Rotational Diffusion Dynamics Research Articles

Molecular-Scale Interactions in the Choline Chloride-Ethylene Glycol Deep Eutectic Solvent System: The Importance of Chromophore Charge in Mediating Rotational Dynamics.

We report on the rotational diffusion dynamics of three chromophores (disodium fluorescein, oxazine 725, and perylene) in a series of choline chloride-ethylene glycol (ChCl:EG) deep eutectic solvent (DES) systems. We observe behavior independent of DES bulk viscosity for the cationic and neutral probes and behavior that is consistent with stick-limit interactions for the modified Debye-Stokes-Einstein model for the anionic probe. This finding indicates that the anionic species is integral to the interactions between DES constituent species that are responsible for local organization, consistent with previous MD simulations that showed higher interaction energies associated with both the hydrogen bond donor (EG) and hydrogen bond acceptor (Ch+) interactions with Cl- in ChCl:EG mixtures. The reorientation data reported here also indicate a region around 15 mol % ChCl where the stoichiometric relationship between the species gives rise to changes in the details of intermolecular interactions.

Diffusion dynamics of an overdamped active ellipsoidal Brownian particle in two dimensions

Shape asymmetry is the most abundant in nature and has attracted considerable interest in recent research. The phenomenon is widely recognized: a free ellipsoidal Brownian particle displays anisotropic diffusion during short time intervals, which subsequently transitions to an isotropic diffusion pattern over longer timescales. We have further expanded this concept to incorporate active ellipsoidal particles characterized by an initial self-propelled velocity. This paper provides analytical and simulation results of diffusion dynamics of an active ellipsoidal particle. The active ellipsoidal particle manifests three distinct regimes in its diffusion dynamics over time. In the transient regime, it displays diffusive behavior followed by a super-diffusive phase, and in the longer time duration, it transitions to purely diffusive dynamics. We investigated the diffusion dynamics of a free particle as well as a particle in a harmonic trap, and a particle subject to a constant field force. Moreover, we have studied the rotational diffusion dynamics and torque production resulting from an external constant force field. Furthermore, our investigation extends to the examination of the scaled average velocity of an ellipsoidal active particle, considering both a constant force field and a one-dimensional ratchet.

Nanorod Diffusion near the Solid-Liquid Interface with Varied Wall Nonuniformity.

The complex diffusion behaviors of rod-shaped nanoparticles near the solid-liquid interface are closely related to various biological processes and technological applications. Despite recent advancements in understanding the diffusion dynamics of nanoparticles near some specific solid-liquid interfaces, systematical studies to tune the interfacial interaction or fabricating nonuniform wall to see their effects on the nanorod (NR) diffusion are still lacking. This work utilized molecular dynamics simulations to investigate the rotational and translational diffusion dynamics of a single NR near the solid-liquid interface. We constructed a patterned wall featuring adjustable nonuniformity, which was accomplished by modifying the interaction between NR and the wall, noting that the resulting nonuniformity limits both the translational and rotational diffusion of NR, evident from decreases in diffusion coefficients and exponents. By trajectory analysis, we categorized the diffusion modes of NRs near the patterned wall with varied nonuniformities into three types: Fickian diffusion, desorption-mediated flight, and in-plane diffusion. Furthermore, energy analysis based on the adsorption-desorption mechanism has demonstrated that the three diffusion states are driven by interactions between the NR and the wall, which are primarily influenced by rotational diffusion. These results could significantly deepen the understanding of anisotropic nanoparticle interfacial diffusion and would provide new insights into the transport mechanisms of nanoparticles within confined environments.

Effects of Nanoconfinement on Dynamics in Concentrated Aqueous Magnesium Chloride Solutions.

Water behavior in various natural and manufactured settings is influenced by confinement in organic or inorganic frameworks and the presence of solutes. Here, the effects on dynamics from both confinement and the addition of solutes are examined. Specifically, water and ion dynamics in concentrated (2.5-4.2 m) aqueous magnesium chloride solutions confined in mesoporous silica (2.8 nm pore diameter) were investigated using polarization selective pump-probe and 2D infrared spectroscopies. Fitting the rotational and spectral diffusion dynamics measured by the vibrational probe, selenocyanate, with a previously developed two-state model revealed distinct behaviors at the interior of the silica pores (core state) and near the wall of the confining framework (shell state). The shell dynamics are noticeably slower than the bulk, or core, dynamics. The concentration-dependent slowing of the dynamics aligns with behavior in the bulk solutions, but the spectrally separated water-associated and Mg2+-associated forms of the selenocyanate probe exhibit different responses to confinement. The disparity in the complete reorientation times is larger upon confinement, but the spectral diffusion dynamics become more similar near the silica surface. The length scales that characterize the transition from surface-influenced to bulk-like behavior for the salt solutions in the pores are discussed and compared to those of pure water and an organic solvent confined in the same pores. These comparisons offer insights into how confinement modulates the properties of different liquids.

Rotational dynamics study of structurally similar (medium sized) coumarin dyes in aqueous mixtures of DMSO and DMA

The rotational diffusion dynamics of four medium sized, structurally similar, polar Coumarin dyes namely, Coumarin-478 (C478), Coumarin-480 (C480), Coumarin-519 (C519), and Coumarin-523 (C523) has been studied at room temperature in aqueous DMSO and aqueous DMA by using steady state and time resolved fluorescence depolarization techniques. All the probes exhibited faster rotation in organic solvent rich zone than in water rich zone that resulted in a downward bent “hook profile” of rotational reorientation time as a function of viscosity. A faster rotational diffusion is observed for C523 in contrast to the other three solutes in both the aqueous solvent mixtures. The difference between τr values at iso-viscous points is smaller in case of aqueous DMA than in aqueous DMSO which reveals the importance of dielectric friction. Since both solutes and solvents are polar in nature, the Nee-Zwanzig (NZ) and van der Zwan and Hynes (ZH) dielectric friction theories have been used along with Stokes-Einstein-Debye (SED) hydrodynamic theory to assess the experimental results and understand the microfriction experienced by the solute. An important aspect of this work is to establish a relation between viscosity and hydrogen bond strengths at varying compositions of solvent mixtures as well as hydrogen bond strength between solute and solvents with the help of Gaussian 09 software. The H-bond strength thus calculated is found to be higher at a composition where the viscosity is the maximum. It provides an additional support to the experimental results.

Assessing the impact of increase in the number of hydroxyl groups on the microscopic behaviors of ammonium-based room temperature ionic liquids: A combined fluorescence up-conversion, fluorescence correlation and NMR spectroscopic study

The current study aims to understand the impact of variation of number of hydroxyl groups on the cationic head of ammonium-based room temperature ionic liquids (RTILs) towards inter/intra molecular hydrogen bonding interaction, local structural organization and dynamics of the solvent systems. For this purpose, three hydroxyl functionalized ammonium based RTILs (HFILs) bearing different numbers of hydroxyl groups on the cationic head as well as a non-hydroxyl ammonium based RTIL have been examined using both ensembled average and single-molecule spectroscopy techniques. Investigation of solvent relaxation dynamics of all the concerned RTILs by the combination of femto-second fluorescence up-conversion techniques and time corelated single photon counting techniques reveals a bimodal solvent relaxation behaviour having a very fast sub-picosecond and a relatively slower picosecond to nanosecond solvation time component for all the RTILs. Interestingly, analysis of the rotational and translational diffusion dynamics of a few particular solutes shows that the solvent–solvent interaction in the poly-hydroxyl-based HFILs is substantially stronger than the solute–solvent interaction. Additionally, analysis of the rotational diffusion data reveals that all RTILs exhibit significant dynamic heterogeneity, which increases with increase the number of hydroxyl groups on the cationic head of HFILs. Moreover, PFG-NMR study have shown that the HFILs had considerably greater hydrodynamic radii than the non-hydroxyl RTILs, which is likely due to the result of stronger hydrogen bonding interaction between the hydroxyl groups and the constituent of the HFILs. The outcomes of all these investigations have essentially demonstrated that subsequent addition of hydroxyl functionalities to the cationic head of the RTILs significantly alter the intra/inter molecular interaction, local structural organisation and heterogeneity of the medium.

Rotational Diffusion Dynamics of Fluorescein Derivatives in Binary Mixtures of Solvents: An Experimental and Computational Study

With a view to understand the nature of solute solvent interactions, rotational reorientation times (τr) of three medium sized dipolar laser dyes viz., dichlorofluorescein (DCF), sodium fluorescein (SF) and kiton red (KR) in two binary mixtures namely, aqueous-DMSO and aqueous-1-propanol have been determined employing steady state fluorescence depolarization technique. The experimental results are analyzed in the light of SED hydrodynamic and of Gierer and Wirtz (GW) and Dote, Kivelson and Schwartz (DKS) quasihydrodynamic models. Rotational reorientation times (τr) are plotted as function of viscosity (η) on the binary solvent mixtures. An interesting hook shaped profile is observed in both the binary mixtures of solvents that is likely to shed light on solute-solvent interactions. Further, theoretical study has been carried out using Gaussian 09 software. The optimized geometry, HOMO-LUMO, energy gap and molecular electron potential map (MEPM) were extracted from DFT/B3LYP 6-311g(d) basis set. The hyper conjugation or intra-molecular delocalization was estimated from NBO analysis. Strong interactions were observed between nO33→σ*C31, πN38→σ*C12 and πO32→π*(C31- O33) with E(2) energies of 203.58, 121.89 and 39.92 kJ/mol for SF, KR and DCF.

Rotational diffusion dynamics of Alexa flour dyes in aqueous organic environment

The rotational reorientation times of three dye probes namely Alexa fluor-350 (neutral but polar), Alexa fluor-430 (monoanion) and Alexa fluor-488 (dianion) were determined in series of binary mixtures of DMSO-water, DMA-water, and 2-propanol-water. All the three series of mixtures show bivalued profile for viscosity as a function of mole fraction of organic solvent in water. The dielectric properties such as dielectric constant (ε) and Debye dielectric relaxation time (τD) of solutions change considerably across the composition range. The variation of rotational reorientation time (τr) with viscosity (η) for all the probes is studied. Alexa fluor 350 and alexa fluor 488 show hook type profile in all the three series of aqueous mixtures with rotational reorientation time (τr) being longer in organic solvent rich zone compared to water rich zone mainly due to dielectric friction and hydrogen bonding. Alexa fluor 430 shows hook type profile in 2-propanol-water mixtures similar to other two probes but in DMSO-water and DMA-water it has almost linear profile as rotational reorientation dynamics is almost similar in both organic solvent rich zone and water rich zone. The hook type profiles obtained suggest the importance of local molecular structure of binary mixture and its interaction with probe. Results obtained are discussed in light of SED (hydrodynamic) theory, dielectric friction theories and friction due to hydrogen bonding.

Multistable interaction between a spherical Brownian particle and an air-water interface.

We report the measurement of the interaction energy between a charged Brownian polystyrene particle and an air-water interface. The interaction potential is obtained from the Boltzmann equation by tracking particle interface distance with a specifically designed Dual-Wave Reflection Interference Microscopy (DW-RIM) setup. The particle has two equilibrium positions located at few hundreds of nanometers from the interface. The farthest position is well accounted by a DLVO model complemented by gravity. The closest one, not predicted by current models, more frequently appears in water solutions at relatively high ions concentrations, when electrostatic interaction is screened out. It is accompanied by a frozen rotational diffusion dynamics that suggests an interacting potential dependent on particle orientation and stresses the decisive role played by particle surface heterogeneities. Building up on both such experimental results, the important role of air nanobubbles pinned on the particle interface is discussed.

Proton Abstraction Mediates Interactions between the Super Photobase FR0-SB and Surrounding Alcohol Solvent.

We report on the motional and proton transfer dynamics of the super photobase FR0-SB in the series of normal alcohols C1 (methanol) through C8 (n-octanol) and ethylene glycol. Steady-state and time-resolved fluorescence data reveal that the proton abstraction dynamics of excited FR0-SB depend on the identity of the solvent and that the transfer of the proton from solvent to FR0-SB*, forming FR0-HSB+*, fundamentally alters the nature of interactions between the excited molecule and its surroundings. In its unprotonated state, solvent interactions with FR0-SB* are consistent with slip limit behavior, and in its protonated form, intermolecular interactions are consistent with a much stronger interaction of FR0-HSB+* with the deprotonated solvent RO-. We understand the excited-state population dynamics in the context of a kinetic model involving a transition state wherein FR0-HSB+* is still bound to the negatively charged alkoxide, prior to solvation of the two charged species. Data acquired in ethylene glycol confirm the hypothesis that the rotational diffusion dynamics of FR0-SB* are largely mediated by solvent viscosity while proton transfer dynamics are mediated by the lifetime of the transition state. Taken collectively, our results demonstrate that FR0-SB* extracts solvent protons efficiently and in a predictable manner, consistent with a ca. 3-fold increase in dipole moment upon photoexcitation as determined by ab initio calculations based on the equation-of-motion coupled-cluster theory.

Liquid Structure and Dynamics of Tetraalkylammonium Bromide-Based Deep Eutectic Solvents: Effect of Cation Chain Length.

Deep eutectic solvents (DESs) have emerged in recent years as environmentally sustainable media across several fields. However, knowledge of liquid structure, dynamics, and solute-solvent interactions in many DESs that is essential for exploiting their potential is still lacking. In this work, we make an attempt to obtain some insight into these aspects of a set of less-explored DESs comprising tetraalkylammonium bromide salts and ethylene glycol (EG) by monitoring the fluorescence response of some carefully chosen dipolar (C153 and 4-AP) and nonpolar (9-PA) solutes in these media. Specifically, we have studied the translational and rotational diffusion dynamics of these molecular systems using single-molecule-based fluorescence correlation spectroscopy technique and ensemble-based time-resolved fluorescence anisotropy measurements. These results point to spatial and dynamic heterogeneity of these DESs, which becomes prominent in systems comprising cations with a longer alkyl chain length. This study reveals that diffusion dynamics of the probe molecules is determined not only by the solvent bulk viscosity but also dependent on their microenvironments and solute-solvent interactions experienced in these media.

Photophysics and rotational diffusion dynamics of large prolate non-polar laser dyes

The present work deals with experimental determination of steady state fluorescence anisotropies, fluorescence lifetimes and consequentially the rotational reorientation times of three large, nonpolar laser dyes that are modelled as prolate ellipsoids. Steady state and time resolved fluorescence spectroscopic measurements on Exalite 404 (E404), Exalite 417 (E417) and Exalite 428 (E428) dyes in series of alkane and alcohol solutions are discussed. All the three probes are observed to exhibit significantly shorter reorientation times in series of alcohols as compared to alkanes. The experimental results are explained in light of SED hydrodynamic and quasihydrodynamic theories. It is for the first time DKS theory is found to correctly predict the experimental results in alkanes with precision for all the three probes. Particularly in case of E417 DKS theory correlates exceptionally well with predictions of slip hydrodynamics. Interestingly, the largest probe (E428) being reported for the first time, exhibits slip behaviour in alkanes and alcohols; behaviour in higher alcohols as well as alkanes. This suggests the existence of nonhydrodynamic forces and speculates that the straightforward relation between the probe size and the nature of their behaviour may not be appropriate. Further, the nature and geometries of probes were fully explored and characterized using NBO and DFT studies employing Gaussian09 program. Optimized geometries, energy band gap and HOMO-LUMO levels were determined from DFT exchange-correlation function B3LYP with 6-311g basis set. Inter and intra hyper-conjugative interactions were estimated from NBO analysis. A very strong interactions between π(C19C21) → π⁎(C24C25), π(C1C6) → π⁎(C2C3) and π(C33C34) → π⁎(C28C30) with E(2) energies 21.44, 21.75 and 22.75 kcal/mol were observed for E404, E417 and E428, respectively. Electron occupancies and p-character were also determined for these molecules.

Solute Rotation and Translation Dynamics in an Ionic Deep Eutectic Solvent Based on Choline Chloride.

Deep eutectic solvents (DESs) are an emerging class of environment-friendly media useful in a variety of applications. However, the microscopic structure of these liquids is quite unclear, and issues like whether spatial and dynamic heterogeneity is a generic feature of the ionic DESs and whether the solute molecules experience similar environment and interactions with the medium irrespective of their charge are still open. In this work, we have attempted to address some of these issues for ethaline, a less viscous and ionic DES consisting of a mixture of 1:2 mole ratio of choline chloride and ethylene glycol by monitoring the fluorescence response of a number of carefully chosen neutral and charged probe molecules in ensemble and single molecule conditions. Specifically, we have examined the liquid state structure of ethaline by studying the rotational and translational diffusion dynamics of the solutes measured by monitoring the time dependence of fluorescence anisotropy in ensemble condition and fluorescence correlation signal of extremely dilute samples diffusing through confocal volume. These studies clearly reveal dynamic heterogeneity of the medium, though no spatial heterogeneity is observable through excitation wavelength dependent fluorescence measurements. The insights obtained from this study will be helpful in understanding the nature of solute-solvent interactions in this type of complex media.

Charge-Induced Long-Range Order in a Room-Temperature Ionic Liquid.

We report direct evidence for charge-induced long-range (ca. 100 μm) order in the room-temperature ionic liquid (IL) 1-butyl-3-methylimidazolium tetrafluoroborate (BMIM(+)BF4(-)), supported on a silica surface. We have measured the rotational diffusion dynamics of anionic, cationic, and neutral chromophores as a function of distance from a silica surface. The results reflect the excess charge density gradient induced in the IL by the (negative) charge present on the silica surface. Identical measurements in ethylene glycol reveal spatially invariant reorientation dynamics for all chromophores. Capping the silica support with Me2SiCl2 results in spatially invariant reorientation dynamics in the IL. We understand these data in the context of the IL exhibiting a spatially damped piezoelectric response mediated by IL fluidity and disorder.

Probing molecular dynamics at the nanoscale via an individual paramagnetic centre.

We demonstrate a protocol using individual nitrogen-vacancy centres in diamond to observe the time evolution of proton spins from organic molecules located a few nanometres from the diamond surface. The protocol records temporal correlations among the interacting protons, and thus is sensitive to the local dynamics via its impact on the nuclear spin relaxation and interaction with the nitrogen vacancy. We gather information on the nanoscale rotational and translational diffusion dynamics by analysing the time dependence of the nuclear magnetic resonance signal. Applying this technique to liquid and solid samples, we find evidence that liquid samples form a semi-solid layer of 1.5-nm thickness on the surface of diamond, where translational diffusion is suppressed while rotational diffusion remains present. Extensions of the present technique could be exploited to highlight the chemical composition of molecules tethered to the diamond surface or to investigate thermally or chemically activated dynamical processes such as molecular folding.

Detection and characterization of liquid|solid and liquid|liquid|solid interfacial gradients of water nanodroplets in wet N-octyl-2-pyrrolidone.

We report on the rotational diffusion dynamics and fluorescence lifetime of lissamine rhodamine B sulfonyl chloride (LRSC) in two thin-film experimental configurations. These are liquid|solid interfaces, where N-octyl-2-pyrrolidone (NOP) containing water and ethylene glycol (EG) thin films are each supported on glass, and a liquid|liquid|solid interface where thin films of water and NOP, both supported on glass, are in contact with one another, forming an NOP|water interface. The reorientation dynamics and fluorescence lifetime of LRSC are measured as a function of distance from the NOP|glass and EG|glass interfaces and from the NOP|water and NOP|glass interfaces in the liquid|liquid|solid experimental configuration. Fluorescence anisotropy decay data from the liquid|solid systems reveal a liquid film depth-dependent gradient spanning tens of micrometers from the NOP|glass interface into the wet NOP phase, while this gradient is absent in EG. We interpret these findings in the context of a compositional gradient in the NOP phase. The spatially resolved fluorescence lifetime and anisotropy decay data for an NOP|water|glass interfacial structure exhibits the absence of a gradient in the anisotropy decay profile normal to the NOP|water interface and the presence of a fluorescence lifetime gradient as a function of distance from the NOP|water interface. The compositional heterogeneity for both interfacial systems is in the form of water nanodroplets in the NOP phase. We understand this compositional gradient in the context of the relative surface energies of the water, NOP, and glass components.

Nanodynamics of Dendritic Core–Multishell Nanocarriers

The molecular dynamics of polymeric nanocarriers is an important parameter for controlling the interaction of nanocarrier branches with cargo. Understanding the interplay of dendritic polymer dynamics, temperature, and cargo molecule interactions should provide valuable new insight for tailoring the dendritic architecture to specific needs in nanomedicine, drug, dye, and gene delivery. Here, we have investigated polyglycerol-based core-multishell (CMS) nanotransporters with incorporated Nile Red as a fluorescent drug mimetic and CMS nanotransporters with a covalently bound fluorophore (Indocarbocyanine) using fluorescence spectroscopy methods. From time-resolved fluorescence depolarization we have obtained the rotational diffusion dynamics of the incorporated dye, the nanocarrier, and its branches as a function of temperature. UV/vis and fluorescence lifetime measurements provided additional information on the local dye environment. Our results show a distribution of the cargo Nile Red within the nanotransporter shells that depends on solvent and temperature. In particular, we show that the flexibility of the polymer branches in the unimolecular state of the nanotransporter undergoes a temperature-dependent transition which correlates with a larger space for the mobility of the incorporated hydrophobic drug mimetic Nile Red and a higher probability of cargo-solvent interactions at temperatures above 31 °C. The measurements have further revealed that a loss of the cargo molecule Nile Red occurred neither upon dilution of the CMS nanotransporters nor upon heating. Thus, the unimolecular preloaded CMS nanotransporters retain their cargo and are capable to transport and respond to temperature, thereby fulfilling important requirements for biomedical applications.

Phospholipid vesicle stability and temporal variations in acyl chain organization

We report on our investigation of the long-term dimensional stability and acyl chain organization of unilamellar vesicles containing 1,2-dimyristoyl-sn-phosphatidylcholine (DMPC) and DMPC with cholesterol. Vesicles of 100% DMPC, 80% DMPC/20% cholesterol and 70% DMPC/30% cholesterol, formed by extrusion in aqueous buffer solution (pH 8) were shown to remain dimensionally stable for periods in excess of 600h by dynamic light scattering (DLS) measurements. The rotational diffusion dynamics of perylene confined in the vesicle acyl chain region revealed structural evolution that was dependent on vesicle composition. Re-extrusion of the vesicles caused no changes in the average diameter or size distribution, but did give rise to diminished organization in the lipid acyl chain region for DMPC vesicles. Cholesterol-containing vesicles exhibited somewhat less pronounced change in organization on re-extrusion, suggesting a structurally mediating role for cholesterol.

A theoretical study of rotational and translational diffusion dynamics of molecules with a six-fold point symmetry adsorbed on a hexagonal lattice by neutron scattering

A complete analytical model for the rotational and translational diffusion of molecules with a six-fold point symmetry on a hexagonal lattice is presented. It can be applied, in particular, to the diffusion of benzene molecules adsorbed flat on the basal plane of graphite in the case of incoherent scattering. Under the weak hindered approximation, the classical mechanics framework and making use of the van Hove formalism of correlation functions, the intermediate scattering function and its Fourier transform, the scattering law, are both obtained. They can be expressed as sums of exponential decays or Lorentzian functions, respectively, containing the contribution of each of the dynamical processes taking place. In the case of benzene lying flat on the substrate we expect translational diffusion, continuous rotations of isolated molecules and hindered rotations of molecules within clusters. Each particular diffusive mechanism can be recognized owing to its particular signature in the dependence of the quasi-elastic broadening on the momentum transfer.

Evaluating the Sensitivity of Lipid Headgroup-Bound Chromophores to Their Local Environment

We report on the steady state and time-resolved fluorescence behavior of the chromophore 1,2-dimiryristoyl-sn-glycero-3-phosphoethanolamine-N-lissamine rhodamine B sulfonyl ammonium salt (SR-DMPE) in a series of solution phase and lipid bilayer environments. The issue of interest is whether or not the lipid headgroup-bound chromophore is sensitive to its local environment under conditions where vesicles have not been formed in lipid-containing mixtures and where unilamellar vesicles have been formed by extrusion. Our data point to the strong interaction of SR-DMPE with 1,2-dimirystoyl-sn-glycero-phosphocholine (DMPC) in solution whether or not the solution has undergone extrusion. The amount of SR-DMPE in the lipid-containing systems affects both the steady state and time-resolved spectroscopic response. Excitation of the chromophore to the S(2) state deposits sufficient excess energy into the system to influence its rotational diffusion dynamics, demonstrating significant interactions between SR-DMPE and DMPC. Comparison of SR-DMPE reorientation dynamics in DMPC-containing solutions with corresponding data on SR-DMPE in aqueous solution indicates that the lipids impose a restrictive local environment on the chromophore that is a factor of ca. 10 more viscous than an aqueous environment. The similarity of the reorientation data in all DMPC-containing solutions suggests that SR-DMPE is a local probe that is not sensitive to longer range organization.