot spots around the negatively curved waist and Ag domains. The L-shaped Janus Au NDs@Ag NPs exhibited significantly plasmonic spectrum properties with four apparent LSPR peaks that cover from visible to near-infrared range and higher surface-enhanced Raman scattering (SERS) activity compared with the original Au NDs. The best SERS enhancement factor of 1.41 × 107 was achieved. This synergistic surface energy effect-based method involving the asymmetric growth of silver coating on gold nanoparticles with negatively curved surface presents a new method to design and fabricate nanometer optical devices based on asymmetric multicomponent nanoparticles.

Au@Ag Nanopencil with Au Tip and Au@Ag Rod: Multimodality Plasmonic Nanoprobe based on Asymmetric Etching for the Detection of SCN- and ClO.

In this paper, Au@Ag nanopencil is designed as a multimodality plasmonic nanoprobe based on asymmetric etching for the detection of SCN- and ClO- . Au@Ag nanopencil with Au tip and Au@Ag rod is prepared by asymmetric tailoring of uniformly grown silver-covered gold nanopyramids under the combined effect of partial galvanic replacement and redox reaction. By asymmetric etching in different systems, Au@Ag nanopencil exhibits diversified changes in the plasmonic absorption band: O2 •- facilitated by SCN- etches Au@Ag rod from the end to the tip, causing a blue shift of the localized surface plasmon resonance (LSPR) peak as the aspect ratio decreases; while the ClO- can retain Au@Ag shell and etch Ag within rod from the tip to the end, causing a redshift of the LSPR peak as the coupling resonance weakens. Based on peak shifts in different directions, a multimodality detection of SCN- and ClO- has been established. The results demonstrate the detection limits of SCN- and ClO- are 160 and 6.7 nm, and the linear ranges are 1-600 µm and 0.05-13 µm, respectively. The finely designed Au@Ag nanopencil not only broadens the horizon of designing heterogeneous structures, but also enriches the strategy of constructing multimodality sensing platform.

Core-satellite nanostructures and their biomedical applications.

Plasmonic core-satellite nanostructures assembled from simple building blocks have attracted extensive attention since they were reported by the way of DNA-directed assembly in 1998, because of their unique enhanced and synergistic optical properties and widespread potential applications in biosensing, imaging, drug delivery, and diagnostics. In this review, we introduce the synthetic methods of core-satellite nanostructures, emphazising the bottom-up synthesis method, including DNA, molecular, protein, peptide, amino acids, metal ion-assisted assembly, electrostatic adsorption assembly, clicked-to-assembly, and in situ deposition. Than we review and discuss their morphology classification, and summarize influencing factors of morphology. This is followed by overviews on optical properties, including localized surface plasmon resonance, surface-enhanced Raman scattering, surface-enhanced fluorescence and quenching, and applications in the biomedical field. Finally, the challenges and prospects of these kinds of nanostructures are discussed.

Multiplex Sensing Based on Plasmonic Optics of Noble Metallic Nanostructures.

Since the colorimetric method has the characteristics of being simple and low cost, the fluorescence spectrum has the characteristics of a strong signal, and Surface-enhanced Raman scattering (SERS) detection has the characteristics of high sensitivity and strong specificity, people usually use these three methods for detection, but the detection of a single sample takes more time. If multiple samples can be tested at the same time, the detection efficiency and sensitivity can be improved, and the selectivity and reliability will be greatly improved. Multiplex sensing also provides a new direction for researchers. To fully understand the research of multiplex sensing based on the plasmonic optics of noble metal nanostructures, this review summarizes all the results previously reported in this field. It also discusses the principles of various detection methods and the biochemical application of multiple detections and finally summarizes the challenges and prospects.

Fluorescence quenching properties of Au-Ag-Pt tri-metallic nanorod: The application in specific detection of alpha-fetoprotein.

In this paper, the fluorescence quenching characteristics of Au-Ag-Pt core-shell nanorods have been studied.Due to nonradiative energy transformation, the fluorescence emission intensity of bovine serum albumin (BSA) could be greatly quenched.It has been found that the quenching effect of Au-Ag-Pt core-shell nanorods could be optimized by adjusting the concentration of chloroplatinic acid.Based on the fluorescence quenching properties of Au-Ag-Pt core-shell nanorods, Au-Ag-Pt trimetal fluorescence quenching nanoprobe has been prepared, and the specificity of alpha-fetoprotein (AFP) detection has also been realized.In order to guarantee the sensing specificity, the surface modification including carboxyl replacement, carboxyl activation and antibody connection have been performed on Au-Ag-Pt core-shell nanorods.By using the principle of specific combination of antigen and antibody, the specific detection of AFP has been realized with a lower detection limit of 4.0 pg/mL, and the linear detection range spans a scope from 0.03 to 0.5 ng/mL.Interference experiments and the actual samples detection results show that the Au-Ag-Pt trimetal core-shell nanorod probes have good anti-interference and repeatability.

Surface etching-dependent geometry tailoring and multi-spectral information of Au@AuAg yolk-shell nanostructure with asymmetrical pyramidal core: The application in Co2+ determination.

In this paper, a novel Au@AuAg yolk-shell heterogeneous nanostructure is designed as plasmonic spectroscopic sensor based on surface etching for ultrasensitive detection of trace cobalt ions (Co2+). Due to the surface diffusion of gold atoms, the Ag at one end of the core gold nanobipyramids (Au NBPs) is retained, and Au@AuAg yolk-shell nanostructure with asymmetric core is prepared. The alloy shell is coupled to Au NBPs and the interface of asymmetric Ag respectively, the two local surface plasmon resonance bands will have obvious reverse changes depending on the surface morphology of the shell. By using this distinct plasmon response generated by Co2+ induced surface etching, which is driven by discrepancy of double-peaks, a sensing method has been established to realize multi-information spectral detection of Co2+. There is a good linear relationship between the intensity ratio and the Co2+ concentration in the range of 1-100 nM, in which the limit of detection is 0.2 nM. This method further improves the sensing capability by combining multiple pieces of strongly changing spectral information, and demonstrates great advantages and potential of Au@AuAg yolk-shell heterogeneous nanostructure as a multi-information plasmonic sensor based on etched shell surface for trace detection.

Theoretical simulation of nonlinear regulation of wall thickness dependent longitudinal surface plasmon in pentagonal gold nanotubes.

In this paper, the longitudinal plasmon mode optical properties and localized electric field distribution of a single pentagonal gold nanotube are investigated for the first time by the discrete dipole approximation. It is found that pentagonal gold nanotube has stronger electric field distribution compared with circular gold nanotubes when the incident wavelength is located at the plasmon resonance peak. Additionally, we observed that the longitudinal plasmon resonance peak can blue shift nonlinearly with increasing wall thickness, but red shifts linearly with the increase of the length of the pentagonal gold nanotube. The localized electric field analysis reveals that the longitudinal plasmon peak of the pentagonal gold nanotube originates from the dipole resonance mode. The local electric field intensity is controlled by the wall thickness and length. Notably, the effect of wall thickness on the longitudinal plasmon resonance and electric field enhancement can be attributed to the change of the plasmon coupling position and intensity. This work has enriched the theoretical research of pentagonal gold nanotubes and provided ideas for the preparation of high sensitivity nanoprobes biosensors.

Heterodimers of metal nanoparticles: synthesis, properties, and biological applications.

Heterodimers of metal nanoparticles consist of two metals, come in many sizes and adopt various shapes. They offer unique properties due to the presence of two metals and have the extraordinary flexibility needed to serve as a multipurpose platform for diverse applications in areas including photonics, sensing, and catalysis. Heterodimer nanoparticles contain different metals that contribute to extraordinary surface plasmon resonance (SPR), surface-enhanced Raman scattering (SERS), and catalytic properties. These properties make them versatile molecules that can be used in intracellular imaging, as antibacterial agents, as photocatalytic and biological macromolecules and for the detection of chemical substances. Moreover, heterodimer nanoparticles are composed of the two metals within larger molecules that provide more choices for modification and application. In this review, we briefly summarize the lesser-known aspects of heterodimers, including some of their properties, and present concrete examples of recent progress in synthesis and applications. This review provides a perspective on achievements and suggests a framework for future research with a focus on the synthesis and application of heterodimers. We also explore the possible applications of heterodimer nanoparticles based on their unique properties.

Spiky yolk-shell AuAg bimetallic nanorods with uniform interior gap for the SERS detection of thiram residues in fruit juice.

By using gold nanorods with silver coating as the sacrificial templates, we prepared spiky yolk-shell AuAg bimetallic nanorods with uniform interior gap via galvanic replacement reaction. The length and number of Au tips of the spiky yolk-shell AuAg nanorods can be tuned simultaneously by altering HAuCl4 volume. The influence of HAuCl4 volume and the sliver layer thickness on the SERS activity of spiky yolk-shell AuAg nanorods are studied. When the sliver layer is thin, the interior gap has not been shielded completely and the outer shell has obvious tips, thus the surface-enhanced Raman scattering (SERS) activity has the strongest enhancement with an enhancement factor (EF) of 4.9 × 105. The spiky yolk-shell AuAg nanorods with the strongest SERS activity are used as SERS substrates to detect thiram. The results demonstrate that the SERS intensity increases linearly with the logarithmic concentration of thiram in the range of 10-3 M to 10-7 M. The detection limit is as low as 97 nM, which is lower than the maximum pesticide residue limit (29 µM) in fruits stipulated by the US Environmental Protection Agency (EPA). Therefore, the spiky yolk-shell AuAg bimetallic nanorods have important practical application value in pesticide detection.

Recent progress in the optical detection of pathogenic bacteria based on noble metal nanoparticles.

Pathogenic bacteria have become a huge threat to social health and economy for their frighteningly infectious and lethal capacity. It is quite important to make a diagnosis in advance to prevent infection or allow a rapid treatment after infection. Noble metal nanoparticles, due to their unique physicochemical properties, especially optical properties, have drawn a great attention during the past decades and have been widely applied into all kinds of fields related to human health. By utilizing these noble metal nanoparticles, optical diagnosis platforms towards pathogenic bacteria have emerged continually, providing highly sensitive, selective, and particularly facile detection tools for clinic or point-of-care diagnosis. This review summarizes the recent development in this field. It begins with a brief introduction of pathogenic bacteria and noble metal nanoparticles. And then, optical detection methods are systematically discussed in three distinct aspects. In addition to these proof-of-concept methods, corresponding algorithms and point-of-care detection devices are also described. Finally, the review ends up with subjective views on present limitations and some appropriate advice for future research directions.

Selective controlling transverse plasmon spectrum of pentagonal gold nanotube: from visible to near-infrared region.

In this paper, the optical properties and local electric field distribution of transverse plasmon mode of a single pentagonal gold nanotube are studied for the first time by the discrete dipole approximation (DDA). We find that the transverse plasmon peaks can nonlinearly red shift from visible to infrared region via controlling the inner diameter. In addition, the transverse plasmon peak firstly blue shifts and then red shifts in the visible region with the increase of outer diameter. Further analysis shows that the spectra red shift with the increase of outer diameters when scattering is dominant. Local electric field analysis reveals that transverse plasmon resonance peaks of gold nanotube mainly come from dipole resonance. When the tube wall is thin enough, multi-polar plasmon resonance mode will be generated, and the number of peaks will be increased. The surface charges of inner and outer tube walls are changed by tuning the inner diameter and outer diameter parameters of pentagonal gold nanotube. The selective controlling transverse plasmon spectra of gold nanotube are realized, which is of great significance to the study of optical properties of gold nanotube and the application of molecular detection and biological imaging.

Colorimetric determination of cysteine based on inhibition of GSH-Au/Pt NCs as peroxidase mimic.

In this work, we reported a facile and highly sensitive strategy for colorimetric detection of cysteine (Cys) based on the inhibition of catalytic activity of bimetallic nanoclusters induced by Cys. Glutathione-modified gold-platinum nanoclusters (GSH-Au/Pt NCs) with different Au/Pt molar ratios were prepared via one-pot approach and utilized as peroxidase mimics to catalyze the oxidation of 3,3',5,5'-tetramethylbenzidine (TMB) by H2O2. It has been found that Cys could inhibit the peroxidase-like activity of GSH-Au/Pt NCs efficiently, which leads to a decrease of the absorption intensity of the system at 652 nm with a fading of the blue color. These findings provide a worthy method for visualization and quantitative detection of Cys with different concentrations in the range from 0.5 to 30 µM, and the detection limit is 0.154 µM. Moreover, this method displays a promising application in colorimetric analysis of Cys in urine samples.

Gold nanotubes: synthesis, properties and biomedical applications.

This review (with 106 references) summarizes the latest progress in the synthesis, properties and biomedical applications of gold nanotubes (AuNTs). Following an introduction into the field, a first large section covers two popular AuNTs synthesis methods. The hard template method introduces anodic alumina oxide template (AAO) and track-etched membranes (TeMs), while the sacrificial template method based on galvanic replacement introduces bimetallic, trimetallic AuNTs and AuNT-semiconductor hybrid materials. Then, the factors affecting the morphology of AuNTs are discussed. The next section covers their unique surface plasmon resonance (SPR), surface-enhanced Raman scattering (SERS) and their catalytic properties. This is followed by overviews on the applications of AuNTs in biosensors, protein transportation, photothermal therapy and imaging. Several tables are presented that give an overview on the wealth of synthetic methods, morphology factors and biological application. A concluding section summarizes the current status, addresses current challenges and gives an outlook on potential applications of AuNTs in biochemical detection and drug delivery.Graphical abstract.

Detection of ferrous ion by etching-based multi-colorimetric sensing of gold nanobipyramids.

Colorimetric sensing methods based on non-spherically symmetric gold (Au) nanoparticles have become a powerful tool in the field of biomedical detection due to their intriguing plasmonic properties. In this study, Au nanobipyramids (Au NBPs) were used as colorimetric sensing probes to detect ferrous ions (Fe2+) through tip etching. The quick etching of Au NBPs along the longitudinal direction by superoxide radicals generated by the reaction of Fe2+ and H2O2 led local surface plasmon resonance (LSPR) to blue shift and produced vivid color change that could be used for visual inspection. Under the optimal reaction conditions, the peak shift of the Au NBPs and the logarithm of the concentrations of Fe2+ had a linear relationship in the range of 10 nM to 10 µM, with a very low detection limit of 1.29 nM. During the etching process, a different end shape of the Au nanoparticles results in a different process for the morphology transition, which makes the degree of spectral change and detection sensitivity significantly different. In the presence of trace amounts of Fe2+ (<1000 nM), the detection sensitivity of Au NBPs with sharp ends which rely on aspect ratio and truncation is nine times higher than that of gold nanorods with round ends which only rely on aspect ratio. Although the color change of larger-sized Au NBPs was not clear during detection, the LSPR peak shift was more severe. Therefore, the system provides different modes for detecting Fe2+ according to Au NBPs with different sizes and characteristics.

The morphology regulation and plasmonic spectral properties of Au@AuAg yolk-shell nanorods with controlled interior gap.

Au@AuAg yolk-shell nanorods with tunable and uniform interior gap were synthesized through galvanic replacement reaction, where Au@Ag core-shell nanorods served as sacrificial templates and HAuCl4 solution served as reductant. The effects of HAuCl4, Ag shell thickness and aspect ratio (AR) of Au nanorods on the morphology of Au@AuAg yolk-shell nanorods had been investigated systemically. The results clearly indicated that AuAg alloy shell thickness of Au@AuAg yolk-shell nanorods could be increased from 3.6 to 10.0 nm by varying the amount of HAuCl4. Meanwhile, the shape of AuAg alloy shell could be tuned by changing the shape of Ag coating. With the increasing of Ag coating thickness, the interior gap could be finely tuned in the range from 2.6 to 8.1 nm. The uniformity of interior gap could be improved by increasing the AR of Au nanorods. All these tunable geometries can further affect the plasmonic spectral properties of Au@AuAg yolk-shell nanorods. Because of the appearance of interior gap, the longitudinal localized surface plasmon resonance (LSPR) peak of Au@AuAg yolk-shell nanorods was located between that of bare Au nanorods and Au@Ag core-shell nanorods without interior gap. The increase of outer AuAg shell thickness can weaken the coupling between the inner and outer surface of the AuAg shell and lead to the decrease of AR, so the transverse and longitudinal LSPR bands gather together. The decrease of Ag coating thickness can enhance the coupling between inner Au nanorod and outer AuAg shell, which results in the red shift of the longitudinal LSPR band. This paper provides a method for studying the plasmonic coupling between two metal surfaces with a metal layer or a dielectric layer, which is also a new approach for regulating the plasmonic spectral properties of bimetallic nanoparticles. The controllability of Au@AuAg yolk-shell nanorods in both the interior gap and outer alloy shells makes them have potential applications in biomedicine, catalysis, nanoreactors, and energy storage.