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Asymmetric gold nanoparticles synthesized in the presence of maltose-modified poly(ethyleneimine)
(2012)
A self-assembled tube-like network, spontaneously formed by adding maltose-modified poly(ethyleneimine) (mal-PEI5000) to mixed phospholipid vesicles, can be used as a template for the formation of gold nanoparticles. High resolution TEM indicates that the growing process leads not only to the formation of spherical gold nanoparticles with an absorption maximum at 520 nm, but also very flat triangles, hexagons, and long bent rods are formed, revealing an absorption maximum in the NIR at about 850 nm.
One can conclude that nanorods, nanotriangles and nanohexagons are predominantly formed in the tubular network structure.
Fluorescent gold clusters synthesized in a poly(ethyleneimine) modified reverse microemulsion
(2013)
This paper is focused on the formation of gold clusters in a tailor-made polyelectrolyte-modified reverse microemulsion using poly(ethyleneimine) (PEI) as a cationic polyelectrolyte. PEI incorporated into a ternary w/o microemulsion consisting of water/heptanol/zwitterionic surfactant 3-(N,N-dimethyl-dodecylammonio)-propanesulfonate (SB) acts as a reducing and stabilizing agent and shows an additional template effect. The nanoparticle synthesis is performed by a simple mixing of two microemulsions, one containing the PEI and the other one containing the gold chloride precursor. UV-vis measurements in the microemulsion show two pronounced absorption maxima, one at 360 nm and the other one at 520 nm, indicating two particle fractions. The absorption maximum at 360 nm in combination to the unique fluorescence properties indicate the formation of gold clusters. After a complete solvent evaporation the redispersed nanoparticles have been characterized by using UV-vis and fluorescence spectroscopy, in combination to dynamic light scattering and transmission electron microscopy (TEM). In addition to the gold nanoparticle fraction (>5 nm) the fluorescent gold cluster fraction (<2 nm) can be redispersed without particle aggregation. By means of asymmetric flow field flow fractionation (AF-FFF) two different cluster fractions with particle diameter (<2 nm) can be identified.
This Letter is focused on the one-pot formation of CdS nanoparticles in aqueous medium in presence of polyethyleneimine (PEI). Quantum dots can be obtained by adding a pre-cooled aqueous Na2S solution to a pre-cooled aqueous CdCl2 solution dropwise in presence of PEI.
Field flow fractionation in combination with TEM experiments show a time dependent agglomeration of individual quantum dots from 1.6 nm up to 3.2 nm in size. The hyperbranched PEI of moderate molar mass (>20000 g/mol) is an excellent polymer to prevent a further increase of the particle size. Therefore, stable fluorescent PEI-capped CdS quantum dots are available.
By dropping a NaH2PO4 center dot H2O precursor solution to a CaCl2 solution at 90 degrees C under continuous stirring in presence of two biopolymers, i.e. gelatin (G) and chitosan (C), supramolecular calcium phosphate (CP) card house structures are formed. Light microscopic investigations in combination with scanning electron microscopy show that the GC-based flower-like structure is constructed from very thin CP platelets. Titration experiments indicate that H-bonding between both biopolymers is responsible for the synergistic effect in presence of both polymers. Gelatin chitosan water complexes play an important role with regard to supramolecular ordering. FTIR spectra in combination with powder X-ray diffraction show that after burning off all organic components (heating up >600 degrees C) dicalcium and tricalcium phosphate crystallites are formed. From high resolution transmission electron microscopy (HR-TEM) it is obvious to conclude, that individual crystal platelets are dicalcium phosphates, which build up ball-like supramolecular structures. The results reveal that the GC guided crystal growth leads to nano-porous supramolecular structures, potentially attractive candidates for bone repair. (c) 2015 Elsevier B.V. All rights reserved.
This paper focused on the synthesis of triangular nanoplatelets in the presence of a tubular network structure. The tubular network structure is formed by adding a strongly alternating polyampholyte, i.e., PalPhBisCarb, to a mixed vesicle system with a negatively charged bilayer containing phosphatidylcholin and AOT. Using the tubular network as a reducing agent in a one-step procedure, triangular and hexagonal nanoplatelets are formed. One can show that the nanoplatelet yield is enhanced by increasing the temperature and decreasing the reaction time. The platelet edge length can be decreased by heating the system up to 100 A degrees C. Due to specific interactions between PalPhBisCarb and the AOT/phospholipid bilayer, stacking and welding effects lead to the formation of ordered platelet structures. The reaction pathway to flat gold nanotriangles is discussed with regard to the twin plane growth model of gold nanoplates.
Polyplexes between Salmon DNA and non-modified hyperbranched poly(ethyleneimines) of varying molar mass, i.e., PEI(5 k) with 5000 g/mol and PEI(25 k) with 25,000 g/mol, and modified PEI(5 k) with maltose units (PEI-Mal) were investigated in dependence on the molar N/P ratio by using dynamic light scattering (DLS), zeta potential measurements, micro differential scanning calorimetry (mu-DSC), scanning-transmission electron microscopy (STEM), and cryo-scanning electron microscopy (cryo-SEM). A reloading of the polyplexes can be observed by adding the unmodified PEI samples of different molar mass. In excess of PEI a morphological transition from core-shell particles (at N/P 8) to loosely packed onion-like polyplexes (at N/P 40) is observed. The shift of the DSC melting peak from 88 degrees C to 76 degrees C indicates a destabilization of the DNA double helix due to the complexation with the unmodified PEI. Experiments with the maltose-modified PEI show a reloading already at a lower N/P ratio. Due to the presence of the sugar units in the periphery of the polycation electrostatic interactions between DNA become weaker, but cooperative H-bonding forces are reinforced. The resulting less-toxic, more compact polyplexes in excess of the PEI-Mal with two melting points and well distributed DNA segments are of special interest for extended gene delivery experiments. (C) 2015 Elsevier B.V. All rights reserved.
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.
Polyplexes, composed of Salmon DNA and very small gold nanoparticles embedded into a dendritic glycopolymer architecture of sugar-modified poly(ethyleneimine) (PEI-Mal) with a molar mass of about 25,000 g/mol, were characterized by dynamic light scattering (DLS), zeta potential measurements, micro differential scanning calorimetry (mu-DSC) and transmission electron microscopy (TEM). The PEI-Mal-entrapped gold nanoparticles of about 2 nm in diameter influence the polyplex formation of the hyperbranched PEI containing bulky maltose, and in consequence the DNA is more compactized in the inner part of spherical polyplex particles of about 150 nm in diameter. The resulting more compact core shell polyplex particles with embedded gold nanoparticles in the outer polymer shell will be used as components in forthcoming gene delivery experiments. (C) 2017 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.
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.
Hypothesis: Bimetallic magnetite-gold nanostructures are interesting candidates to combine and enhance individual properties of each metal element in catalytic and analytical applications. Microemulsions have been employed in templated synthesis of nanoparticles, and their combination with different types of nanoparticles can further mediate interactions at the water-oil interface, providing new forms of hybrid nanostructures.
Experiments: Reverse water-in-oil microemulsions of droplet sizes below 50 nm were prepared from ternary mixtures of Aerosol-OT (AOT) as surfactant, incorporating 4 nm sized superparamagnetic nanoparticles (MNPs) to the hexane-pentanol oil phase and 5 nmsized polyethyleneimine-stabilized gold nanoparticles (Au(PEI)-NPs) to the water phase. The resulting isotropic L-2 phase, Winsor phases and organized nanostructures were investigated using conductometry, calorimetry, UV-Vis spectroscopy, cryoSEM and HRTEM.
Findings: Droplet-droplet interactions, morphology and surfactant film properties of AOT microemulsions could be modulated in different ways by the presence of the different nanoparticles from each liquid phase. Additionally, phase separation into Winsor phases allows the formation upon solvent evaporation of films with bimetallic heterostructures on the micrometer scale. This demonstrates a new way of nanoparticle templated assembly at liquid interfaces by assisted interactions between microemulsions and nanoparticles, as a promising strategy to obtain thin films of small, isotropic nanoparticles with hierarchical ordering.