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The mechanism of nanotriangle formation in multivesicular vesicles (MMV) is investigated by using time-dependent SAXS measurements in combination with UV-vis spectroscopy, light, and transmission electron microscopy. In the first time period 6.5 nm sized spherical gold nanoparticles are formed inside of the vesicles, which build up soft nanoparticle aggregates. a) In situ SAXS experiments show a linear increase of the volume and molar mass of nanotriangles in the second time period. The volume growth rate of the triangles is 16.1 nm(3)/min, and the growth rate in the vertical direction is only 0.02 nm/min. Therefore, flat nanotriangles with a thickness of 7 nm and a diameter of 23 nm are formed. This process can be described by a diffusion limited Ostwald ripening growth mechanism. TEM micrographs visualize soft coral-like structures with thin nanoplatelets at the periphery of the aggregates, which disaggregate in the third time period into nanotriangles and spherical particles. The 16 times faster growth of nanotriangles in the lateral than that in the vertical direction is related to the adsorption of symmetry breaking components, i.e., AOT and the polyampholyte PalPhBisCarb, on the {111} facets of the gold nanoplatelets in combination with confinement effects of the vesicular template phase.
The aim of this study was to develop a one-step synthesis of gold nanotriangles (NTs) in the presence of mixed phospholipid vesicles followed by a separation process to isolate purified NTs. Negatively charged vesicles containing AOT and phospholipids, in the absence and presence of additional reducing agents (polyampholytes, polyanions or low molecular weight compounds), were used as a template phase to form anisotropic gold nanoparticles. Upon addition of the gold chloride solution, the nucleation process is initiated and both types of particles, i.e., isotropic spherical and anisotropic gold nanotriangles, are formed simultaneously. As it was not possible to produce monodisperse nanotriangles with such a one-step procedure, the anisotropic nanoparticles needed to be separated from the spherical ones. Therefore, a new type of separation procedure using combined polyelectrolyte/micelle depletion flocculation was successfully applied. As a result of the different purification steps, a green colored aqueous dispersion was obtained containing highly purified, well-defined negatively charged flat nanocrystals with a platelet thickness of 10 nm and an edge length of about 175 nm. The NTs produce promising results in surface-enhanced Raman scattering.
Watching the Vibration and Cooling of Ultrathin Gold Nanotriangles by Ultrafast X-ray Diffraction
(2016)
We study the vibrations of ultrathin gold nanotriangles upon optical excitation of the electron gas by ultrafast X-ray diffraction. We quantitatively measure the strain evolution in these highly asymmetric nano-objects, providing a direct estimation of the amplitude and phase of the excited vibrational motion. The maximal strain value is well reproduced by calculations addressing pump absorption by the nanotriangles and their resulting thermal expansion. The amplitude and phase of the out-of-plane vibration mode with 3.6 ps period dominating the observed oscillations are related to two distinct excitation mechanisms. Electronic and phonon pressures impose stresses with different time dependences. The nanosecond relaxation of the expansion yields a direct temperature sensing of the nano-object. The presence of a thin organic molecular layer at the nanotriangle/substrate interfaces drastically reduces the thermal conductance to the substrate.
The Marangoni contraction of sessile drops of a binary mixture of a volatile and a nonvolatile liquid has been investigated experimentally and theoretically. The origin of the contraction is the locally inhomogeneous evaporation rate of sessile drops. This leads to surface tension gradients and thus to a Marangoni flow. Simulations show that the interplay of Marangoni flow, capillary flow, diffusive transport, and evaporative losses can establish a quasistationary drop profile with an apparent nonzero contact angle even if both liquid components individually wet the substrate completely. Experiments with different solvents, initial mass fractions, and gaseous environments reveal a previously unknown universal power-law relation between the apparent contact angle and the relative undersaturation of the ambient atmosphere: theta(app) similar to (RHeq - RH)(1/3). This experimentally observed power law is in quantitative agreement with simulation results. The exponent can also be inferred from a scaling analysis of the hydrodynamic-evaporative evolution equations of a binary mixture of liquids with different volatilities.
We report ultrasonically generated pH-responsive Pickering Janus emulsions of olive oil and silicone oil with controllable droplet size and engulfment. Chitosan was used as a pH-responsive emulsifier. The increase of pH from 2 to 6 leads to a transition from completely engulfed double emulsion droplets to dumbbell-shaped Janus droplets accompanied by a significant decrease of droplet diameter and a more homogeneous size distribution. The results can be elucidated by the conformational change of chitosan from a more extended form at pH 2 to a more flexible form at pH 4-5. Magnetic responsiveness to the emulsion was attributed by dispersing superparamagnetic nanoparticles (Fe3O4 with diameter of 13 +/- 2 nm) in the olive oil phase before preparing the Janus emulsion. Incorporation of magnetic nanoparticles leads to superior emulsion stability, drastically reduced droplet diameters, and opened the way to control movement and orientation of the Janus droplets according to an external magnetic field.
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. (C) 2018 Elsevier B.V. All rights reserved.
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 degrees 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 similar to 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.
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 X 10(5), which can be related to the silver hot spots at the periphery of the undulated gold nanoplatelets.
A one-step moderate energy vibrational emulsification method was successfully employed to produce thermo-responsive olive/silicone-based Janus emulsions stabilized by poly(N,N-diethylacrylamide) carrying 0.7 mol% oleoyl side chains. Completely engulfed emulsion droplets remained stable at room temperature and could be destabilized on demand upon heating to the transition temperature of the polymeric stabilizer. Time-dependent light micrographs demonstrate the temperature-induced breakdown of the Janus droplets, which opens new aspects of application, for instance in biocatalysis.
Due to the enhanced electromagnetic field at the tips of metal nanoparticles, the spiked structure of gold nanostars (AuNSs) is promising for surface-enhanced Raman scattering (SERS). Therefore, the challenge is the synthesis of well designed particles with sharp tips. The influence of different surfactants, i.e., dioctyl sodium sulfosuccinate (AOT), sodium dodecyl sulfate (SDS), and benzylhexadecyldimethylammonium chloride (BDAC), as well as the combination of surfactant mixtures on the formation of nanostars in the presence of Ag⁺ ions and ascorbic acid was investigated. By varying the amount of BDAC in mixed micelles the core/spike-shell morphology of the resulting AuNSs can be tuned from small cores to large ones with sharp and large spikes. The concomitant red-shift in the absorption toward the NIR region without losing the SERS enhancement enables their use for biological applications and for time-resolved spectroscopic studies of chemical reactions, which require a permanent supply with a fresh and homogeneous solution. HRTEM micrographs and energy-dispersive X-ray (EDX) experiments allow us to verify the mechanism of nanostar formation according to the silver underpotential deposition on the spike surface in combination with micelle adsorption.
This work describes the synthesis of hybrid particles of gold nanotriangles (AuNTs) with magnetite nanoparticles (MNPs) by using 1-mercaptopropyl-3-trimethoxysilan (MPTMS) and L-cysteine as linker molecules. Due to the combination of superparamagnetic properties of MNPs with optical properties of the AuNTs, nanoplatelet-satellite hybrid nanostructures with combined features become available. By using MPTMS with silan groups as linker molecule a magnetic "cloud" with embedded AuNTs can be separated. In presence of L-cysteine as linker molecule at pH > pH(iso) a more unordered aggregate structure of MNPs is obtained due to the dimerization of the L-cysteine. At pH < pH(iso) water soluble positively charged AuNTs with satellite MNPs can be synthesized. The time-dependent loading with MNP satellites under release of the extinction and magnetization offer a hybrid material, which is of special relevance for biomedical applications and plasmonic catalysis.
By adding hyaluronic acid (HA) to dioctyl sodium sulfosuccinate (AOT)-stabilized gold nanotriangles (AuNTs) with an average thickness of 7.5 +/- 1 nm and an edge length of about 175 +/- 17 nm, the AOT bilayer is replaced by a polymeric HA-layer leading to biocompatible nanoplatelets. The subsequent reduction process of tetrachloroauric acid in the HA-shell surrounding the AuNTs leads to the formation of spherical gold nanoparticles on the platelet surface. With increasing tetrachloroauric acid concentration, the decoration with gold nanoparticles can be tuned. SAXS measurements reveal an increase of the platelet thickness up to around 14.5 nm, twice the initial value of bare AuNTs. HRTEM micrographs show welding phenomena between densely packed particles on the platelet surface, leading to a crumble formation while preserving the original crystal structure. Crumbles crystallized on top of the platelets enhance the Raman signal by a factor of around 20, and intensify the plasmon-driven dimerization of 4-nitrothiophenol (4-NTP) to 4,4 '-dimercaptoazobenzene in a yield of up to 50 %. The resulting crumbled nanotriangles, with a biopolymer shell and the absorption maximum in the second window for in vivo imaging, are promising candidates for biomedical sensing.