Molecular dynamics simulations of the freezing of gold nanoparticles

A set of molten gold clusters, each with 1157 gold atoms, was studied by molecular dynamics simulations as the clusters underwent freezing at three different temperatures. Most of the clusters attained an icosahedral structure upon freezing, a structure found to be stable to mild annealing. Other structures observed were imperfect truncated decahedral, truncated octahedral and hexagonal close packed structures. The role of kinetics in the process of cluster solidification is discussed. Received 6 November 2000     

Surface property modification of well-dispersed amphiphilic gold nanoparticles as individuals

Amphiphilic gold nanoparticles (AuNPs) functionalized with mixed monolayers consisting of hydrophobic and hydrophilic ligands find widespread applications in biosensing, drug delivery, and bioimaging. One important aspect of amphiphilic AuNPs in such applications is the tuning of the surface properties of these AuNPs by modifying the composition of the ligands. In this study, well-dispersed AuNPs as individuals with mixed monolayers of hydrophobic and hydrophilic ligands were synthesized and the ratios of hydrophilic and hydrophobic ligands on the AuNP surfaces with varying ligand lengths were investigated by electrostatic titration. We demonstrated that longer hydrophobic ligands have higher affinity for the AuNP surface, and that the relative ligand length plays an important role in determining the maximum hydrophobic coverage on the AuNP surface at which the ratio of the amount of hydrophobic to that of hydrophilic ligands on the AuNP surface is the largest, for AuNPs to remain as individuals. We expect that the AuNPs synthesized with diverse ratios of hydrophobic and hydrophilic ligands on the surface can be useful in biological applications.

Open image in new window

Graphical abstract ?

     

Surface bubble nucleation stability

Recent research has revealed several different techniques for nanoscopic gas nucleation on submerged surfaces, with findings seemingly in contradiction with each other. In response to this, we have systematically investigated the occurrence of surface nanobubbles on a hydrophobized silicon substrate for various different liquid temperatures and gas concentrations, which we controlled independently. We found that nanobubbles occupy a distinct region of this parameter space, occurring for gas concentrations of approximately 100%-110%. Below the nanobubble region we did not detect any gaseous formations on the substrate, whereas micropancakes (micron wide, nanometer high gaseous domains) were found at higher temperatures and gas concentrations. We moreover find that supersaturation of dissolved gases is not a requirement for nucleation of bubbles.     

Melting, freezing and nucleation in nanoclusters of potassium chloride

Molecular dynamics simulations of the melting, freezing and nucleation are presented for unconstrained nanoclusters of KCl with a number of ions between 512 and 10648. The maximum extent of the probed liquid supercooling is analysed to the light of theoretical predictions and compared with experimental data. The fraction of the solid-like ions in the supercooled liquid is used as an indicator of heterogeneities within the liquid. Induced nucleation by seeding the supercooled liquid indicates that solid-liquid coexistence is stable, and sustained during the lifetime of the clusters, relatively to the supercooled liquid. A phenomenological analysis on the relaxation times of the crystal growth process is made. Critical nuclei sizes computed from the effectiveness of the seeds in the heterogeneous nucleation of the supercooled liquid, and from the residual crystallites in clusters not totally melted, are presented as a function of the temperature. The behavior of the systems is followed through various properties such as liquid and solid molar fractions, enthalpies of melting, heat capacities, self-diffusion coefficients and relaxation times related to the freezing process. The consistency of the simulation results for the heterogeneous nucleation is assessed by means of a classical nucleation model, from which an estimate of the interfacial surface tension is also worked out and compared with experimental data.     

Surface nucleation in the crystallisation of polyethylene droplets

The division of semi-crystalline polymeric material into small domains is an effective tool for studying crystal nucleation. The scaling behavior of the nucleation rate as a function of domain size can reveal important information about the mechanism responsible for the birth of a crystal nucleus. We have investigated the process of crystal nucleation in a system of dewetted polyethylene droplets. Through the use of a correlation sample analysis, we are able to differentiate between heterogeneous and homogeneous nucleation mechanisms in a droplet sample. An analysis of the dependence of the nucleation rate on droplet size reveals that the nucleation probability scales with the surface area of the droplet.     

Localization of the electromagnetic field in the vicinity of gold nanoparticles: Surface modification of different substrates

Theoretical predictions and experimental results for nanosized modification of metal (Au), semiconductor (Si), or dielectric (soda lime glass) substrates using near-electromagnetic field enhancement in the vicinity of gold nanoparticles are presented. The near field properties for the system consisting of an isolated gold nanoparticle or nanoparticle aggregate deposited on the substrates, which is irradiated by electromagnetic wave, are investigated using Finite Difference Time Domain Simulation technique. The influence of the substrate material on the near field distribution characteristics is predicted. The results reveal that the field on the substrate surface is enhanced in the three investigated cases, but its spatial distribution and magnitude depend on the substrate material. In the case of the metal and semiconductor substrate the enhanced near field is strongly localized in the vicinity of the contact point with the particle, in an area with diameter smaller than the particle's one. The intensity of the enhanced field on the glass is more than an order of magnitude lower than the case of using silicon substrate. The properties of the near field on the substrate surface also depend on the particle arrangement. For a two-dimensional gold nanoparticle array, when the particles are closely arrayed, the intensity of the enhanced field on the substrate surface is minimal. With the increase of the interparticle distance the near field intensity increases. The validity of the obtained theoretical results is confirmed experimentally.     

Surface modification of gold nanoparticles and their monolayer behavior at the air/water interface

Gold nanoparticles were prepared by two different methods. The first method was chemically grafting the particles with different lengths of alkylthiol (C₆SH, C₁₂SH and C₁₈SH). For the second method, the Au particles were surface modified first by mercaptosuccinic acid (MSA) to render a surface with carboxylic acid groups which play a role to physically adsorb cationic surfactant in chloroform. This method was termed physical/chemical method. In the first method, the effects of alkyl chain length and dispersion solvent on the monolayer behavior of surface modified gold nanoparticles was evaluated. The gold nanoparticles prepared by 1-hexanthiol demonstrated the narrowest size distribution. Most of them showed narrower particle size distributions in chloroform than in hexane. For the physical/chemical method, the particles can spread more uniformly on the water surface which is attributed to the amphiphilic character of the particles at the air/water interface. However, the particles cannot pack closely due to the relatively weak particle-particle interaction. The effect of alkyl chain length was also assessed for the second method.     

Surface nucleation and growth in the system of interacting particles

Recent experiments on epitaxial growth of metals on graphene have shown a strong dependence of island densities on coverage. These investigations cannot be explained by the standard mean-field nucleation theories. To understand them, we extend to higher coverage the former theory of rate equations developed for the initial state of nucleation, in a system where adsorbate interaction is included. We account for that, in the case of high coverage, the repulsive interaction influences both the attachment of monomers to clusters and the mobility of atoms. In our work we analyze the modification of the dependence of the island density on coverage, temperature and F/D ratio. In some regimes our theory results in the experimentally observed substantial growth of island density with coverage for a high deposited amount and a weak dependence on deposition rate F. We also find out the local maxima in temperature dependence of island density, as a consequence of long-range repulsive interactions.     

Surface freezing on patterned substrates

We show that the structure of a substrate pattern drastically influences the nature of surface freezing. By using phenomenological theory and computer simulations of a hard sphere fluid next to a substrate formed by a periodic array of fixed spheres, we find that a pattern which is commensurate with the bulk crystal induces complete surface freezing through a cascade of layering transitions. A rhombic pattern, on the other hand, either generates a crystalline sheet which is unstable as a bulk phase or prohibits surface freezing completely.     

Shape evolution of gold nanoparticles

The tetraoctylammonium bromide-stabilized gold nanoparticles have been successfully fabricated. The shape evolution of these nanoparticles under different annealing temperatures has been investigated using high-resolution transmission electron microscopy. After an annealing at 100 °C for 30 min, the average diameters of the gold nanoparticles change a little. However, the shapes of gold nanoparticles change drastically, and facets appear in most nanoparticles. After an annealing at 200 °C for 30 min, not only the size but also the shape changes a lot. After an annealing at 300 °C for 30 min, two or more gold nanoparticles coalesce into bigger ones. In addition, because of the presence of Cu grid during the annealing, some gold particles become the nucleation sites of Cu₂O nanocubes, which possess a microstructure of gold-particle core/Cu₂O shell. These Au/Cu₂O heterostructure nanocubes can only be formed at a relatively high temperature (≥300 °C). The results can provide some insights on controlling the shapes of gold nanoparticles.     

Ripening of nanowire-supported gold nanoparticles

Gold nanoparticles have applications ranging from catalysts for low temperature oxidation of CO to solar energy capture in the infrared. For all these applications, particle size and shape are critical. In this study, nanoparticle gold formed on GaN nanowires by plasma-enhanced chemical vapor deposition was annealed at temperatures ranging from 150 to 270 °C for 24 h. Particle size was measured before and after annealing using a field emission scanning electron microscope. Ripening of the gold particles was observed even at the lowest annealing temperatures of the study. The particle growth kinetics showed an Arrhenius relationship with activation energy of 27.38 kJ/mol. This value suggests that ripening occurs by particle migration and coalescence rather than adatom diffusion.     

Initial nucleation stages and properties of CuCl nanoparticles in glasses

The time variation and temperature dependence of a CuCl phase nucleation in a glass was studied by exciton spectroscopy. The phase formation kinetics at three temperatures was measured. A time delay in attaining a stationary rate of the new phase growth was observed at all temperatures, in agreement with the Zeldovich theory. The kinetic parameters of the CuCl phase formation were determined in the initial stage, when the critical nuclei possessing a zero surface energy (and an effective radius below 1.3 nm) appear in the glass matrix. The first-order phase transition in the new phase is 200 K below the melting temperature of CuCl single crystals. The temperature dependence of the CuCl phase nucleation rate reveals the second and third stages of the new phase formation. The activation energies for diffusion of the CuCl phase components in the glass matrix are determined.     

Solidification of gold nanoparticles in carbon nanotubes

The structure and the solidification of gold nanoparticles in a carbon nanotube are investigated using molecular dynamics simulations. The simulations indicate that the predicted solidification temperature of the enclosed particle is lower than its bulk counterpart, but higher than that observed for clusters placed in vacuum. A comparison with a phenomenological model indicates that, in the considered range of tube radii (R(CNT)) of 0.5 < R(CNT) < 1.6 nm, the solidification temperature depends mainly on the length of the particle with a minor dependence on R(CNT).     

Surface segregation analysis of martensite nucleation in model systems

In this work the study of the dependence of the critical temperatureM _s for the onset of martensite in noble metal (NM)-based ternary alloys in extended to some new cases of interest, for which experimental data are now available.A recently developed model connecting surface segregation and martensite nucleation is applied, which on the one hand gives information in agreement with experimental data, and on the other allows for a critical comparison between the obtained results and the theoretical predictions in the framework of related predictive theories for surface segregation.     

Narrowband luminescence of copper in the presence of gold nanoparticles

Narrow bands were experimentally revealed in the spectrum of copper under a layer of gold nanoparticles. Luminescence was excited with a He–Ne laser (6328 Å). The spectra of films of individual metals contained no similar bands. Experimental conditions and recorded spectra were presented, and some possible explanations of the observed effect were discussed.     

Computer simulation of water vapor nucleation on charged nanoparticles

The Monte Carlo method is applied to the study of the formation of condensed-phase nuclei from water vapor on electrically charged silver iodide nanocrystals. This study is a continuation of the investigations carried out earlier in [1] with electrically neutral nucleation centers. Nanoparticles with a size of up to 4 nm and flat nanoparticles with a size of up to 10 nm are investigated. The free energy, entropy, and the work of formation of nuclei with a size of up to 6729 molecules are calculated at the atomic level by the bicanonical statistical ensemble (BSE) method at a temperature of 260 K. Thermodynamic stability of nuclei is investigated depending on the size, shape, and charge of nanocrystal nucleation centers, as well as depending on the presence of crystal defects and the degree of spatial localization of charge on the surface of nanoparticles. The excess charge has a crucial effect on the work of formation of a nucleus only in the case of strong spatial localization of the latter near a point crystal defect; however, this effect is restricted to a relatively small size of the nuclei and therefore cannot substantially enhance the ice-forming activity of nanoparticles. A nucleus that grows on the surface of a nanoparticle evolves through three stages that differ in molecule retention mechanism and thermodynamic stability. The charge of a nanoparticle has a small effect on these factors. The leading factor that determines the ice-forming activity of ion nanocrystals is their intrinsic electric field due to the nonuniform distribution of charge within a unit cell of the crystal lattice.     

芯帽纳米颗粒的光热性质

贵金属纳米结构中的光热效应在肿瘤光热治疗、光热成像、纳米药物等领域具有重要的应用价值.各向异性的芯帽纳米结构以其丰富的可调结构参数和对激发光偏振态敏感的特性,可灵活地在近红外波段获得理想的光学吸收性质,从而可以实现温度的高效调节.本文基于有限元方法研究了颗粒物纳米结构参数对其光热效果的作用规律,数值结果表明:通过对结构参数的微量改变(包括金壳厚度、芯壳比、芯径、金属表面覆盖率等)可实现温度的显著调整;在偏振态的旋转范围(30?—70?)内可快速地产生大温变光热的准线性调整.其不弱于纳米芯壳和纳米棒结构的光热性能可为纳米光热生医研究提供一种新的选择.     

Chemical composition of surface-functionalized gold nanoparticles

The composition of surface-functionalized gold nanoparticles (diameter of the metallic core: 17–20 nm) was determined by elemental analysis (C, H, N, S, Au, Na) after preparation of a larger batch. Gold nanoparticles were prepared and functionalized with citrate according to the classical Turkevich method. The citrate-functionalized nanoparticles contained about 3.1 wt% of organic material (135 ng cm⁻² or 3.1 molecules nm⁻²). A partial exchange of citrate was accomplished by tris(sodium-m-sulfonato-phenyl)phosphine (TPPTS) which led to 2.1 wt% of citrate (90 ng cm⁻² or 2.1 molecules nm⁻²) and 1.4 wt% TPPTS (61 ng cm⁻² or 0.6 molecules nm⁻²). The citrate coating was quantitatively exchanged by poly(N-vinyl pyrrolidone) (PVP) after immersion in solutions with concentrations of 33, 66 and 128 mg L^-1, respectively, leading to contents of 4 to 6 wt% of PVP (171–271 ng cm⁻² or 9–15 PVP monomer units nm⁻²).     

Agglomeration behavior of lipid-capped gold nanoparticles

The current investigation deciphers aggregation pattern of gold nanoparticles (AuNPs) and lipid-treated AuNPs when subjected to aqueous sodium chloride solution with increasing ionic strengths (100–400 nM). AuNPs were synthesized using 0.29 mM chloroauric acid and by varying the concentrations of trisodium citrate (AuNP1 1.55 mM, AuNP2 3.1 mM) and silver nitrate (AuNP3 5.3 μM, AuNP4 10.6 μM) with characteristic LSPR peaks in the range of 525–533 nm. TEM analysis revealed AuNPs to be predominantly faceted nanocrystals with the average size of AuNP1 to be 35?±?5 nm, AuNP2 15?±?5 nm, AuNP3 30?±?5 nm, and AuNP4 30?±?5 nm and the zeta-average for AuNPs were calculated to be 31.23, 63.80, 26.08, and 28 nm respectively. Induced aggregation was observed within 10 s in all synthesized AuNPs while lipid-treated AuNP2 (AuNP2-L) was found to withstand ionic interferences at all concentration levels. However, lipid-treated AuNPs synthesized using silver nitrate and 1.55 mM trisodium citrate (AuNP3, AuNP4) showed much lower stability. The zeta potential values of lipid-treated AuNPs (AuNP1-L-1x/200, ??17.93?±?1.02 mV; AuNP2-L-1x/200, ??21.63?±?0.70; AuNP3-L-1x/200, ??14.54?±?0.90; AuNP3-L-1x/200 ??13.77?±?0.83) justified these observations. To summarize, AuNP1 and AuNP2 treated with lipid mixture 1 equals or above 1x/200 or 1x/1000 respectively showed strong resistance against ionic interferences (up to 400 mM NaCl). Use of lipid mixture 1 for obtaining highly stable AuNPs also provided functional arms of various lengths which can be used for covalent coupling.

Open image in new window

Graphical abstract Agglomeration behavior of gold nanoparticles before and after lipid capping