Birefringence and scattering of light in colloidal solutions of magnetite in kerosene

The birefringence and dynamic and static scattering of light in colloidal solutions of magnetite nanoparticles in kerosene with different concentrations of the solid phase have been investigated. It is shown that these solutions contain both individual colloidal particles about 12 nm in diameter and their aggregates up to 100?600 nm in diameter. The largest aggregates are formed in solutions with the lowest concentration (on the order of 0.001 vol % or lower). The presence of relatively large aggregates makes it possible to observe specific features of optical anisotropy relaxation in these solutions, which are related to the non-Rayleigh character of light scattering from magnetite-particle aggregates.     

Characterization of the structure and the size distribution of branched polymers formed by co-polymerization of MMA and EGDMA

Free radical co-polymerization of methyl methacrylate (MMA) and ethyl glycol dimethyl methacrylate (EGDMA) in solution leads to the formation of polydisperse branched PMMA which grows in size until the system gels. The structure and the size distribution of the PMMA aggregates were characterized at infinite dilution using static and dynamic light scattering and size exclusion chromatography (SEC). The reaction extent was measured using SEC and Raman spectroscopy. The results show that the structure and size distribution of PMMA aggregates formed close to the gel point are compatible with those of percolating clusters. The structure factor of semi-dilute solutions of PMMA aggregates is the same as that of dilute solutions at distance scales much smaller than the correlation length of the concentration fluctuations (). However, the cut-off function of the pair correlation function at for semi-dilute solutions is more gradual than the cut-off function at for dilute solutions. Received 11 May 1998 and Received in final form 22 October 1998     

Molecular Properties and Aggregation of Porphyrin-modified Polysiloxane in Solutions

Molecular properties and aggregation behavior of a polysiloxane with grafted side chain groups consisting of asymmetrical hydroxy-functionalized porphyrin were studied in dilute solutions. In order to understand the mechanism of aggregation of the polymeric porphyrin derivatives, several analyses of chloroform solutions were performed permitting comparison of the data obtained by means of different techniques. Molar mass and hydrodynamic size of the macromolecules were obtained using the methods of analytical ultracentrifugation, isothermal translational diffusion, and viscometry. Long distance interactions between macromolecules in dilute solutions were detected with static light scattering. With increasing the concentration of the solutions, the electronic and fluorescence spectra bands assigned to generation of H and J aggregates became apparent. The organization of aggregates, which seemed to be favored by chloroform, was visualized by atomic force microscopy images that displayed sponge-like morphology, small triangular particles, characteristic of H aggregates, and nano or micro-structured ring geometries obtained by the side-by-side J-process, coexisting together.     

Liquid crystalline states of surfactant solutions of isotropie micelles

We consider micellar solutions whose surfactant molecules prefer strongly to form small, globular aggregates in the absence of intermicellar interactions. At sufficiently high volume fraction of surfactant, the isotropic phase of essentially spherical micelles is shown to be unstable with respect to an orientationally ordered (nematic) state of rodlike aggregates. This behavior is relevant to the phase diagrams reported for important classes of aqueous amphiphilic solutions.     

Characterization of Nanoparticles and Colloids in Aquatic Systems 1. Small Angle Neutron Scattering Investigations of Suwannee River Fulvic Acid Aggregates in Aqueous Solutions

Fulvic acids (FA) and humic acids (HA) constitute 30–50% of dissolved organic matter in natural aquatic systems. In aqueous solutions, a commonly accepted view is that FA and HA exist as soluble macroligands at low concentration and as supramolecular aggregates at higher concentration. The size, shape and structure of these aggregates are still the subject of ongoing debate in the environmental chemistry literature. In this article, we use small angle neutron scattering (SANS) to assess the effects of solute concentration, solution pH and background electrolyte (NaCl) concentration on the structures of Suwannee River FA (SRFA) aggregates in D₂O. The qualitative features of the SANS curves and data analysis are not consistent with the view point that SRFA forms micelle-like aggregates as its concentration in aqueous solution increases. We find that SRFA forms fractal aggregates in D₂0 with size greater than 242 nm. The SRFA aggregates undergo a significant degree of restructuring in compactness as solution pH, solute concentration and NaCl concentration increase.     

Form-factors for different aggregation models of micelles

Spherical micelles in ionic micellar solutions, often aggregate to form spherical, cylindrical or chain-like aggregates on addition of salt to the solution. It is known that the technique of small angle neutron scattering (SANS) can be used to distinguish spherical and cylindrical aggregates. To examine if SANS can be used to distinguish the latter two aggregation processes, we have calculated the angular distribution of scattered neutrons from 0.002 M CTAB solutions. These calculations show that aggregation of CTAB micelles results in large changes in SANS spectra. The shapes of SANS spectra are different for the above three types of aggregates, suggesting that technique of SANS can indeed be used to distinguish the three aggregation processes. The size of the aggregate can also be obtained from such studies.     

Influence of the degree if dispersion of uranine in solutions on the fluorescence light intensity

From scattering measurements of light which does not excite fluorescence, it is found that acetone, dioxan or ethanol in low concentrations reduce the aggregates in an aqueous solution of uranine. In contrast, concentrated solutions of acetone, dioxan and ethanol enhance these aggregates. A correlation is found between the intensity of the light scattered by the aggregates and the fluorescence light intensity.     

半花菁LB膜的时间分辨荧光研究

利用紫外－可见吸收,稳态和时间分辨荧光等方法研究了半花菁与花生酸交替Ｙ型ＬＢ膜中分子聚集体的性质;吸收光谱和稳态荧光光谱峰位的蓝移说明ＬＢ膜中Ｈ聚集体的存在。从荧光衰工线得到了聚集体的组份含量、大小和寿命。     

Dust agglomeration

Dust agglomeration plays an important role in astrophysics and atmospheric sciences as well as in industrial processes. This article reviews the current knowledge of the physical interactions that lead to particle sticking in gaseous environments as well as the morphologies of the resulting dust aggregates. With this basic knowledge of dust–dust interactions, the development of ensembles of interacting dust particles can be treated using Smoluchowski's equation. Considering analytical solutions and simplified physical conditions, the temporal evolution and the mass distribution functions of dust aggregates are discussed. Based on this, general dust aggregation phenomena can be modelled and introduced into more complex scenarios.     

Orientational averaging of integrated cross sections in the discrete dipole method

Using the discrete dipole method, exact and approximate analytical solutions for orientation-averaged cross sections for extinction, absorption, and scattering of light are obtained. The analytical solutions can be applied to the calculation of integrated cross sections of fractal clusters formed by primary particles with different optical properties (soot in air and aqueous suspensions of aggregates of polystyrene, gold, and silver nanoparticles). It is shown that two models of aggregates that differ only in trajectories (ballistic or Brownian) of primary particles and intermediate clusters and in average fractal dimensions give close values of averaged extinction cross sections.     

A structural study of biocompatible magnetic nanofluid with synchrotron radiation-based X-ray scattering techniques

In this paper, water colloidal solutions of nanoparticles of magnetite (magnetic nanofluids, (MNFs)) are investigated by synchrotron X-ray diffraction (XRD) and small-angle scattering (SAXS). To prevent aggregation, nanoparticles are coated with polyacrylic acid (PAA) in a single solution and citric (CA) in the other solutions. In both cases, the maxima of the particle size distribution from SAXS (9?C10 nm) correspond to the sizes of the magnetite crystallites that were estimated from the broadening of the diffraction lines. In addition, the SAXS data indicate the presence of a significant proportion of aggregates (up to 60 nm in diameter) in both colloidal solutions, although fundamental differences in the structures of aggregates between the MNFs stabilized by PAA and CA were not observed. In this study determination of the structural characteristics of MNFs were carried out in order to obtain stable dispersive non-aggregating nanoparticles of magnetite for use as contrast agents in magnetic resonance tomography, drug carriers, and other biomedical applications.     

Magnetooptical studies of aggregates of nanoparticles in colloidal solutions of magnetite

The birefringence in a colloidal solution of nanosized magnetite particles in kerosene exposed to constant, alternating, and pulsed magnetic fields is studied. Data on the birefringence kinetics in nonstationary magnetic fields is used to determine the hydrodynamic radius of particle aggregates in solutions. The permanent dipole moment of aggregates and the anisotropy of the magnetic susceptibility are calculated based on the data of magnetooptical experiments. It is shown that the induced dipole moment plays a significant role in an orientation of aggregates of magnetic nanoparticles under the effect of a field.     

The effect of solvation on spectral-luminescence properties of 2,2-difluoro-4-methylnaphto-[2,1-<Emphasis Type="Italic">е</Emphasis>]-1,3,2-dioxaborine

The processes of formation and dissociation of aggregates and formation of solvates of 2,2-difluoro- 4-methylnaphto-[2,1-е]-1,3,2-dioxaborine (1) with the chloroform molecule have been investigated by the methods of stationary and time-resolved spectroscopy. It has been revealed that, in the case of solutions in chloroform, a slow (within 1 h) dissociation of aggregates under the effect of solvent molecules takes place. It has been demonstrated that using chloroform as a solvent allows varying the content of luminophor aggregates in the polymeric composite and, thus, controlling the material spectral-luminescence properties.     

Raman spectroscopic investigations on intermolecular interactions in aggregates and crystalline forms of trans‐astaxanthin

Astaxanthin is a carotenoid naturally found in microbial organisms, microalgae, and many crustaceans. Its consumption has led to beneficial effects such as pigmentation of marine animals, and it favorably addresses several human health issues as a result of its high important antioxidant property. Several companies produce synthetic trans‐astaxanthin for dietary purposes in aquaculture, where it is mainly used for pigmentation. It is known that trans‐astaxanthin manifests itself as a monomer in organic solvents, as aggregates in aqueous solutions of organic solvents, or as crystalline solids. These forms display unique optical and structural properties, which have an impact on biological systems. In this work, we report on detailed Raman investigations, in conjunction with optical absorption spectroscopy, of monomer, aggregates, and crystalline forms of trans‐astaxanthin. The Raman and optical absorption spectroscopic investigations of trans‐astaxanthin aggregates were performed as a function of time, showing the formation of card‐packed aggregates after 2 h, and head‐to‐tail aggregates after 24 h in a 10% acetone–water astaxanthin solution. For the crystalline trans‐astaxanthin, a pointwise Raman mapping evidenced the presence of two distinct crystal structures. The Raman modes of these crystal structures (A and B) were correlated with the intermolecular interactions present in chloroform solvated (AXT‐Cl) and unsolvated (un‐AXT) trans‐astaxanthin single crystals. Both crystal structure A and the card‐packed aggregates have similar intermolecular π stacking interactions as AXT‐Cl. The crystal structure B and the head‐to‐tail aggregates showed linear chain features as in un‐AXT. This work also clearly demonstrates that Raman spectroscopy is a powerful tool to distinguish the crystal structures present in crystalline powder of trans‐astaxanthin. Copyright © 2012 John Wiley & Sons, Ltd.     

Sensitive Spectroscopic Detection of Large and Denatured Protein Aggregates in Solution by Use of the Fluorescent Dye Nile Red

The fluorescent dye Nile red was used as a probe for the sensitive detection of large, denatured aggregates of the model protein β-galactosidase (E. coli) in solution. Aggregates were formed by irreversible heat denaturation of β-galactosidase below and above the protein’s unfolding temperature of 57.4°C, and the presence of aggregates in heated solutions was confirmed by static light scattering. Interaction of Nile red with β-galactosidase aggregates led to a shift of the emission maximum (λ _max) from 660 to 611 nm, and to an increase of fluorescence intensity. Time-resolved fluorescence and fluorescence correlation spectroscopy (FCS) measurements showed that Nile red detected large aggregates with hydrodynamic radii around 130 nm. By steady-state fluorescence measurements, it was possible to detect 1 nM of denatured and aggregated β-galactosidase in solution. The comparison with size exclusion chromatography (SEC) showed that native β-galactosidase and small aggregates thereof had no substantial effect on the fluorescence of Nile red. Large aggregates were not detected by SEC, because they were excluded from the column. The results with β-galactosidase demonstrate the potential of Nile red for developing complementary analytical methods that overcome the size limitations of SEC, and can detect the formation of large protein aggregates at early stages.     

Micellar effects on the molecular aggregation and fluorescence properties of benzazole-derived push-pull butadienes

The absorption and fluorescence spectral behaviour of 1-(2-benzoxazolyl)-4-(p-dimethylaminophenyl)buta-1,3-diene and its benzothiazolyl analogue (abbreviated as BODB and BTDB, respectively) have been investigated in dioxane-water mixtures and micellar environments using steady-state techniques. In water, water-rich mixtures or premicellar solutions, BODB and BTDB tend to form molecular aggregates labelled as H-aggregates. These aggregates dissociate on adding surfactants forming micellized monomers. In all micellar media the fluorescence quantum yield is greatly enhanced along with a large hypsochromic shift. Also, in TX-100, CTAB and SDS both dienes show dual emission from the locally excited (LE) and intramolecular charge transfer (ICT) states. For BTDB in TX-100 and DODB in all solutions, the LE fluorescence predominates, while for BTDB in CTAB and SDS, the ICT fluorescence is the predominant. The fluorescence shifts suggest that the fluorescing molecules penetrate the core of the micellar unit in TX-100, whereas in CTAB and SDS they occupy the interfacial region. The binding constants and the micelle properties (such as polarity and CMC) have been determined using both dienes as probes.     

Dynamics of optical response of solutions of pseudoisocyanine <Emphasis Type="Italic">J</Emphasis> aggregates upon pico- and subnanosecond excitation

The luminescence kinetics of solutions of pseudoisocyanine iodide (PIC) J aggregates is studied upon excitation by pico- and subnanosecond laser pulses into the main superintense long-wavelength absorption band. The dependences of the transmission and luminescence energy on the pump energy are measured. It is found that the shape of the luminescence kinetics depends on the recording and excitation spectral regions, which is obviously related to the energy transfer between coherently coupled fragments of J aggregates.     

Selective cleaning of ions of heavy metals from water solutions using the H-form of todorokite synthesized by the hydrothermal method

A phase of Mg-todorokite with a size of structural tunnels of ～10 Å has been synthesized by the hydrothermal method in the form of lamellar crystalline aggregates 50–100 nm in size. Topotactic interaction with concentrated nitric acid results in the formation of the H-form of todorokite, having a high ability to adsorb Cs⁺, Pb²⁺, and Ba²⁺ ions from water solutions. H-todorokite can be used as an ion filter for cleaning ions of heavy metals from water solutions.     

New Insights on the 7-azaindole Photophysics: The Overlooked Role of Its Non Phototautomerizable Hydrogen Bonded Complexes

In this paper we explore the formation and the photophysical properties of the scarcely studied open hydrogen bonded aggregates of 7-Azaindole, 7AI. Thus, we have analyzed the influence that the increase of the 7AI concentration and the decrease of the temperature have on the 7AI photophysics. To help the interpretation of the results, the 7AI-Pyridine system has been used as the model for the analysis of the photophysical properties attributable to the open N_pyrrolic ? HN_pyridinic hydrogen bonded aggregates. Also, the hydrogen bond interactions have been studied by means of the atom in molecule approach from the Bader theory. Experimental and theoretical results support that the formation of open hydrogen bonded aggregates, (?7AI-)_n with n?≥?2 can efficiently compete with that of the profusely studied centro-symmetric cyclic dimer (7AI)₂. Moreover, these aggregates suffer a proton-driven electron transfer process that strongly quenches their room temperature fluorescence and, therefore, masks their presence in the 7AI solutions. Therefore, because most of the studies on the 7AI photophysics have been interpreted without considering the existence of such aggregates and, more important, ignoring its quenching process, many conclusions obtained from these studies should be carefully revised.     

Synthesis, characterization, and controlled aggregation of biotemplated polystyrene nanodisks

Cross-linked polystyrene nanodisks were prepared by controlled polymerization of styrene and divinylbenzene in the interior of bicelles, discoidal lipid aggregates. Aggregation behavior of polymer nanodisks was studied in water, organic solvents, and solid phase. Nanodisks form stable dispersions in aqueous solutions of surfactants, such as sodium dodecyl sulfate (SDS). Varying SDS/nanodisk ratio allowed us to control the size of nanodisk aggregates. Nanodisks are readily solubilized in nonpolar organic solvents, such as toluene and carbon tetrachloride, to yield stable monodisperse suspensions. These findings open opportunities for creating nanodisk-based nanocomposite materials. Stable nanodisk suspension in toluene enabled small angle neutron scattering (SANS) measurements. SANS data confirmed the nanodisk diameter and allowed accurate measurement of nanodisk thickness (19.5 ± 1.0 Å). In solid phase, nanodisks aggregate in sub-micron platelets.