Gold Nanotriangles Research Articles

Green Synthesis of Gold Nanoparticles Using Three Medicinal Plant Extracts as Efficient Reducing Agents

The aim of this work is a green synthesis of gold nanoparticles using the aqueous extract of Anthriscus sylvestris, Ferula gummosa, and Achillea eriohora leaf and stems as the reducing agents. The effects of reducing agent concentration in the reaction mixture and temperature on the size of the gold nanotriangles were studied. The nanoparticles were characterized using UV–Vis spectroscopy, XRD, and SEM. XRD studies show that the particles are crystalline in the cubic phase. However, the reduction of gold ions by plant extracts resulted in the formation of spherical gold nanoparticles with diameters from 18 to 56 nm.

Effect of gold nanoparticle shape on the photophysicochemical properties of sulphur containing metallophthalocyanines

In this work tetrakis–[(thiopheneethoxy) phthalocyaninato] zinc(II) (1), tetrakis–[(thiopheneethoxy) phthalocyaninato] indium (II) chloride (2), tetrakis [(benzo [d]thiazol-2-yl phenoxy) phthalocyaninato] zinc(II) (3), and tetrakis [(benzo [d]thiazol-2-yl phenoxy)phthalocyaninato] indium (II) chloride (4) were linked to both gold nanospheres (AuNSs) and gold nanotriangles (AuNTs) via Au-S and Au-N (the latter for complexes 3 and 4 only) self assembly. The photophysicochemical behaviour of complexes and their conjugates were studied. The conjugates yielded improved triplet and singlet quantum yields, with nanospheres displaying better properties than nanotriangles. The conjugates with a benzothiazole phenoxy substituent also yielded better properties than their thiophene ethoxy counterpart. These conjugates especially those with a benzothiazole phenoxy substituent have potential as photosensitisers for photodynamic therapy applications.

Gold Nanotriangles as Selective Catalysts for Cyclohexanol and Cyclohexanone Production

The search for sustainable catalytic oxidation processes remains a challenge. One process of utmost industrial and economic importance is the selective oxidation of cyclohexane, in the route of nylon-6,6 production, which requires urgent improvement. Herein, Au nanotriangles (Au NTs) were prepared following a three-step (seed preparation, growth and shaping) procedure and applied, for the first time, as catalysts for the selective oxidation of neat cyclohexane to ketone and alcohol (KA) oil (cyclohexanol and cyclohexanone mixture). The Au NTs successfully yield KA oil (up to 14%) under mild conditions (50 °C), using an alternative energy source (microwave irradiation) as reaction promotor.

Tunable metallic nanostructures using 3D printed nanosphere templates

The use of two-photon 3D printing to create templates for fabricating reproducible and tunable metallic nanostructures is described. The approach allows the structure of the template to be designed specifically for particular applications, e.g., fluid flow control, surface enhanced Raman spectroscopy, metal enhanced fluorescence etc. Here, we show that this method offers excellent control of the size, pitch and packing of spheres on both conducting and insulating substrates, unlike nanosphere lithography. Gold is deposited through these templates and the template then removed using a plasma etching method. In this way, gold nanotriangles, nanodiamonds and nanocavities have been created and characterized using SEM to determine the accuracy of the structures compared to the software designs.

Monolayer and thin h–BN as substrates for electron spectro-microscopy analysis of plasmonic nanoparticles

The influence of four substrates [thin Si3N4, few-layer graphene (FLG), thin h–BN, and monolayer h–BN] on plasmon resonances of metallic nanoparticles was studied using electron energy loss spectroscopy. The h–BN monolayer is an excellent substrate for the study of plasmonic particles due to its large bandgap, negligible charging under electron irradiation, and negligible influence on the plasmon resonance full width at half maximum and peak positions. These effects were evidenced in experiments with gold nanotriangles focusing on dipolar modes. Nanotriangles on h–BN exhibit the lowest influence from the substrate compared to Si3N4 and FLG. In a dataset containing 23 triangles of similar sizes, the dipolar mode was found to have smaller redshifts, sharper peak widths, and higher resonance quality factors on h–BN, showing that it has nearly no effect on the plasmon absorption properties, provided that it is free from carbon contamination. However, light emission (cathodoluminescence) decreases as a function of electron irradiation for triangles on h–BN, even though the electron energy loss signal stays unchanged. This indicates the creation of non-radiative decay channels.

Plasmonic Enhancement of NIR to UV Upconversion by a Nanoengineered Interface Consisting of NaYF4:Yb,Tm Nanoparticles and a Gold Nanotriangle Array for Optical Detection of Vitamin B12 in Serum.

A nanoengineered interface fabricated by self-assembly enables the online determination of vitamin B12 via a simple luminescence readout in serum without any pretreatment. The interplay of Tm3+-doped NaYF4 nanoparticles (UCNPs) and a gold nanotriangle array prepared by nanosphere lithography on a glass slide is responsible for an efficient NIR to UV upconversion. Hot spots of the gold assembly generate local electromagnetic-field enhancement, favoring the four-photon upconversion process at the low-power excitation of approximately 13 W·cm-2. An improvement by about 6 times of the intensity for the emission peaking at 345 nm is achieved. The nanoengineered interface has been applied in a proof-of-concept sensor for vitamin B12 in serum, which is known as a marker for the risk of cancer; Alzheimer disease; or, during pregnancy, neurological abnormalities in newborn babies. Vitamin B12 can be detected in serum down to 3.0 nmol·L-1 by a simple intensity-based optical readout, consuming only 200 μL of a sample, which qualifies as easy miniaturization for point-of-care diagnostics. Additionally, this label-free approach can be used for long-term monitoring because of the high photostability of the upconversion nanoparticles.

Biological Synthesis of Gold Nanospheres and Nanotriangles

Biological Synthesis of Gold Nanospheres and Nanotriangles

The surface chemistry of near-infrared resonant gold nanotriangles obtained via thiosulfate synthesis

Gold nanoparticles with NIR absorption are promising for photothermal therapy applications. Different syntheses have been proposed and, among them, that based on the reduction of Au(III) with thiosulfate is important because it yields gold nanotriangles (AuNTs) with strong absorption in the near-infrared region. It has been previously reported by others that the nanoparticle surface is covered by relatively weak adsorbed S species (mostly sulfate), which would render the surface easy to functionalize in order to improve biocompatibility and therapeutic effects. In this work we have used XPS, XANES, UV–vis–NIR spectroscopy, HRTEM and AFM to demonstrate that, in contrast to the previous reports, these AuNTs are covered by strongly adsorbed sulfur species (sulfide and polysulfide). A reaction pathway is proposed to explain the presence of reduced sulfur species and the absence of adsorbed sulfates and thiosulfates. Preliminary cytotoxicity assays show that the S-capped AuNTs do not show a deleterious effect for Au concentrations larger than those needed for in vivo photothermal treatments.

In-Situ Deposition of Plasmonic Gold Nanotriangles and Nanoprisms onto Layered Hydroxides for Full-Range Photocatalytic Response towards the Selective Reduction of p-Nitrophenol

In this work, we present photocatalysis as a greener alternative to conventional catalysis where harsh reaction conditions, temperature and/or pressure are needed. Photodegradation of organic pollutants is a cost-effective, eco-friendly solution for the decontamination of water and air, and is a field that has been continuously growing over the last decade. Plasmonic metal nanoparticles absorb light irradiation that is transferred to the chemical reaction in a different fashion. Furthermore, plasmonic nanostructures can be combined with other materials, such as semiconductors or a basic support, to create hybrid systems capable of overcoming certain challenges that photocatalysis is facing nowadays and to expand the photocatalytic response towards the whole visible-near infrared (Vis-NIR) ranges. The main objective of this work has been to in-situ synthesize plasmonic anisotropic gold nanoparticles onto hydrotalcite (HT) and calcined hydrotalcite (CHT) supports by way of a sequential deposition-reduction (DR) process and to evaluate their efficiency as heterogeneous catalysts towards the selective oxidation of p-nitrophenol (hereafter 4-NP), a well-known model contaminant, either in the absence or the presence of full-range light irradiation sources (LEDs) spanning the whole UV-Vis-NIR range. Special attention has been paid to the optimization of the catalyst preparation parameters, including the pH and the concentration of reducing and stabilizing agents. Interestingly, the use of thermally modified hydrotalcites has enabled a strong metal-support interaction to induce the preferential formation of triangular-shaped Au nanoparticles with ca. 0.8 wt.% loading while increasing the colloidal stability and surface area of the catalyst with respect to the commercial untreated HT supports.

Systematic Investigation of the Wavelength-Dependent Upconversion Enhancement Induced by Single Plasmonic Nanoparticles

A convenient method was developed to systematically study the wavelength-dependent upconversion enhancement induced by single plasmonic nanoparticles to overcome unavoidable variations of nanoparticle geometry in practical synthesis techniques. Gold nanospheres and gold nanotriangles coupled to an upconversion nanoparticle monolayer were selected to compare emission and excitation resonance couplings, respectively. The emission intensity of a upconversion nanoparticle monolayer coupled with gold nanospheres (i.e., emission coupling) was found to be slightly lower than that of a reference upconversion nanoparticle monolayer, independent of pumping power. In turn, the emission intensity of a upconversion nanoparticle monolayer coupled with a gold nanotriangle (i.e., excitation coupling) showed an enhancement factor of the emission intensity of about 3.26 at low pumping power, which decreased to 0.48 at high pumping power because of a local heating effect. Our method could provide a convenient strategy for m...

Analysis of metallic nanoparticles embedded in thin film semiconductors for optoelectronic applications

This paper reports about a study of the local plasmonic resonance (LSPR) produced by metal nanoparticles embedded in a dielectric or semiconductor matrix. It is presented an analysis of the LSPR for different nanoparticle metals, shapes, and embedding media composition. Metals of interest for nanoparticle composition are Aluminum and Gold. Shapes of interest are nanospheres and nanotriangles. We study in this work the optical properties of metal nanoparticles diluted in water or embedded in amorphous silicon, ITO and ZnO as a function of size, aspect-ratio and metal type. Following the analysis based on the exact solution of the Mie theory and DDSCAT numerical simulations, it is presented a comparison with experimental measurements realized with arrays of metal nanospheres. Simulations are also compared with the LSPR produced by gold nanotriangles (Au NTs) that were chemically produced and characterized by microscope and optical measurements.

Passively Q-Switched Nd:YVO4 Laser Using a Gold Nanotriangle Saturable Absorber**Supported by the National Natural Science Foundation of China under Grant No 61475086, and the Natural Science Foundation of Shandong Province under Grant Nos ZR2015FM018 and ZR2014FM028.

A passively Q-switched Nd:YVO4 laser at 1064 nm is demonstrated based on a gold nanotriangle saturable absorber (GNT SA). Under a pump power of 3.82 W, the maximum average output power of 218 mW is achieved, corresponding to a slope efficiency of 12.9%. The minimum pulse width is 165 ns and the maximum pulse repetition rate is 300 kHz at the pump power of 3.48 W. Our results prove that the GNT SA is a promising saturable absorber for near-infrared lasers.

Gold nano-triangles as saturable absorbers for a dual-wavelength passively Q-switched Nd:GYSGG laser

In this paper, gold nano-triangles (GNTs) were used as saturable absorbers (SAs) in a dual-wavelength Nd:GYSGG laser for the first time, to our best knowledge. The maximum average output power was 75 mW with the shortest pulse width of 374 ns at pulse repetition rates of 250 kHz, corresponding to a single pulse energy of 300 nJ. The laser operated at dual wavelengths of 1059.6 and 1062.4 nm under a pump power of 8.5 W. Our work demonstrated that GNTs are promising SAs for Q-switching dual-wavelength solid state lasers.

Nanosecond-pulsed Q-switched Nd:YAG laser at 1064 nm with a gold nanotriangle saturable absorber

Gold nanotriangles (GNTs) were successfully employed as a saturable absorber (SA) to achieve passively Q-switched lasers for the first time. The performance of the Q-switched Nd:YAG laser at 1064 nm has been systematically investigated. The corresponding shortest pulsewidth, the threshold pump power and the maximum Q-switched average output power were 275.5 ns, 1.37 W, and 171 mW, respectively. To our knowledge, this is the shortest pulsewidth and the lowest threshold in a passively Q-switched laser at approximately 1.1 µm based on a gold nanoparticle SA (GNPs-SA). Our experimental results proved that the GNTs-SA can be used as a promising saturable absorber for nanosecond-pulsed lasers.

Toxicological investigations of "naked" and polymer-entrapped AOT-based gold nanotriangles.

Negatively charged ultrathin gold nanotriangles (AuNTs) were synthesized in a vesicular dioctyl sodium sulfosuccinate (AOT)/phospholipid-based template phase. These "naked" AuNTs with localized surface plasmon resonances in the NIR region at about 1300 nm and special photothermal properties are of particular interest for imaging and hyperthermia of cancerous tissues. For these kinds of applications the toxicity and the cellular uptake of the AuNTs is of outstanding importance. Therefore, this study focuses on the toxicity of "naked" AOT-stabilized AuNTs compared to polymer-coated AuNTs. Polymeric coating consisted of non-modified hyperbranched poly(ethyleneimine) (PEI), maltose-modified poly(ethyleneimine) (PEI-Mal) and heparin. The toxicological experiments were carried out with two different cell lines (embryonic kidney carcinoma cell line HEK293T and NK-cell leukemia cell line YTS). This study revealed that the heparin-coating of AuNTs improved biocompatibility by a factor of 50 when compared to naked AuNTs. Of note, the highest nontoxic concentration of the AuNTs coated with PEI and PEI-Mal is drastically decreased. Overall, this is mainly triggered by the different surface charges of polymeric coatings. Therefore, AuNTs coated with heparin were selected to carry out uptake studies. Their promising high biocompatibility and cellular uptake may open future studies in the field of biomedical applications.

Tuned Surface-Enhanced Raman Scattering Performance of Undulated Au@Ag Triangles

Negatively charged ultraflat gold nanotriangles (AuNTs) stabilized by the anionic surfactant dioctyl sodium sulfosuccinate (AOT) were reloaded with the cationic surfactant benzylhexadecyldimethylammonium chloride (BDAC). Because of the spontaneous formation of a catanionic AOT micelle/BDAC bilayer onto the surface of the reloaded AuNTs, a reduction of Ag+ ions leads to the formation of spherical silver nanoparticles (AgNPs). With increasing concentration of AgNPs on the AuNTs, the localized surface plasmon resonance (LSPR) is shifted stepwise from 1300 to 800 nm. The tunable LSPR enables to shift the extinction maximum to the wavelength of the excitation laser of the Raman microscope at 785 nm. Surface-enhanced Raman scattering (SERS) experiments performed under resonance conditions show an SERS enhancement factor of the analyte molecule rhodamine RG6 of 5.1 × 105, which can be related to the silver hot spots at the periphery of the undulated gold nanoplatelets.

Undulated Gold Nanoplatelet Superstructures: In Situ Growth of Hemispherical Gold Nanoparticles onto the Surface of Gold Nanotriangles.

Negatively charged flat gold nanotriangles, formed in a vesicular template phase and separated by an AOT-micelle-based depletion flocculation, were reloaded by adding a cationic polyelectrolyte, that is, a hyperbranched polyethylenimine (PEI). Heating the system to 100 °C in the presence of a gold chloride solution, the reduction process leads to the formation of gold nanoparticles inside the polymer shell surrounding the nanoplatelets. The gold nanoparticle formation is investigated by UV-vis spectroscopy, small-angle X-ray scattering, and dynamic light scattering measurements in combination with transmission electron microscopy. Spontaneously formed gold clusters in the hyperbranched PEI shell with an absorption maximum at 350 nm grow on the surface of the nanotriangles as hemispherical particles with diameters of ∼6 nm. High-resolution micrographs show that the hemispherical gold particles are crystallized onto the {111} facets on the bottom and top of the platelet as well as on the edges without a grain boundary. Undulated gold nanoplatelet superstructures with special properties become available, which show a significantly modified performance in SERS-detected photocatalysis regarding both reactivity and enhancement factor.

Seeded Growth Synthesis of Gold Nanotriangles: Size Control, SAXS Analysis, and SERS Performance.

We studied the controlled growth of triangular prismatic Au nanoparticles with different beveled sides for surface-enhanced Raman spectroscopy (SERS) applications. First, in a seedless synthesis using 3-butenoic acid (3BA) and benzyldimethylammonium chloride (BDAC), gold nanotriangles (AuNTs) were synthesized in a mixture with gold nanooctahedra (AuNOCs) and separated by depletion-induced flocculation. Here, the influence of temperature, pH, and reducing agent on the reaction kinetics was initially investigated by UV-vis and correlated to the size and yield of AuNT seeds. In a second step, the AuNT size was increased by seed-mediated overgrowth with Au. We show for the first time that preformed 3BA-synthesized AuNT seeds can be overgrown up to a final edge length of 175 nm and a thickness of 80 nm while maintaining their triangular shape and tip sharpness. The NT morphology, including edge length, thickness, and tip rounding, was precisely characterized in dispersion by small-angle X-ray scattering and in dry state by transmission electron microscopy and field-emission scanning electron microscopy. For sensor purposes, we studied the size-dependent SERS performance of AuNTs yielding analytical enhancement factors between 0.9 × 104 and 5.6 × 104 and nanomolar limit of detection (10-8-10-9 M) for 4-mercaptobenzoic acid and BDAC. These results confirm that the 3BA approach allows the fabrication of AuNTs in a whole range of sizes maintaining the NT morphology. This enables tailoring of localized surface plasmon resonances between 590 and 740 nm, even in the near-infrared window of a biological tissue, for use as colloidal SERS sensing agents or for optoelectronic applications.

Q-switched Nd:GdVO4 laser based on gold nanotriangles saturable absorbers

The saturable absorption properties of gold nanotriangles (GNTs) around 1 μm were investigated in a passively Q-switched Nd:GdVO4 lasers. With the GNTs film as the saturable absorber (SA), the shortest pulse width of 237.5 ns was achieved at the transmittance of 4% (T = 4%) under the pump power of 2.4 W with the average output power of 136.7 mW and maximum pulse repetition rates of 190 kHz, while the shortest pulse width was 268.6 ns at T = 10.8% under the pump power of 3.7 W, corresponding to the average output power and maximum pulse repetition rates of 191.5 mW and 200 kHz, respectively. These results indicated a great potential of the GNTs film as SA in the near-infrared region.

Interplay of Nanoparticle Resonance Frequency and Array Surface Coverage in Live-Cell Plasmon-Enhanced Single-Molecule Imaging

Super-resolution imaging has provided new insights into nanoscale optics. Plasmonic gold nanotriangle arrays created by nanosphere lithography can enhance single-molecule fluorescence intensity to further improve imaging. Here, gold nanotriangle arrays on glass coverslips were used as inexpensive, facile, and broadly applicable imaging substrates for living Vibrio cholerae cells expressing photoactivatable fluorescent proteins—the red PAmCherry or the green PAGFP—and resulted in fluorescence enhancements upon coupling living cells to nanotriangle arrays. Within the requirements for this wide-field coupling geometry, we analyze and optimize the coupling as a function of local surface plasmon resonance frequency and particle coverage.