Triangular Nanoprisms Research Articles

Copper Sulfide Nanodisks and Nanoprisms for Photoacoustic Ovarian Tumor Imaging.

Transvaginal ultrasound is widely used for ovarian cancer screening but has a high false positive rate. Photoacoustic imaging provides additional optical contrast to supplement ultrasound and might be able to improve the accuracy of screening. Here, we report two copper sulfide (CuS) nanoparticles types (nanodisks and triangular nanoprisms) as the photoacoustic contrast agents for imaging ovarian cancer. Both CuS nanoprisms and nanodisks were ~6 nm thick and ~26 nm wide and were coated with poly(ethylene glycol) to make them colloidally stable in phosphate buffered saline (PBS) for at least 2 weeks. The CuS nanodisks and nanoprisms revealed strong localized surface plasmon resonances with peak maxima at 1145 nm and 1098 nm, respectively. Both nanoparticles types had strong and stable photoacoustic intensity with detection limits below 120 pM. The circular CuS nanodisk remained in the circulation of nude mice (n=4) and xenograft 2008 ovarian tumors (n=4) 17.9-fold and 1.8-fold more than the triangular nanoprisms, respectively. Finally, the photoacoustic intensity of the tumors from the mice (n=3) treated with CuS nanodisks was 3.0-fold higher than the baseline. The tumors treated with nanodisks had a characteristic peak at 920 nm in the spectrum to potentially differentiate the tumor from adjacent tissues.

Synthesis of uniform hexagonal Ag nanoprisms with controlled thickness and tunable surface plasmon bands

In this work, we synthesized monodispersed hexagonal Ag nanoprisms in high yields in a system of poly(vinylpyrrolidone) (PVP) in N-methylpyrrolidone (NMP). A blue shift occurred and was strongly dependent on the thickness of the uniform Ag nanoprisms, which had almost the same radial area. When the Ag nanoprisms grew thicker, their in-plane dipole resonance peaks markedly shifted toward shorter wavelengths (i.e., blue shift). PVP played a critical role of favoring vertical growth of the Ag nanoplates, preventing aggregation, and inducing the formation of Ag hexagonal nanoprisms (HNPs) through the transformation from thin Ag triangular nanoprisms (TNPs). Compared with similar previous research, the present study provides quite uniform Ag hexagonal nanoplates, which makes the blue shift related more solely and distinctly to the thickness of the Ag nanoprisms. The findings of this work provide a new perspective toward understanding the unique optical characteristics of Ag HNPs with different aspect ratios.

Buffer-layer-assisted morphological manipulation of metal nanoparticle arrays by laser irradiation

We evaluate the performance of an adhesion buffer layer between ordered metal nanoparticle arrays and dielectric substrates on the particles' morphological manipulation by pulsed laser irradiation. The experiments are performed irradiating with only one nanosecond pulse at 355 nm, triangular nanoprism arrays fabricated by nanosphere lithography (polystyrene spheres with 1030 nm in diameter), followed by film deposition by magnetron sputtering. The reshaping of the nanoprisms into spheres as result of laser-induced melting is investigated for three different materials: prisms made of Cr, Au and Au with a buffer layer made of Cr (Au/Cr). These elements are chosen because their interfacial interaction with the substrates (soda-lime glass and fused silica) is quite different. Our results show that single pulse irradiation at fluences above the metal melting threshold allows the formation of disorder spheres for the case of Au, but ordered spheres for the cases of Cr and Cr/Au. Therefore, the function of the buffer layer is to improve the adhesion between the prisms and the substrate, thus allowing their reshaping by laser-induced melting but preserving their position. The strong interaction between Cr and the substrate is also exploited for the nanostructuration of the substrate by the formation of ordered holes with sub-micrometer dimensions. These findings reboot laser postprocessing of ordered structures fabricated by nanosphere lithography exploit to explore new capacities of nanostructuration.

Robust Synthesis of Size-Dispersal Triangular Silver Nanoprisms via Chemical Reduction Route and Their Cytotoxicity.

Triangular silver nanocrystals, well-known as nanoprisms (Ag-NPrs), were successfully developed via a robust and straightforward direct chemical reduction synthetic approach, producing desirable tiny and well-controlled Ag-NPrs. This procedure was accomplished by fabricating a mixture of di-sodium succinate hexa-hydrate (DSSH) and tri-sodium citrate di-hydrate (TSCD) as capping agents at optimal synthetic conditions and under an open-air condition, which proved to be an enormous challenge. Additionally, the Ag-NPrs were fully characterized by UV-vis spectra, X-ray diffraction (XRD), scanning electron microscope (SEM), and dynamic light scattering (DLS). Likewise, the formation stages from spherical silver nanoparticles (Ag-NPs) to triangular Ag-NPrs were also captured simultaneously via transmission electron microscope (TEM) and high-resolution transmission electron microscope (HR-TEM) images. More interestingly, an active thin silica-shell was efficiently applied on the Ag-NPrs outer-layer to increase their functionality. Furthermore, to confirm their biocompatibility, we also carried out cell viability assays for the Ag-NPs, Ag-NPrs, and Ag-NPrs@SiO2 with different concentrations at 62.5, 125, and 250 µg/mL after 12, 24, and 48 h of exposure time, respectively, on a regular African green monkey kidney cell line. The cell viability test results exemplified that the three silver nanostructures were toxic-free and suitable for further potential biological applications in the near future.

Spectroscopic characterization and photodynamic antimicrobial chemotherapy of phthalocyanine-silver triangular nanoprism conjugates when supported on asymmetric polymer membranes

Silver triangular nanoprisms were synthesized and conjugated to zinc (ZnPc) and indium (InPc) phthalocyanines prior to embedding in asymmetric membranes. Conjugation of nanoparticles increased triplet state and singlet oxygen quantum yields of the phthalocyanines as well as enhancing photodynamic antimicrobial chemotherapy (PACT) activity against bacteria (S. aureus). The ZnPc derivative showed higher PACT activity when compared to the InPc, possibly due to degradation of the latter in aqueous media.

Plasmon resonance in nanopatch antennas with triangular nanoprisms

We calculate scattering, absorption, and extinction spectra for triangular silver nanoprisms and plasmonic nanopatch antennas (NPAs). We demonstrate that for the nanopatch antennas involving nanoprisms with a lateral size of 40–120 nm absorption prevails over scattering. Plasmon resonance for the nanoprism in water and for the NPA is redshifted relative to that for the nanoprism in air. For a single NPA plasmon resonance is redshifted with increasing the nanoprism lateral dimensions, and blue-shifted with increasing its height. We provide a guideline to optimization of the NPA design with the NPAs involving 630 nm quantum dots taken as an illustrative example.

Green synthesis and characterization of gold triangular nanoprisms using extract of Juniperus communis L.

In this study, we report the green synthesis of gold nanoparticles (AuNPs) with the use of easily available, safe to handle juniper extract (Juniperus communis L.) as a reducing and stabilizer agent. The AuNPs were characterized by UV–Vis absorption spectroscopy, atomic force microscopy (AFM), and transmission electron microscopy (TEM). Their growth was examined by UV–Vis spectroscopy over 24 h during storage at room temperature. Absorption measurements showed that the plasmon resonance wavelength appears around 530 and 700 nm. Electron-dispersive X-ray analysis (EDX) and selected area electron diffraction (SAED) of AuNPs evidenced the presence of Au (fcc) phases. TEM analysis showed spherical AuNPs and gold triangular nanoprisms. Differences in size and shape of the AuNPs were observed. ATR–FTIR confirmed the typical functional groups of polyphenols and their oxidation products on the AuNPs’ surface.

A cost-effective nanoparticle-gap-film SERS sensor using graphene nanospacer by one-step transfer-free mechanical milling

To develop operative surface-enhanced Raman spectroscopy (SERS) sensors, nanostructures with high signal enhancement and ease of production are highly desired. The SERS-active nanoparticle-gap-film (NGF) sandwich substrate using graphene as the gap nanospacer is of particular interest due to its strong local field enhancement associated with the atomically thin graphene gap. However, the complexity in fabricating such nanostructures, especially the often involved high-temperature and vacuum processes, ultimately hampers practical applications. Here, a simple and low-cost SERS-active NGF sensor is demonstrated in which a graphene-based nanospacer was prepared by a one-step transfer-free mechanical milling process under amiable conditions. Notably, the milling process can readily produce and deposit the graphene nanospacer in a single fabrication step onto the desired metal substrates. To further enhance SERS performance, shape-anisotropic triangular silver nanoprisms were introduced into the NGF system, which offered enhanced Raman gain compared to spherical silver nanoparticles. Using Rhodamine 6G as the probe, the NGF SERS sensors exhibited a high sensitivity with a low detection limit of 5 × 10−9M with an enhancement factor of 2.7 × 105. This study opens up a new route for the facile production of cost-effective graphene-based NGF substrates for various SERS sensing applications.

Direct Imaging of Surface Plasmon-Driven Hot Electron Flux on the Au Nanoprism/TiO2.

Direct measurement of hot electron flux from a plasmonic Schottky nanodiode is important for obtaining fundamental insights explaining the mechanism for electronic excitation on a surface. Here, we report the measurement of photoinduced hot electrons on a triangular Au nanoprism on TiO2 under incident light with photoconductive atomic force microscopy (pc-AFM), which is direct proof of the intrinsic relation between hot electrons and localized surface plasmon resonance. We find that the local photocurrent measured on the boundary of the Au nanoprism is higher than that inside the Au nanoprism, indicating that field confinement at the boundary of the Au nanoprism acts as a hot spot, leading to the enhancement of hot electron flow at the boundary. Under incident illumination with a wavelength near the absorption peak (645 nm) of a single Au nanoprism, localized surface plasmon resonance resulted in the generation of a higher photoinduced hot electron flow for the Au nanoprism/TiO2, compared with that at a wavelength of 532 nm. We show that the application of a reverse bias results in a higher photocurrent for the Au nanoprism/TiO2, which is associated with a lowering of the Schottky barrier height caused by the image force. These nanoscale measurements of hot electron flux with pc-AFM indicate efficient photon energy transfer mediated by surface plasmons in hot electron-based energy conversion.

Plasmoelectronic-Based Ultrasensitive Assay of Tumor Suppressor microRNAs Directly in Patient Plasma: Design of Highly Specific Early Cancer Diagnostic Technology.

It is becoming understood that microRNAs hold great promise for noninvasive liquid biopsies for screening for different types of cancer, but current state-of-the-art RT-PCR and microarray techniques have sensitivity limitations that currently restrict their use. Herein, we report a new transduction mechanism involving delocalization of photoexcited conduction electrons wave function of gold triangular nanoprism (Au TNP) in the presence of -ssDNA/microRNA duplexes. This plasmoelectronic effect increases the electronic dimension of Au TNPs and substantially affects their localized surface plasmon resonance (LSPR) properties that together allow us to achieve a sensitivity for microRNA assay as low as 140 zeptomolar concentrations for our nanoplasmonic sensors. We show that the position of a single base-pair mismatch in the -ssDNA/microRNA duplex dramatically alters the LSPR properties and detection sensitivity. The unprecedentedly high sensitivity of nanoplasmonic sensors has allowed us to assay four different microRNAs (microRNA-10b, -182, -143, and -145) from bladder cancer patient plasma (50 μL/sample). For the first time, we demonstrate the utility of a label-free, nanoplasmonic sensor in quantification of tumor suppressor microRNAs, the level of tumor suppressor microRNAs goes down in a cancer patient as compared to normal healthy individuals, in metastatic and nonmetastatic bladder cancer patient plasma. Our statistical analysis of patient samples unequivocally suggests that the tumor suppressor microRNAs are more specific biomarkers ( p-value of <0.0001) than oncogenic microRNAs for differentiation between metastatic and nonmetastatic bladder cancer, and nonmetastatic cancer from healthy individuals. This work demonstrating the electron wave functions delocalization dependent ultrasensitive LSPR properties of noble metal nanoparticles has a great potential for fabrication of miniaturized and extremely powerful sensors to investigate microRNA properties in other cancers (for example breast, lung, and pancreatic) through liquid biopsy.

PH-controlled growth of triangular silver nanoprisms on a large scale.

A simple, mild, and reproducible one-pot approach was developed to synthesize triangular silver nanoprisms (TSNPRs) on a large scale. The TSNPR size was tailored from 30 to 100 nm by varying the dosage of a sodium hydroxide pentanol solution in the water/polyvinylpyrrolidone/n-pentanol ternary system. The use of the sodium hydroxide pentanol solution modified the initial pH of the water/polyvinylpyrrolidone/n-pentanol system and made the synthesis of TSNPRs highly reproducible and independent of the polyvinylpyrrolidone pH. N,N-dimethyl formamide and formamide were used to control the system pH and improved the resultant TSNPRs in both syntheses repeatedly to have a well-defined shape. The extinction bands of the TSNPRs were relatively narrow, which makes them promising for chemical and biological applications.

Plasmon-enhanced two-photon excitation fluorescence of rhodamine 6G and an Eu-diketonate complex by a picosecond diode laser.

Two-photon excited fluorescence (TPEF) of rhodamine 6G (Rh6G) and tris(dibenzoylmethane) mono(5-aminophenanthroline) europium (Eu-TDPA) was measured using a pulsed diode laser head (<45 mW, 975 nm, 90 ps pulse width, 40 MHz). Fluorophores were cast on a glass slide modified with triangular silver nanoprisms. A photon-counting photomultiplier detected the TPEF of Rh6G on a glass substrate (1361 Hz) and on the nanoprisms (6322 Hz). On the other hand, Eu-TDPA did not exhibit TPEF on a glass substrate. TPEF was only observed when the extinction of the nanoprisms on the substrates was larger than 0.1. The nanoprisms enhanced the TPEF of these two fluorophores up to the detectable level using a low-power laser diode.

Melamine detection in liquid milk based on selective porous polymer monolith mediated with gold nanospheres by using surface enhanced Raman scattering.

A rapid and fast detection of trace amounts of melamine in milk is reported by using Gold Nano Spheres embedded monolith conjugates. Monolith was synthesized by the polymerization of Glycidyl Methacrylate (GMA) and Ethylene Dimethacrylate(EDMA) (cross linker and functional monomer), Cyclohexanol (Porogen formation) and 2, 2-Dimethoxy-2-phenyl-acetophenone (photo-initiator) on gold coated silicon wafer. In order to gauge the influence of monolith on SERS signal activity, three shapes of gold nanoparticles namely Gold Nano Spheres (GNSs), Gold Nanorods (GNRs) and Triangular Gold Nanoprisms (GNPrs) were immobilized on monolithic surface and analyzed by the signal molecule Rhodamine (R6G). The Raman Enhancement efficiency of the above three shapes incorporated with monolith was monitored by calculating their maximum enhancement factors. Among three morphologies, Gold Nano Spheres integrated in GMA-EDMA Monolith Sensor (GNS@GEMS) was found more effective for detection of R6G than two others and was therefore projected in analysis of melamine sensing in commercial milk. A linear relationship of regression model (R2 = 0.99) was observed between melamine SERS intensity (at 710 cm-1) and varied concentrations (6.5 < mg/L < 0.125). The lower limit of detection (LOD) and limit of quantification (LOQ) for melamine was determined 0.11 mg/L and 0.38 mg/L respectively. The time window for detection of melamine was 10 min and hence our method is compatible with the FDA's tolerance limit in USA and China (1 mg/L).

Direct imaging of Indium-rich triangular nanoprisms self-organized formed at the edges of InGaN/GaN core-shell nanorods

Higher indium incorporation in self-organized triangular nanoprisms at the edges of InGaN/GaN core-shell nanorods is directly evidenced by spectral cathodoluminescence microscopy in a scanning transmission electron microscope. The nanoprisms are terminated by three 46 nm wide a-plane nanofacets with sharp interfaces forming a well-defined equilateral triangular base in the basal plane. Redshifted InGaN luminescence and brighter Z-contrast are resolved for these structures compared to the InGaN layers on the nanorod sidewalls, which is attributed to at least 4 % higher indium content. Detailed analysis of the inner optical and structural properties reveals luminescence contributions from 417 nm up to 500 nm peak wavelength proving the increasing indium concentration inside the nanoprism towards the nanorod surface.

Corrigendum to “Nanoporous Ag-Au Bimetallic Triangular Nanoprisms Synthesized by Galvanic Replacement for Plasmonic Applications”

Corrigendum to “Nanoporous Ag-Au Bimetallic Triangular Nanoprisms Synthesized by Galvanic Replacement for Plasmonic Applications”

Heteroepitaxy of Fin-Shaped InGaN Nanoridge Using Molecular Beam Epitaxy

We have demonstrated a well-ordered In-rich single crystalline InGaN nanoridge array grown on GaN/sapphire substrate using the integration of top-down etching and bottom-up molecular beam epitaxy. During the initial growth of InGaN on a patterned GaN/sapphire substrate, a (1011) r-plane predominantly forms, suppressing the growth in [1011] crystal direction and resulting in a triangular InGaN nanoprism. As the growth proceeds further, a narrow (∼50 nm) single-crystal fin-shaped InGaN nanoridge forms atop the InGaN nanoprism structure. The resulting narrow fin-shaped InGaN nanoridge structure shows extremely strong photoluminescence (PL) intensity with a center wavelength at 524–560 nm and narrow distribution compared to the epitaxially grown planar InGaN layer or InGaN nanowire. High-resolution scanning transmission electron microscopy (STEM) combined with an energy-dispersive X-ray (EDS) map reveals that a sharply faceted single-crystal InGaN nanoridge (∼50 nm width) forms along the top of each InGaN n...

Plasma resonance of nanopatch antennas with triangular nanoprisms

In the last few years, a great interest has attracted structures called plasmonic nanopatch antennas (PNA). As a rule, the nanopatch antenna consists of a metallic nanoparticle located above the metal surface and separated from it by a layer of dielectric. In PNA, significant amplification of local electromagnetic fields is possible, which allows reaching high densities of the local electronic states of the emitter placed inside the PNA. In such structures it is possible to achieve the Purcell factor of the order of 103, which gives an advantage to PNA in comparison with dielectric one, where the Purcell factor is several units. High Purcell factor allows to create sources of single photons with a frequency of up to 100 GHz. In this paper, calculations of plasmon resonance dependences on various structure parameters on the example of PNA with a triangular silver nanoprism are carried out.

Nanoporous Ag-Au Bimetallic Triangular Nanoprisms Synthesized by Galvanic Replacement for Plasmonic Applications

Galvanic replacement is a versatile method of converting simple noble metallic nanoparticles into structurally more complex porous multimetallic nanostructures. In this work, roughened nanoporous Ag-Au bimetallic triangular nanoprisms (TNPs) are synthesized by galvanic replacement between smooth Ag triangular plates and AuCl4− ions. Transmission electron microscope and the elementary mapping measurements show that numerous protrusions and pores are formed on the {111} facets, and Ag and Au atoms are homogeneously distributed on the triangular plates. Due to the additional “hot spots” generated by the surface plasmon coupling of the newly formed protrusions and pores, the roughened nanoporous Ag-Au TNP aggregates demonstrate a higher surface-enhanced Raman scattering enhancement factor (seven times larger) and better reproducibility than that of smooth Ag triangular particle aggregates. These synthesized roughened nanoporous Ag-Au bimetallic TNPs are a promising candidate for the applications in analytical chemistry, biological diagnostics, and photothermal therapy due to their excellent plasmonic performances and good biocompatibility.

One-pot synthesis of Au@Pt star-like nanocrystals and their enhanced electrocatalytic performance for formic acid and ethanol oxidation

The current bottleneck facing further developments in fuel cells is the lack of durable electrocatalysts with satisfactory activity. In this study, a simple and fast one-pot wet-chemical method is proposed to synthesize novel Au@Pt star-like bimetallic nanocrystals (Au@Pt SLNCs) with a low Pt/Au ratio of 1:4, which show great electrocatalytic properties and outstanding stability toward the electro-oxidation reactions commonly found in fuel cells. The star-like Au core (90 ± 20 nm) is partially coated with 5 nm Pt nanocluster shells, a morphology which creates a large amount of boundaries and edges, thus tuning the surface electronic structure as demonstrated by X-ray photoelectron spectroscopy and CO-stripping measurements. This promotes excellent electrocatalytic performance towards the formic acid oxidation reaction in acidic media and the ethanol oxidation reaction in alkaline media, compared to commercial Pt or Au@Pt triangular nanoprisms, in which the Au core is fully coated by a Pt shell. Au@Pt SLNCs have the highest current density within the dehydrogenation potential range, needing the least potential to achieve a certain current density as well as the highest long-term stability. Because of the small amount of Pt usage, very fast synthesis, excellent electrocatalytic activity and durability, the proposed Au@Pt SLNCs have a promising practical application in fuel cells.

Colorimetric and fluorometric determination of uric acid based on the use of nitrogen-doped carbon quantum dots and silver triangular nanoprisms.

A dual-read detection system is described for non-enzymatic and non-aggregation based analysis of uric acid (UA). Silver triangular nanoprisms (AgTNPs) were used as colorimetric probes, while the reduction in the fluorescence of nitrogen-doped carbon quantum dots (N-CQDs) served as the fluorometric readout. The absorption band of the AgTNPs overlaps the emission band of N-CQDs (with a peak at 440nm). Therefore, fluorescence is reduced owing to an inner filter effect. The AgTNPs are etched if exposed to H2O2, and round nanodiscs are formed. In the presence of UA, etching of the AgTNPs is suppressed because the facets of the AgTNPs are coated with UA. The absorbance, best measured at 683nm, increases with the concentration of the pre-added UA. The colorimetric assay works in the 0.1-45μM UA concentration range, and the fluorometric assay between 1 and 42μM of UA. The respective detection limits are 50 and 200nM, respectively. The probe can be used for direct visualization of UA. The method was successfully applied to the determination of UA in urine samples. Graphical abstract The fluorescence of nitrogen-doped carbon quantum dots (N-CQDs) is quenched by AgTNPs (silver triangular nanoprisms). As the AgTNPs are etched by H2O2, fluorescence recovers in the system after H2O2 is added, and alsoundergoes a color change. Uric acid (UA) protects the AgTNPs from etching because the facets of the AgTNPs are coated with UA. The fluorescence of N-CQDs decreases. Thus, a dual-read probe is developed for determination of UA.