Experimental investigation of C60/NMP/toluene solutions by UV-Vis spectroscopy and small-angle neutron scattering

The transformation of the C₆₀ fullerene cluster state into C₆₀/N-methylpyrrolidone (NMP) solution after the addition of a nonpolar solvent (toluene, electric permittivity ?= 2.4) is studied. The results of ultraviolet-visible spectroscopy and small-angle neutron scattering measurements are used for comparison of the C₆₀/NMP/toluene system with C₆₀/NMP mixtures with a high-polar solvent (water, ? = 80). As to the observed reorganization of the cluster state, the C₆₀/NMP/toluene system is similar to the C₆₀/NMP/water system. This effect is explained by the formation of charge-transfer complexes in the initial C₆₀/NMP solution. These complexes are thought to be soluble in both binary mixtures. The connection between the cluster-reorganization effect and solvatochromism is discussed.     

Calculation of the cluster size distribution functions and small-angle neutron scattering data for C60/N-methylpyrrolidone

The aggregate growth in a C₆₀/N-methylpyrrolidone (NMP) solution has been considered in the framework of the approach developed earlier for describing the cluster growth kinetics in fullerene polar solutions. The final cluster size distribution functions in model solutions have been estimated for two fullerene aggregation models including the influence of complex formation on the cluster growth using extrapolations of the characteristics of the cluster state and distribution parameters. Based on the obtained results, the model curves of small-angle neutron scattering have been calculated for a C₆₀/NMP solution at various values of the model parameters.     

Impact of a physiological medium on the aggregation state of C<Subscript>60</Subscript> and C<Subscript>70</Subscript> fullerenes

The C₆₀ and C₇₀ fullerene-cluster size distribution in aqueous solutions and a physiological medium is studied via dynamic light scattering. The initial aqueous solutions of fullerenes obtained via different methods are found to contain clusters with a characteristic size of about 100 nm. The additional aggregation of fullerenes is observed after their transfer into a physiological medium (0.9% NaCl) and is established to depend on the preparation method. The cluster-size distribution in a fullerene–pectic-acid mixture is found to vary in water and a physiological medium. The results reveal the need for additional studies of the structure and properties of C₆₀ and C₇₀ molecules, as well as their complexes with medicines, in a physiological medium for medical applications.     

Small-angle neutron scattering in aqueous solutions of fullerene-containing oligopropylene oxides

Propylene-oxide oligomers in heavy water (their molecular mass is ～500, and the concentration C varies from ～0.6 to 5.0 g/dL) and similar systems with C₆₀ and C₇₀ fullerenes and C₆₀(OH) _x fullerenols (x ～ 20), i.e., functionalized oligopropylene oxides, are studied via small-angle neutron scattering. The initial oligomers are found to create spherical micelles (～40 molecules) in the solution. It is ascertained that, in oligopropylene-oxide solutions, the C₆₀, C₇₀, and C₆₀(OH) _x derivatives (～1 wt % of fullerene relative to the oligomer) modify its molecular organization, acting as physical bonds whereby micelles are joined into large-scale linear, twisted, and branched chain superstructures.     

Laser light scattering in micellar solutions

Summary The laser light scattering apparatus used for both total intensity and quasi-elastic light scattering experiments on micellar solutions is described in detail. The absolute calibration of the scattered intensity is obtained by exploiting the existence of a lower critical consolution point in a low-concentration aqueous solution of a nonionic amphiphile (C₁₂E₈). The obtained results suggest that micellar solutions may represent a very convenient light scattering standard for both static and dynamic experiments. Paper presented at the “Meeting on Lyotropics and Related Fields”, held in Rende, Cosenza, September 13—18, 1982.     

Specifics of C<Subscript>60</Subscript> Fullerene Cluster Formation in a Solvent Mixture of Toluene and <Emphasis Type="Italic">N</Emphasis>-Methyl-2-Pyrollidone

The two-level organization of C₆₀ fullerene clusters in solutions of C₆₀ in pure toluene and toluene/N-methyl-2-pyrrolidone solvent mixtures is studied by small-angle X-ray scattering (SAXS). The SAXS data for freshly prepared solutions are compared with the data obtained by dynamic light scattering, a technique we use to assess the temporal stability of the prepared solutions. For all solutions in the mixed solvent, regardless of the ratio between the polar and nonpolar components, the UV?Vis absorption spectra tend to become featureless with time. We attribute this behavior primarily to the presence of the polar component in the molecular environment of fullerene molecules.     

On the Supermolecular Structure of Fullerene C60 Solutions

Small angle X‐ray scattering (SAXS) and wide angle X‐ray scattering (WAXS) techniques were used for investigation of fullerene C₆₀ solutions in toluene and p‐xylene. On all SAXS curves, intensity decreases to some constant value of I_C with increase of scattering angle. The value of I_C depends on concentration non‐monotonically: it first slightly increases, then drops sharply to some minimal value, and then increases again. A qualitative explanation of such dependence is offered. It is supposed that the presence of fullerene C₆₀ in solution suppresses thermal fluctuations of density in the solvent. In combination with the X‐ray data the results obtained for solutions of fullerene C₆₀ by various others techniques (calorimetry, densimetry, etc.) are discussed. Possible models of a supermolecular structure of fullerene C₆₀ solutions in good solvents are considered.     

Formation of fullerene clusters in carbon disulfide: Data on small-angle neutron scattering and molecular dynamics

Fullerene solutions in carbon disulfide are studied by small-angle neutron scattering (SANS). In addition to earlier experiments on the given system, the range of measured transmitted impulses is extended and the influence of solution preparation methods on C₆₀ cluster formation in these solutions is studied. It is shown that the formation of large C₆₀ clusters (with a size of about 10 nm) is due to nonequilibrium methods of solution preparation. For nonequilibrium dissolution, there is a 10% excess of the observed fullerene size in the solution over the calculated value. It has been established by simulation of the C₆₀/CS₂ interface by molecular dymanics methods that inclusion of how solvent molecules are organized on the C₆₀ surface leads to a decrease in the fullerene size in the solution, observed by using SANS. In this paper, the effect of excess R _g is explained by the presence of small clusters in the solution (approximately 10% of dissolved C₆₀ molecules). It is discovered that there is a time variation in the concentration of the saturated solution. The explanation of this effect using a model of formation and sedimentation of large clusters (with a size of 100 nm or more) is proposed.     

Low-frequency Raman scattering in a polycrystalline C60 film: The role of orientational disorder

Low-frequency Raman scattering in the orientationally disordered phase of a polycrystalline C₆₀ film is investigated. By analogy with disordered media (glasses), the low-frequency Raman spectra are interpreted in terms of light scattering by localized vibrational states.     

Determination of C60/C70 ratios in fullerene mixtures and film characterization by scanning tunneling microscopy

Fullerene powder mixtures with different C₆₀/C₇₀ ratios have been analyzed by a variety of techniques, and results have been compared. The fullerence mixtures have been characterized as solutions in n-hexane by high-pressure liquid chromatography (HPLC) and UV-VIS spectroscopy. Thin films of fullerenes on Au(111) have been prepared from the mixtures by sublimation. The sublimation process has been studied by simultaneous thermogravimetric and differential thermal analyses. Thin fullerene films on Au(111) have been investigated by scanning tunneling microscopy (STM). The STM images show primarily two types of ballshaped molecules arranged in a lattice with hexagonal symmetry (fcc(111) face, nearest neighbour distance: 1 nm). The two species differ in diameter. STM images of films made of mixtures of different C₆₀/C₇₀ ratios show that C₇₀ molecules display a larger apparent diameter (0.8 nm) and corrugation than C₆₀ molecules (0.7 nm). The C₆₀/C₇₀ ratios obtained by counting the corresponding molecular species in the STM images of the thin films are compared to the C₆₀/C₇₀ ratios determined by HPLC on hexane solutions of the mixtures. The observed differences might be explained by different rates of sublimation for the two species. The STM images reveal film defects (vacancies and boundaries) and dynamic processes (displacement of C₇₀ molecules and vacancies). In films prepared to have a C₆₀ coverage of less than one monolayer, stable structural units of the C₆₀(111) surface consisting of three or seven C₆₀ molecules are revealed by STM. Occasionally, substructure within individual fullerene molecules is observed.     

Bimodal dependence of light scattering/fluctuations on the concentration of aqueous solutions

Two concentration ranges (from 10^?5 to 10^?9 and from 10^?13 to 10^?18 M) corresponding to enhanced fluctuations of Rayleigh and Raman scattering of second-harmonic (527 nm) pulses of YVO₄:Nd³⁺ laser are found for aqueous solutions of antioxidant potassium phenosan. A correlation is revealed between the rise in elastic Rayleigh scattering intensity and its fluctuations and the shift of the center of OH Raman band of water toward the ice component characteristic frequency (3200 cm^?1). The development of phase-equilibrium instabilities is analyzed based on the model of fluctuations of the number of hydrogen bonds on the assumption of formation/destruction of ordered hydration layer of phenosan molecules in water.     

Dispersion of the acoustic phonon concerned with C66 of KD2PO4 observed by light scattering

we vector dependence of the light scattering spectra of DKDP is investigated for the scattering angles π/4, π/2 and 3π/4. Brillouin shift concerned with an elastic stiffness C₆₆ is obtained from the angular dependence of the quasi-longitudinal and quasi-transverse mode frequencies in the ab plane observed in the VV scattering. The results indicate that the phase velocity associated with C₆₆ decreases slightly near T_tr in the case of π/4 scattering, but does not in π/2 and 3π/4 scatterings.     

The effect of water on the stability of C<Subscript>60</Subscript> fullerene nanowhiskers

The morphology of C₆₀ precipitates synthesized by using isopropyl alcohol (IPA) added with water was investigated in order to know the effect of water on the growth of C₆₀ nanowhiskers (C₆₀NWs) in C₆₀–toluene–IPA solution systems. The stability of C₆₀NWs decreased and granular crystals of C₆₀ were formed in the solutions when IPA added with an excess amount of water was used in the liquid–liquid interfacial precipitation method. The C₆₀NWs were found to be destabilized with time in the solutions added with water. The C₆₀NWs dried in air showed similar Raman profiles irrespective of the use of IPA with and without water addition. The Raman profiles of granular C₆₀ single crystals showed the base lines much flatter than those of C₆₀NWs, indicating that C₆₀NWs possess a disordered crystal structure. By optimizing the growth condition, short C₆₀NWs with aspect ratios ranging from 3 to 10 and an average length of about 1.8 μm were successfully fabricated. The short C₆₀NWs are expected to be applicable for electrodes of organic thick film solar cells.     

Dynamic light scattering by charged silicon nanoparticles in colloid

The experimental results of diameter measurament silicon nanoparticles with using dynamic light scattering method are presented in this article. Colloids of nanosilicon in acetone, in methanol and in water were studied. The measurements were taken with nanotrak device (“Photocor complex,” dynamic light scattering instrument, produced by Photocor Instruments Inc.) during regular time intervals (about several minutes). The results from each solution were compared with the results in other solutions and the stable ones were examined. Results obtained in water appeared to be nonrecurrent. Electrical double layer of nanosilicon particles in liquid had been measured for all samples. It was established that the reason of such behavior of n-Si in water solution was double charge layer which changed hydrodynamical parameters of water.     

Polarized-neutron scattering in aqueous solutions of fullerenols in a magnetic field

The aqueous solutions of mixtures (T = 25°C) of paramagnetic Gd@C₈₂(OH) _x and diamagnetic C₈₂(OH) _x fullerenols, where x ～ 30, are studied via small-angle polarized-neutron scattering under the conditions of transition from diluted to concentrated systems whose solubility threshold is close to that of fullerenols. When the induction B of an external field varies from 0.001 to 1.0 T, the molecular correlation radius of solutions is R _C ～ 15–20 nm and the aggregation number reaches ～5 × 10⁴ with increasing fullerenol content (C = 0.04?2.0 wt %). Such changes are coupled with both paramagnetic Gd@C₈₂(OH) _x molecules and interactions between the induced diamagnetic moments of fullerenols introduced into aggregates.     

Velocity of hypersounds in lithium hydride by spontaneous brillouin scattering

The elastic constants of lithium hydride have been measured, at room temperature, by means of Brillouin scattering for frequencies of about 60 GHz. The results are C₁₁=6.71, C₁₂=1.7 andC₄₄=4.60 (units 10¹⁰Nm^-2). The values of C₁₁ and C₁₂ are slightly higher than that obtained for ultrasonic frequencies. The strong departure from the Cauchy relation is corroborated.     

Study of CdSe/CdS quantum dots in solutions and gels by small-angle X-ray scattering

The sizes of semiconductor nanocrystals of CdSe/CdS quantum dots (QDs) synthesized by the colloidal method were estimated using small-angle X-ray scattering. The distribution of QD nanocrystals in organic solvents of different polarities and in polymer gels and matrices is studied. Structural invariants of scattering QD particles (heterogeneities of the electron density)—namely, inertia radii and sizes, forms, and dispersive composition of particles—are determined. The contribution of scattering by QDs in solutions and gels is calculated. The effective sizes of particles and their aggregates are determined, and the parameters of the distribution over the QD sizes in organic solvents and polymer matrices are estimated. The typical distance between particles in samples is determined. The position of the maximum at the beginning of the small-angle scattering curves corresponds to the distance d _m = 2π/h ₀ between the planes (here, h ₀ is the position of the maximum on the scale h). It is 74–76.9 ? for solutions, 60 ? for gels, and 99 ? for polymer matrices with concentrations of up to 0.15% and 77 ? for those with the concentrations exceeding 0.15%, which is close to the estimation of the sizes of separate CdSe QDs that was obtained from the distribution histograms (60–80 ?). This result shows that CdSe/CdS QDs introduced in the polymer matrices disperse to form either separate particles or small aggregates and located at a distance on the order of 80 ? from each other.     

Analysis of dynamic light scattering of poly(N-isopropylacrylamide) across the collapse transition

Summary We analyse data from the dynamic light scattering of poly(N-isopropylacrilamide) in water solution as we cross the collapse transition. Experimental data are interpreted by the Gaussian self-consistent Zimm model that takes into account two- and three-body excluded-volume effects, and Oseen hydrodynamic interactions, as well as by the standard cumulant and Contin analyses. By fitting the dynamic structure factor we extract the temperature dependence of the diffusion coefficientD and the first relaxation time τ₁ across the collapse transition for a range of scattering angles. The relaxation time τ₁ possesses a characteristic peak at about 32.4 °C due to slowing of the internal motions of the polymer at the theta-point, and a minimum at 33.4 °C. We interpret this as a combination of collapse closely followed by the growth of critical correlations. At large scattering angles we reach the universalk ³ regime, and observe that this behaviour vanishes at the onset of collapse transition. Paper presented at the I International Conference on Scaling Concepts and Complex Fluids, Copanello, Italy, July 4–8, 1994.     

Effect of Mannosylerythritol lipid-A on light scattering of AOT/D<Subscript>2</Subscript>O/Octane

The light scattering technique is used for the study of interaction of Mannosylerythritol lipid-A on AOT/D₂O/Octane. The collective diffusion of AOT/D₂O droplets soluble in Octane mixed with lipid is founded from a correlation function of light scattering. We focus on the variation of the dynamic behavior of droplets as a function of the lipid concentrations and the size of droplets. The increase of concentration of Mannosylerythritol lipid-A on microemulsion decreases the dynamic of droplets. The SAXS experiment shows the size and the interaction of the droplets change by increase of Mannosylerythritol lipid-A concentration. A hard sphere model can describe the interaction of lipid with AOT/D₂O droplets.