Depolarized Dynamic Light Scattering Research Articles

Determination of Translational and Rotational Diffusivities of Anisotropic Nanoparticles by Heterodyne Polarized and Depolarized Dynamic Light Scattering

Determination of Translational and Rotational Diffusivities of Anisotropic Nanoparticles by Heterodyne Polarized and Depolarized Dynamic Light Scattering

Understanding the Droplet Diffusion in Ionic Liquid Microemulsions.

Ionic liquids (ILs) as polar components in nonaqueous microemulsions are complex formulations that have interesting transport and structural properties, and offer broader applicability of ILs in areas such as drug delivery and cleaning technology. The phase behavior, electrical conductivity, and nanostructures of these formulations have been investigated for quite some time, but the characteristics of the diffusion of nanodroplets were rarely explored─ and hence little understood. This work investigates the droplet diffusion processes in a series of IL-microemulsions containing 1-butyl-3-methylimidazolium tetrafluoroborate ([C4mim]BF4) by means of viscosity and depolarized dynamic light scattering (DDLS) measurements. The intensity correlation functions are strikingly similar to polymeric solutions in nonaqueous media and aqueous microemulsions containing block copolymers─having bimodal relaxations that are separated by three to four decades of correlation delay times. The "faster" diffusion process is likely a collective process characterizing the correlated motions of droplets in droplet clusters. The collective diffusion coefficient Dcol values are quite comparable to aqueous microemulsions. The "slower" diffusion is likely due to the "caging" effect caused by nearby clusters and/or bulk solvent─this mode may be linked to the microemulsion bulk viscosity. Interestingly, the Dcol variations on increasing [C4mim]BF4 concentration are strongly correlated to the microemulsion viscosity changes as well as locations of these compositions on the microemulsion phase diagram.

Experimental examination of dipole-dipole cross-correlations by dielectric spectroscopy, depolarized dynamic light scattering, and computer simulations of molecular dynamics.

The contribution of cross- and self-correlations to the dielectric and light-scattering spectra of supercooled polar glass formers has recently become a most challenging problem. Herein, we employ dielectric spectroscopy, depolarized dynamic light scattering (DDLS), and rheology to thoroughly examine the dynamics of van der Waals liquid 1,2-Diphenylvinylene. Carbonate (DVC), which is a polar counterpart of canonical glass former ortho-Terphenyl (OTP). We show that the light-scattering data correspond well with the dielectric permittivity function over a wide T range. This pattern is very different from the peaks' separation ω_{max}^{DDLS}/ω_{max}^{BDS}=3.7 reported recently for tributyl phosphate (TBP), despite the same dielectric characteristics of these two glass formers (β_{KWW}=0.75,Δɛ=20 for both TBP and DVC; KWW stands for Kohlrausch-Williams-Watts). This indicates different influence of orientational correlations in both methods for these two systems. We also show the results of the computer simulations of the model, polar molecules, which clearly indicate that the contribution of the cross-term to the correlation function probed in the DDLS experiment can be significant.

Dimensions of Cellulose Nanocrystals from Cotton and Bacterial Cellulose: Comparison of Microscopy and Scattering Techniques.

Different microscopy and scattering methods used in the literature to determine the dimensions of cellulose nanocrystals derived from cotton and bacterial cellulose were compared to investigate potential bias and discrepancies. Atomic force microscopy (AFM), small-angle X-ray scattering (SAXS), depolarized dynamic light scattering (DDLS), and static light scattering (SLS) were compared. The lengths, widths, and heights of the particles and their respective distributions were determined by AFM. In agreement with previous work, the CNCs were found to have a ribbon-like shape, regardless of the source of cellulose or the surface functional groups. Tip broadening and agglomeration of the particles during deposition cause AFM-derived lateral dimensions to be systematically larger those obtained from SAXS measurements. The radius of gyration determined by SLS showed a good correlation with the dimensions obtained by AFM. The hydrodynamic lateral dimensions determined by DDLS were found to have the same magnitude as either the width or height obtained from the other techniques; however, the precision of DDLS was limited due to the mismatch between the cylindrical model and the actual shape of the CNCs, and to constraints in the fitting procedure. Therefore, the combination of AFM and SAXS, or microscopy and small-angle scattering, is recommended for the most accurate determination of CNC dimensions.

Orientational dynamics in supercooled glycerol computed from MD simulations: self and cross contributions.

The orientational dynamics of supercooled glycerol is probed using molecular dynamics simulations for temperatures ranging from 323 K to 253 K, through correlation functions of first and second ranks of Legendre polynomials, pertaining respectively to dielectric spectroscopy (DS) and depolarized dynamic light scattering (DDLS). The self, cross, and total correlation functions are compared with relevant experimental data. The computations reveal the low sensitivity of DDLS to cross-correlations, in agreement with what is found in experimental work, and strengthen the idea of directly comparing DS and DDLS data to evaluate the effect of cross-correlations in polar liquids. The analysis of the net static cross-correlations and their spatial decomposition shows that, although cross-correlations extend over nanometric distances, their net magnitude originates, in the case of glycerol, from the first shell of neighbouring molecules. Accessing the angular dependence of the static correlation allows us to get a microscopic understanding of why the rank-1 correlation function is more sensitive to cross-correlation than its rank-2 counterpart.

Precise measurement of gold nanorods by using depolarized dynamic light scattering apparatus

A precise and noninvasive method for the size and shape measurement of gold nanorods (GNRs) has been proposed based on depolarized dynamic light scattering (DDLS). A home-made DDLS apparatus has been established. By applying depolarized optical path with precise alignment method, the signal-to-noise ratio (SNR) of this apparatus is highly improved. GNRs with three different diameter and length has been precisely measured by using DDLS method as well as scanning electron microscopy (SEM). The thickness of adsorption layer of cetyltrimethylammonium bromide (CTAB) in solution has been taken into consideration. Results show that size measurement of GNRs by using DDLS method agrees very well with that by using SEM. In addition, it is shown that the extinction spectroscopy strongly limited the application of DDLS method by affecting the effective scattering light intensity. Proper laser wavelength should be chosen before the application of this method.

Mesoscale Aggregates and Dynamic Asymmetry in Ionic Liquids: Evidence from Depolarized Dynamic Light Scattering.

Nanoscale structures in ionic liquids (ILs) are usually identified by X-ray or neutron scattering techniques and occur when the alkyl chains of the cations are long enough to show the tendency to segregate into apolar domains. In search of dynamic evidence for these nanostructures, different experimental techniques recently reported bimodal dynamic susceptibility spectra. In all cases, the faster process observed was ascribed to the structural α-relaxation and the slower one to the relaxation of long-lived aggregates. By contrast, we show by depolarized dynamic light scattering (DDLS) experiments on a systematic series of imidazolium-based ILs that the dynamics of the cation and anion are clearly separated for long alkyl chains. Therefore, the observation of a bimodal behavior is not related to any nanostructure but reflects the two-component nature of ILs. Thus, a consistent picture is obtained across different experimental methods, like dielectric and shear mechanical relaxation. Finally, the actual dynamic signature of nanostructures is identified for the first time as a weak feature in some of the DDLS spectra at even lower frequencies.

Microscopic origin of the logarithmic relaxation in molecular glass-forming liquids

Logarithmic relaxation is a unique relaxation process exhibited by a few molecular liquids and biomolecules. However, the microscopic origin of logarithmic relaxation is still unclear. To understand the origin of this process, we studied two liquids that exhibit logarithmic relaxation in a dissolved state using quasielastic neutron scattering (QENS) and depolarized dynamic light scattering (DDLS). Although the intermolecular potential of the liquids is drastically different in the dissolved state from the bulk liquids, we observed that the logarithmic relaxation still persists. Our results indicate that the intermolecular potential does not play a role in determining the logarithmic relaxation process. The coupling of rotational and translational relaxation processes could be the origin of the logarithmic relaxation process exhibited by the molecular liquids.

Stability and morphology of Ag nanoplatelets probed by depolarized dynamic light scattering

The stability of silver nanoplatelet (NP) suspensions prepared with different concentrations of trisodium citrate (TSC) was studied by depolarized dynamic light scattering (DDLS) and UV–vis spectrometry. The morphology of the nanoparticles, as well as the color and stability of the sols, are tuned by the concentration of the capping agent. The nanoparticles prepared with high TSC concentration (>10−4 M) are blue triangular NPs showing a slight truncation of the tips with aging. When low TSC concentrations are used, the color of the sols changes from blue to yellow with aging time and a strong modification of the morphology occurs: the nanoparticle shape changes from triangular to spherical. Remarkably, they show a high degree of anisotropy. The aging process was followed by the UV–vis spectra and by measuring the rotational diffusion coefficient by DDLS, providing information on the nanoparticle size and shape evolution. The high intensity of depolarized signal and the high value of rotational diffusion coefficient suggest that the aging process increases the thickness and the roughness of the nanoparticles

Debye Process and β-Relaxation in 1-Propanol Probed by Dielectric Spectroscopy and Depolarized Dynamic Light Scattering.

We revisit the reorientational dynamics of 1-propanol as a prototype of a monohydroxy alcohol and H-bonding system by dielectric spectroscopy (DS) and depolarized dynamic light scattering (DDLS). In particular, we address the question of whether the Debye relaxation, which is seen as a dominant process in DS, is visible in light scattering and discuss how the Johari-Goldstein (JG) β-process, which is also a prominent feature of the dielectric spectrum, appears in photon correlation spectroscopy. For that purpose we performed depolarized photon correlation experiments with an improved setup and performed additional time domain dielectric experiments which gives us the possibility to compare dielectric and light scattering data in a broad temperature range. It turns out that the improved setup allows to unambiguously identify the JG β-process, which shows almost identical properties in DDLS as in the dielectric spectra, but a Debye relaxation is not present in the DDLS data and can be excluded down to a level of 2.5% of the α-process amplitude.

Solvent-Regulated Mesoscale Aggregation Properties of Dilute PBTTT-C14 Solutions

Contrasting mesoscale aggregate features of a promising conjugated polymer, poly(2,5-bis(3-tetradecylthiophene-2-yl)thieno[3,2-b]thiophenes) (pBTTT-C14), that result from the use of two slightly different aromatic solvents, i.e., toluene and chlorobenzene, for a range of dilute solutions (0.5–1.2 mg/mL) are systematically explored using depolarized dynamic light scattering (DDLS), dynamic/static light scattering (DLS/SLS), small-angle X-ray scattering (SAXS), and scanning transmission electron/scanning electron/transmission electron microscopy (STEM/SEM/TEM) analysis schemes. The central findings are as follows: (1) DDLS and all EM features reveal that whereas pBTTT-C14 aggregate clusters fostered in toluene (a poorer solvent) are moderately anisotropic (cylindrical; aspect ratio ∼3) in shape, they are nearly isotropic (spherical) in chlorobenzene (a better solvent), with mean sizes in the range of a few hundred nanometers. (2) Combined DDLS/DLS/SLS/SAXS analyses indicate that the aggregate clusters in bo...

A new angle on dynamic depolarized light scattering: number-averaged size distribution of nanoparticles in focus.

Size polydispersity is a common phenomenon that strongly influences the physicochemical properties of nanoparticles (NPs). We present an analytical approach that is universally applicable to characterizing optically anisotropic round NPs and determines directly the number-averaged size distribution and polydispersity via depolarized dynamic light scattering (DDLS). To demonstrate, we use aqueous suspensions of Au NPs of different sizes and surface functionalization.

Resonant depolarized dynamic light scattering of silver nanoplatelets

Polarized and depolarized dynamic light scattering (DDLS) methodology was carried out on silver nanoplatelets showing strong plasmon-enhanced scattering. The hydrodynamic properties of the nanoparticles were determined by measuring the translation diffusion coefficient for “out resonant” condition and the rotational diffusion coefficient for “in resonant” condition. The results have been interpreted by applying an oblate ellipsoidal model, which allows a direct evaluation of nanoplatelets’ size and shape in agreement with scanning electron microscopy. The characterised nanoplatelets reveal a transversal size of 20 nm and a longitudinal length in the range 65–92 nm. Our investigation shows that DDLS in resonant condition is a simple and powerful technique to determine the size and shape of plasmonic nanoparticles and it can be successfully applied to characterise the dynamics of metallic nanoplatelets.

Depolarized Dynamic Light Scattering a method to analyse Particle Shape and Size

"Dynamic Light Scattering (DLS) is already a widely used method for small particle size distribution analysis [1]. The main purpose of this method is the determination of particle sizes, respectively the hydrodynamic radius in the sub-microscopic range, i.e. 1 nm up to few µm. It is based on the Brownian motion of those particles. Light scattering methods are non-invasive and therefore a great advantage in the field of particle analysis [2a]. The next generation of Dynamic Light Scattering devices will apply depolarized dynamic light scattering (DDLS) [2b]. This technique allows to obtain beside radius distributions also information about the particle shape. However, for some time technical drawbacks made it almost unfeasible to use it for biological samples. In cooperation with the University of Hamburg we developed the first experimental set-up of a DDLS system to be used in the laboratory to analyze and characterize protein solutions as well as suspensions of nano crystals, suitable for Free-Electron-Laser applications. The fundamental difference to so far known ""standard"" DLS is that the scattered light is separated into two signal pathways, a vertically and a horizontally polarized component, applying a special designed beam splitter. DDLS allows to measure the translational diffusion and the rotational constants simultaneously. Both constants are derived from the decay times of the autocorrelation functions. With the equations of Perrin the system is capable of calculating the axis ratio of the particles, approximating the real particle shape as a rotational ellipsoid. For calibration and tests gold rod particles of 575 nm in length and 25 nm diameter were applied. The first biological sample, which was analyzed by DDLS was hemocyanin from Limulus polyphemus hemolymph [3a], which occurrs predominantly as hexamers, dodecamers and traces of higher aggregates occur at high pH. In summary, together with additional advantages like viscosity independent measurements and ten times higher resolution compared to DLS, the DDLS-technique is optimal to characterize biological samples to be used for crystallization experiments and to score solutions and suspensions of nano-crystals to be used for Free-Electron Laser applications [3b]."

Observation of the slow, Debye-like relaxation in hydrogen-bonded liquids by dynamic light scattering

The slow, Debye-like relaxation in hydrogen-bonded liquids has largely remained a dielectric phenomenon and has thus far eluded observation by other experimental techniques. Here we report the first observation of a slow, Debye-like relaxation by both depolarized dynamic light scattering (DLS) and dielectric spectroscopy in a model hydrogen-bonded liquid, 2-ethyl-4-methylimidazole (2E4MIm). The relaxation times obtained by these two techniques are in good agreement and can be well explained by the Debye model of rotational diffusion. On the one hand, 2E4MIm is analogous to the widely studied monohydroxy alcohols in which transient chain-like supramolecular structure can be formed by hydrogen bonding. On the other hand, the hydrogen-bonded backbone of 2E4MIm is much more optically polarizable, making it possible to apply light scattering to study the dynamics of the supramolecular structure. These findings provide the missing evidence of the slow, Debye-like relaxation in DLS and open the venue for the application of dynamic light scattering to the study of supramolecular structures in hydrogen-bonded liquids.

Interplay Between Hydrophobic Aggregation and Charge Transport in the Ionic Liquid Methyltrioctylammonium Bis(trifluoromethylsulfonyl)imide

In order to understand the nature of the exceedingly low ionic conductivity of aprotic ammonium ionic liquids (ILs), we have measured the charge transport and structural dynamics of methyltrioctylammonium bis(trifluoromethylsulfonyl)imide [m3oa][ntf2] over a broad temperature range using broadband dielectric spectroscopy, depolarized dynamic light scattering (DDLS), rheology, and pulsed field gradient nuclear magnetic resonance. We demonstrate that the low level of ionic conductivity in this material is due to the combined effects of reduced ion mobility as well as reduced free ion concentration relative to other types of ILs. Furthermore, detailed analysis of the DDLS spectra reveals a slow process in addition to the structural α relaxation that we attribute to reorientational motion of alkyl aggregates. These findings indicate that hydrophobic aggregation strongly influences the charge transport mechanism of aprotic ammonium ionic liquids with long aliphatic side chains.

Single Laser Pulse Effects on Suspended-Au-Nanoparticle Size Distributions and Morphology

Samples of suspended gold nanoparticles in the diameter range 10 to 100 nm were subjected to a single 7 ns pulse from a 532 nm laser to determine the effect of laser power on particle size distribution, mean size, and morphology. The experimental techniques used were dynamic light scattering (DLS), depolarized dynamic light scattering (DDLS), electrospray-differential mobility analysis (ES-DMA), ultraviolet–visible absorption spectroscopy, and transmission electron microscopy (TEM). For 60 nm particles, a laser pulse of fluence 10 mJ/cm2 was sufficient to produce observable changes. In the range 10–72 mJ/cm2, DLS indicated little change in mean particle size but a more than three-fold reduction in the polydispersity index (significantly tightened distribution) and a decrease in scattering intensity. TEM showed that the particles became highly spherical and that there was a growing population of particles <10 nm in size that could not be detected by DLS and ES-DMA. Fused dimers were also observed, which su...

Dynamic crossover and the Debye–Stokes–Einstein relation in liquid N,N-diethyl-3-methylbenzamide (DEET)

The dynamic glass transition in the molecular liquid DEET is investigated in wide temperature and pressure ranges using depolarized dynamic light scattering (DDLS), broadband dielectric spectroscopy (BDS), calorimetry, and rheology. It is found that the viscosity and structural α relaxation rates all exhibit an identical type of thermal activation in the measured temperature and pressure ranges. In addition, it is shown that these characteristic quantities exhibit a dynamic crossover at 240 ± 5 K at ambient pressure. Contrary to recent assertions in the literature, it is demonstrated that the dynamic crossover by no means generally implies a violation of the Debye–Stokes–Einstein relation in molecular glass forming liquids.

3D Brownian Diffusion of Submicron-Sized Particle Clusters

We report on the translation and rotation of particle clusters made through the combination of spherical building blocks. These clusters present ideal model systems to study the motion of objects with complex shape. Since they could be separated into fractions of well-defined configurations on a sufficient scale and because their overall dimensions were below 300 nm, the translational and rotational diffusion coefficients of particle doublets, triplets, and tetrahedrons could be determined by a combination of polarized dynamic light scattering (DLS) and depolarized dynamic light scattering (DDLS). The use of colloidal clusters for DDLS experiments overcomes the limitation of earlier experiments on the diffusion of complex objects near surfaces because the true 3D diffusion can be studied. When the exact geometry of the complex assemblies is known, different hydrodynamic models for calculating the diffusion coefficients for objects with complex shapes could be applied. Because hydrodynamic friction must be restricted to the cluster surface, the so-called shell model, in which the surface is represented as a shell of small friction elements, was most suitable to describe the dynamics. A quantitative comparison of the predictions from theoretical modeling with the results obtained by DDLS showed an excellent agreement between experiment and theory.

Multiangle Depolarized Dynamic Light Scattering of Short Functionalized Single-Walled Carbon Nanotubes

We introduce the method of multiangle depolarized dynamic light scattering (MA-DDLS) to characterize the length and diameter of covalently functionalized single-walled carbon nanotubes (SWCNTs). MA-DDLS yields simultaneous characterization of the mean translational and rotational diffusivities of dilute solutions of SWCNTs. By using an anisotropic rigid rod model, we uniquely determine the length and diameter of the SWCNTs from the independent measurements of rotational and translational diffusion. The multiangle depolarized light scattering technique is found to be a fast, noninvasive, and reproducible method for identifying the average length and diameter of SWCNTs in solution.