Multiscale modeling of the surfactant mediated synthesis and supramolecular assembly of cobalt nanodots

Multiscale simulations are used to bridge the surfactant templated assembly of individual approximately 1-10 nm cobalt dots, to their ordering into supramolecular arrays. Potential energy surfaces derived from ab initio calculations are input to lattice Monte Carlo simulations at atomic scales. By this process we quantitatively reproduce the experimental cobalt nanoparticle sizes. Crucially, we find that there is an effective short range attraction between pairs of nanodots. Mesoscale simulations show that these attractive interdot potentials are so short ranged that the dots can assemble only into orientally ordered hexatic phases as in the experiments.     

Calculating potential of mean force between like-charged nanoparticles: A comprehensive study on salt effects

Ions are critical to the structure and stability of polyelectrolytes such as nucleic acids. In this work, we systematically calculated the potentials of mean force between two like-charged nanoparticles in salt solutions by Monte Carlo simulations. The pseudo-spring method is employed to calculate the potential of mean force and compared systematically with the inversed-Boltzmann method. An effective attraction is predicted between two like-charged nanoparticles in divalent/trivalent salt solution and such attraction becomes weakened at very high salt concentration. Our analysis reveals that for the system, the configuration of ion-bridging nanoparticles is responsible for the attraction, and the invasion of anions into the inter-nanoparticles region at high salt concentration would induce attraction weakening rather than the charge inversion effect. The present method would be useful for calculating effective interactions during nucleic acid folding.     

Condensation in the Zero Range Process: Stationary and Dynamical Properties

The zero range process is of particular importance as a generic model for domain wall dynamics of one-dimensional systems far from equilibrium. We study this process in one dimension with rates which induce an effective attraction between particles. We rigorously prove that for the stationary probability measure there is a background phase at some critical density and for large system size essentially all excess particles accumulate at a single, randomly located site. Using random walk arguments supported by Monte Carlo simulations, we also study the dynamics of the clustering process with particular attention to the difference between symmetric and asymmetric jump rates. For the late stage of the clustering we derive an effective master equation, governing the occupation number at clustering sites.     

Dynamic colloidal stabilization by nanoparticle halos

We explore the conditions under which colloids can be stabilized by the addition of smaller particles. The largest repulsive barriers between colloids occur when the added particles repel each other with soft interactions, leading to an accumulation near the colloid surfaces. At lower densities these layers of mobile particles (nanoparticle halos) result in stabilization, but when too many are added, the interactions become attractive again. We systematically study these effects--accumulation repulsion, reentrant attraction, and bridging--by accurate integral equation techniques.     

Effect of mono- and multivalent salts on angle-dependent attractions between charged rods

Using molecular dynamics simulations we examine the effective interactions between two like-charged rods as a function of angle and separation. In particular, we determine how the competing electrostatic repulsions and multivalent-ion-induced attractions depend upon concentrations of simple and multivalent salts. We find that with increasing multivalent salt, the stable configuration of two rods evolves from isolated rods to aggregated perpendicular rods to aggregated parallel rods; at sufficiently high concentration, additional multivalent salt reduces the attraction. Monovalent salt enhances the attraction near the onset of aggregation and reduces it at a higher concentration of multivalent salt.     

Detection of invisible phonon modes in individual defect-free carbon nanotubes by gradient-field Raman scattering

We provide an effective method to investigate the field gradient effect in nanoconfined plasmon-matter interaction.Aligned ultralong SWNTs without defects were grown on marked substrates, followed by assembling gold nanoparticle clusters around individual nanotubes. The Raman scattering behavior of a nanotube placed in an atomic scale nanogap between adjacent nanoparticles was studied. In addition to the expected plasmon-induced Raman enhancement up to 103,the defect-free D-mode of an individual SWNT induced by gradient field is found for the first time. When the light is confined at atomic scale, gradient field Raman scattering becomes significant and dipole-forbidden phonon modes can be activated by quadrupole Raman tensor variation, indicating breakdown of the Raman selection rules.     

Enhancement of organic nanoparticle preparation by laser ablation in aqueous solution using surfactants

Nanoparticle and metal phthalocyanine (MPc) transparent colloidal aqueous solutions were directly obtained by 355 nm YAG laser ablation. We found that too long an irradiation time does not contribute to producing nanoparticles and their generation efficiency increases with a low solution temperature. We believe this due to nanoparticle reassociation which is caused by hydrophobicity. To prevent generated nanoparticles from reassociating we performed experiments adding two kinds of ionic and nonionic surfactants into solution. We found five characteristics of nanoparticle generation from adding surfactants to a solution regardless of the type of surfactant used. These characteristics are that: (1) production efficiency increases; (2) stability is better after irradiation; (3) irradiation intensity needed to induce nanoparticle generation becomes lower; (4) mean size of the generated nanoparticles becomes smaller; and (5) crystalline structures of oxo(phthalocyaninato) vanadium (IV) (VOPc) are controllable by changing the surfactant concentration.     

Van der Waals interaction between flux lines in high- superconductors: A variational approach

In pure anisotropic or layered superconductors thermal fluctuations induce a van der Waals attraction between flux lines. This attraction together with the entropic repulsion has interesting consequences for the low field phase diagram; in particular, a first order transition from the Meissner phase to the mixed state is induced. We introduce a new variational approach that allows for the calculation of the effective free energy of the flux line lattice on the scale of the mean flux line distance a, which is based on an expansion of the free energy around the regular triangular Abrikosov lattice. Using this technique, the low field phase diagram of these materials may be explored. The results of this technique are compared with a recent functional RG treatment of the same system. Received: 25 June 1996 / Revised: 18 August 1998 / Accepted: 21 August 1998     

Au-Pd共晶纳米粒子熔化行为的分子动力学研究

采用分子动力学方法结合嵌入原子势, 对Au-Pd共晶纳米粒子的热稳定性进行了模拟研究. 计算结果表明: Au-Pd纳米粒子的熔点明显高于Au单质纳米粒子而低于Pd纳米粒子. 通过计算Lindemann指数发现Au-Pd共晶纳米粒子中的Au原子首先熔化, 然后带动Pd原子的熔化; 熔化所经历的温度区间明显要宽于单质纳米粒子.     

Controlling pattern formation in nanoparticle assemblies via directed solvent dewetting

We have achieved highly localized control of pattern formation in two-dimensional nanoparticle assemblies by direct modification of solvent dewetting dynamics. A striking dependence of nanoparticle organization on the size of atomic force microscope-generated surface heterogeneities is observed and reproduced in numerical simulations. Nanoscale features induce a rupture of the solvent-nanoparticle film, causing the local flow of solvent to carry nanoparticles into confinement. Microscale heterogeneities instead slow the evaporation of the solvent, producing a remarkably abrupt interface between different nanoparticle patterns.     

Van der Waals interaction between flux lines in high- superconductors

In anisotropic or layered superconductors thermal fluctuations as well as impurities induce a van der Waals (vdW) attraction between flux lines, as has recently been shown by Blatter and Geshkenbein in the thermal case [#!BlatterGeshkenbein!#] and by Mukherji and Nattermann in the disorder dominated case [#!NattermannMukherji!#]. This attraction together with the entropic or disorder induced repulsion has interesting consequences for the low field phase diagram. We present two derivations of the vdW attraction, one of which is based on an intuitive picture, the other one following from a systematic expansion of the free energy of two interacting flux lines. Both the thermal and the disorder dominated case are considered. In the thermal case in the absence of disorder, we use scaling arguments as well as a functional renormalization of the vortex-vortex interaction energy to calculate the effective Gibbs free energy on the scale of the mean flux line distance. We discuss the resulting low field phase diagram and make quantitative predictions for pure BiSCCO (Bi₂Sr₂CaCu₂O₈). In the case with impurities, the Gibbs free energy is calculated on the basis of scaling arguments, allowing for a semi-quantitative discussion of the low-field, low-temperature phase diagram in the presence of impurities. Received: 9 February 1998 / Accepted: 17 April 1998     

纳米流体对流换热机理分析

考虑在纳米流体中纳米颗粒做布朗运动引起的对流换热, 基于纳米颗粒在纳米流体中遵循分形分布, 本文得到纳米流体对流换热的机理模型. 本解析模型没有增加新的经验常数, 从该模型发现纳米流体池沸腾热流密度是温度、纳米颗粒的平均直径、 纳米颗粒的浓度、纳米颗粒的分形维数、沸腾表面活化穴的分形维数、基本液体的物理特性的函数. 对不同的纳米颗粒浓度和不同的纳米颗粒平均直径与不同的实验数据进行了比较, 模型预测的结果与实验结果相吻合. 所得的解析模型可以更深刻地揭示纳米流体对流换热的物理机理.     

Chemical sensing based on the plasmonic response of nanoparticle aggregation: Anion sensing in nanoparticles stabilized by amino-functional ionic liquid

We report the synthesis, characterization and modellization of optical anion sensors based on gold nanoparticles (Au NPs) stabilized by amino-functional imidazolium ionic liquids (AFIL). The addition of different salts results in anion exchange of the imidazolium ionic liquid stabilizer leading to a change in the optical response of the original nanoparticle aqueous solution. In all cases except with dodecylbenzenesulfonic acid sodium salt, a sufficient amount of salt concentration (5 times larger than equimolar) leads to the appearance of an absorption band between 600 and 700 nm in the ultravioletvisible (UV-vis) spectrum. The presence of the salt produces aggregation of the particles that localise the optical response and produce a large spectral red shift. Transmission electron microscopy images demonstrated that this optical change was due to the aggregation of the nanoparticles. We simulate the optical response of both situations, before and after salt addition, and interpret the experimental observations in terms of the different response of metallic single nanoparticles and nanoparticle aggregates. Theoretical calculations for single nanoparticle and single nanoparticle dimers demonstrate that the colour change is not due to the enlargement or structural changes of the Au NPs, but due to the formation of NP aggregation. These results show the potential of nanoparticle plasmonics to perform effective chemical sensing.     

Chemical sensing based on the plasmonic response of nanoparticle aggregation: anion sensing in nanoparticles stabilized by amino-functional ionic liquid

We report the synthesis, characterization and modellization of optical anion sensors based on gold nanoparticles (Au NPs) stabilized by amino-functional imidazolium ionic liquids (AFIL). The addition of different salts results in anion exchange of the imidazolium ionic liquid stabilizer leading to a change in the optical response of the original nanoparticle aqueous solution. In all cases except with dodecylbenzenesulfonic acid sodium salt, a sufficient amount of salt concentration (5 times larger than equimolar) leads to the appearance of an absorption band between 600 and 700 nm in the ultravioletvisible (UV-vis) spectrum. The presence of the salt produces aggregation of the particles that localise the optical response and produce a large spectral red shift. Transmission electron microscopy images demonstrated that this optical change was due to the aggregation of the nanoparticles. We simulate the optical response of both situations, before and after salt addition, and interpret the experimental observations in terms of the different response of metallic single nanoparticles and nanoparticle aggregates. Theoretical calculations for single nanoparticle and single nanoparticle dimers demonstrate that the colour change is not due to the enlargement or structural changes of the Au NPs, but due to the formation of NP aggregation. These results show the potential of nanoparticle plasmonics to perform effective chemical sensing.     

On the role of weak interfaces in blocking slip in nanoscale layered composites

Layered composites of Cu/Nb achieve very high strength levels when the individual layer thicknesses are 1–10?nm, attributable to the interfaces acting as barriers to slip. Atomistic models of Cu/Nb bilayers were used to explore the origins of this resistance. The models clearly show that dislocations placed near an interface experience an attraction toward the interface, regardless of the sign of the Burgers vector or the material in which it is placed. This attraction is caused by shear of the interface induced by the stress field of the dislocation. Furthermore, the dislocation, upon reaching the interface, is absorbed by it in the sense that the core spreads within the interface. We develop a model, using a fractional dislocation approach, which provides an estimate of the strength of the attraction as a function of distance from the interface and also the dependence of the interaction on the type of dislocation. A screw dislocation is much more effective in shearing the interface, and the resulting attractive forces on screws are larger than for edge dislocations.     

Trapping and release of citrate-capped gold nanoparticles

An electrical method to trap and release charged gold nanoparticles onto and from the surface of gold electrodes modified by an alkanethiol self-assembled monolayer (SAM) is presented. To form electrodes coated with gold nanoparticles (GNPs), amine-terminated SAMs on gold electrodes were immersed in a solution of negatively charged citrate-capped GNPs. Accumulation of GNPs on the electrode surface was monitored by a decrease in the impedance of the SAM-modified electrode and by an increase in the electrochemical activity at the electrode as shown through cyclic voltammetry (CV). Electrostatic interactions between the GNPs and the amine-terminated SAM trap the GNPs on the electrode surface. Application of a subsequent negative bias to the electrode initiated a partial release of the GNPs from the electrode surface. Impedance spectroscopy, cyclic voltammetry, ultraviolet-visible (UV-Vis) spectroscopy and atomic force microscopy (AFM) were used to monitor and confirm the attraction of GNPs to and release from the aminealkanethiolated gold electrodes. This work describes a method of trapping and release for citrate-capped GNPs that could be used for on-demand nanoparticle delivery applications such as in assessing and modeling nanoparticle toxicology, as well as for monitoring the functionalization of gold nanoparticles.     

Luttinger liquid with one impurity: Equivalent field theory and duality

We derive by functional integral method one-dimensional theory equivalent to Luttinger liquid with one impurity. It is shown that the single quantity has to be calculated for the formulation the effective field theory is the electron density jump at the impurity. We show that duality which relates models with electron-electron attraction and repulsion, and simultaneous exchange of transition and reflection coefficients, is an exact property of the theory.     

Counterion-mediated, non-pairwise-additive attractions in bundles of like-charged rods

Stiff polyelectrolyte chains, such as DNA, can attract each other in solution even though they have the same sign of charge. The attractions are mediated by multivalent counterions, which lead to an effective interaction at the two-chain level that is attractive at short range and repulsive at long range. However, the effective interchain interactions are not pairwise additive. We present a formulation that allows theoretical treatment of the many-chain problem without assuming pairwise additivity. We show that a bundle of chains held together by counterion-mediated attractions can be described in terms of a bulk and surface free energy, and discuss the temperature dependence of the attraction.     

Task-based exposure assessment of nanoparticles in the workplace

Although task-based sampling is, theoretically, a plausible approach to the assessment of nanoparticle exposure, few studies using this type of sampling have been published. This study characterized and compared task-based nanoparticle exposure profiles for engineered nanoparticle manufacturing workplaces (ENMW) and workplaces that generated welding fumes containing incidental nanoparticles. Two ENMW and two welding workplaces were selected for exposure assessments. Real-time devices were utilized to characterize the concentration profiles and size distributions of airborne nanoparticles. Filter-based sampling was performed to measure time-weighted average (TWA) concentrations, and off-line analysis was performed using an electron microscope. Workplace tasks were recorded by researchers to determine the concentration profiles associated with particular tasks/events. This study demonstrated that exposure profiles differ greatly in terms of concentrations and size distributions according to the task performed. The size distributions recorded during tasks were different from both those recorded during periods with no activity and from the background. The airborne concentration profiles of the nanoparticles varied according to not only the type of workplace but also the concentration metrics. The concentrations measured by surface area and the number concentrations measured by condensation particle counter, particulate matter 1.0, and TWA mass concentrations all showed a similar pattern, whereas the number concentrations measured by scanning mobility particle sizer indicated that the welding fume concentrations at one of the welding workplaces were unexpectedly higher than were those at workplaces that were engineering nanoparticles. This study suggests that a task-based exposure assessment can provide useful information regarding the exposure profiles of nanoparticles and can therefore be used as an exposure assessment tool.     

Study of electrical field distribution of gold-capped nanoparticle for excitation of localized surface plasmon resonance

The specific optical characteristics which can be observed from noble metal nanostructured materials such as nanoparticles and nanoislands have wide variety of applications such as biosensors, solar cells, and optical circuit. Because, these noble metal nanostructures induce the increment of light absorption efficiency by the enhancing effect of electrical field from localized surface plasmon resonance (LSPR) excitation. However, the enhancing effects of electrical field from LSPR using simple structured noble metal nanostructures for several applications are not satisfactory. To realize the more effective light absorption efficiency by the enhancing effect of electrical field, quite different noble metal nanostructures have been desired for applying to several applications using LSPR. In this study, to obtain the more effective enhancing effect of electrical field, conditions for LSPR excitation using a gold-capped nanoparticle layer substrate are computationally analyzed using finite-difference time-domain (FDTD) method. From the previous research, LSPR excitation using such gold-capped nanoparticle layer substrates has a great potential for application to high-sensitive label-free monitoring of biomolecular interactions. For understanding of detailed LSPR excitation mechanism, LSPR excitation conditions were investigated by analyzing the electrical field distribution using simulation software and comparing the results obtained with experimental results. As a result of computational analysis, LSPR excitation was found to depend on the particle alignment, interparticle distance, and excitation wavelength. Furthermore, the LSPR optical characteristics obtained from the simulation analysis were consistent with experimentally approximated LSPR optical characteristics. Using this gold-capped nanoparticle layer substrate, LSPR can be excited easily more than conventional noble metal nanoparticle-based LSPR excitation without noble metal nanoparticle synthesis. Hence, this structure is detectable a small change of refractive index such as biomolecular interactions for biosensing applications.