A rapid and readily reproducible seed‐based method for the production of high quality silver nanoprisms in high yield is presented. The edge‐length and the position of the main plasmon resonance of the nanoprisms can be readily controlled through adjustment of reaction conditions. From UV‐vis spectra of solutions of the nanoprisms, the inhomogeneously broadened line width of the in‐plane dipole plasmon resonance is measured and trends in the extent of plasmon damping as a function of plasmon resonance energy and nanoprism size have been elucidated. In addition, an in‐depth analysis of the lamellar defect structure of silver nanoprisms is provided that confirms that the defects can lead to a transformation of the crystal structure in the vicinity of the defects. These defects can combine give rise to lamellar regions, thicker than 1 nm, that extend across the crystal, where the silver atoms are arranged in a continuous hexagonal‐close‐packed (hcp) structure. This hcp structure has a periodicity of 2.50 Å, thus explaining the 2.50 Å lattice fringes that are commonly observed in 〈111〉 oriented flat‐lying nanoprisms. A new understanding of the mechanisms behind anisotropic growth in silver nanoprisms is presented.

Stable dispersions of single-walled carbon nanotubes in deionized water were prepared using six common surfactants: sodium dodecylbenzene sulfonate (SDBS), sodium dodecyl sulfate (SDS), lithium dodecyl sulfate (LDS), tetradecyl trimethyl ammonium bromide (TTAB), sodium cholate (SC), and Fairy liquid (FL). For all nanotube dispersions (C NT ) 1 mg/mL), the optimum concentration of surfactant was found to be close to C Surf ) 10 mg/mL by measuring the fraction of nanotubes remaining after centrifugation for a range of surfactant concentrations. The aggregation state of each nanotube-surfactant dispersion was characterized as a function of nanotube concentration by AFM analysis of large numbers of nanotubes/bundles deposited onto substrates. The dispersion quality could then be quantified by four parameters: the saturation value (at low concentration) of the root-mean-square bundle diameter, the maximum value of the total number of dispersed objects (individuals and bundles) per unit volume of dispersion, the saturation value (at low concentration) of the number fraction of individual nanotubes, and the maximum value of the number of individual nanotubes per unit volume of dispersion. According to these metrics, the dispersion quality of the six surfactant-nanotube dispersions varied as SDS > LDS > SDBS > TTAB > SC > Fairy liquid. It was found that each of these dispersion-quality metrics scaled very well with the measured ζ-potential of the surfactant-nanotube dispersion. This confirms that dispersion quality is controlled by the magnitude of electrostatic repulsive forces between coated nanotubes.

Solution phase triangular silver nanoplates (TSNP) with versatile tunability throughout the visible-NIR wavelengths are presented as highly sensitive localized surface plasmon refractive index sensors. A range of 20 TSNP solutions with edge lengths ranging from 11 to 200 nm and aspect ratios from 2 to 13 have been studied comprehensively using AFM, TEM, and UV-vis-NIR spectroscopy. Studies of the localized surface plasmon resonance (LSPR) peak's sensitivity to refractive index changes are performed using a simple sucrose concentration method whereby the surrounding refractive index can solely be changed without variation in any other parameter. The dependence of the TSNP localized surface plasmon resonance (LSPR) peak wavelength lambda(max) and its bulk refractive index sensitivity on the nanoplate's structure is determined. LSPR sensitivities are observed to increase linearly with lambda(max) up to 800 nm, with the values lying within the upper limit theoretically predicted for optimal sensitivity, notwithstanding any diminution due to ensemble averaging. A nonlinear increase in sensitivity is apparent at wavelengths within the NIR region with values reaching 1096 nm.RIU(-1) at lambda(max) 1093 nm. Theoretical studies performed using a simple aspect ratio dependent approximation method and discrete dipole approximation methods confirm the dependence of the LSPR bulk refractive index sensitivity upon the TSNP aspect ratio measured experimentally. These studies highlight the importance of this key parameter in acquiring such high sensitivities and promote these TSNP sols for sensing applications at appropriate wavelengths for biological samples.

The fact that the motion of solvent molecules defines the reaction coordinate for electron-transfer and other chemical reactions has generated great interest in solvation dynamics, the study of how the solvent responds to changes in a solute's electronic state. In the limit of linear response (LR), when the perturbation caused by the solute is "small", the relaxation of the excited solute's energy gap should behave identically to the relaxation dynamics of the unperturbed solute following a natural fluctuation of the gap away from equilibrium. Despite the fact that the addition of a fundamental unit of charge to a small solute results in a solvation energy that is tens or hundreds of kT, computer simulations of solvation dynamics have found, with only a few exceptions, that LR is obeyed for changes in solute charge. Essentially none of this work, however, accounts for the fact that the solutes in real chemical reactions undergo changes in size and shape as well as in charge distribution. In this paper, we compare the results of molecular simulations of polar and nonpolar solvation dynamics for a simple Lennard-Jones solute in a flexible-water solution to explore the validity of LR. We find that, when short-range forces are involved, LR breaks down dramatically: both the inertial and diffusive components of the relaxation differ from those predicted by LR. For increases in solute size, expansion of the solute drives the first-shell solvent molecules into the second shell. The resulting nonequilibrium relaxation takes advantage of translation-rotation coupling that does not occur at equilibrium, resulting in faster solvation than that predicted by LR. Decreases in solute size, on the other hand, result in inward translational motions of solvent molecules that affect the solute's energy gap by destabilizing the energy of the (unoccupied) ground state. The inward motions involved in the nonequilibrium relaxation are not present at equilibrium because the destabilization of the ground state is much larger than kT. Because the energetically most important solvent molecules, those closest to the solute, are just as likely to be moving away from the solute as toward it at the time of excitation, solvation for decreases in size is much slower than predicted by LR. In the most realistic cases, when both the size and the charge of the solute change, the solvent translational motions resulting from the size change and those resulting from electrostriction, the net ion-dipole attraction between the charged solute and the polar solvent, combine in an additive fashion. When the solute both gains a charge and expands, the translational motions resulting from electrostriction nearly cancel those from the outward solute expansion so that rotational motions dominate the solvent response; the small net expansion that remains results in only a minor breakdown of LR. The additional inward solvent translations beyond those required by electrostriction, which are necessary when the solute becomes charged and its size decreases, on the ...

In recent years, galvanic replacement reactions have been successfully employed to produce hollow bimetallic nanostructures of a range of shapes, yet to date there has been no example of the formation of hollow triangular AuAg nanostructures from a Ag nanoprism template. In this manuscript the first example of the synthesis of enclosed triangular AuAg nanostructures (triangular nanoboxes) via galvanic replacement reactions from Ag nanoprisms is reported. These triangular nanoboxes are studied by TEM and HAADF‐STEM imaging to elucidate their structure. These studies show that the nanostructures are hollow and do not consist of a Ag core surrounded by a Au shell. Discrete dipole approximation calculations for the extinction spectra are carried out and provide additional evidence that the nanostructures are hollow. These new triangular nanoboxes are very attractive candidates for encapsulation and transport of materials of interest such as drugs, radioisotopes, or magnetic materials.