Birefringence of native cellulosic fibers. I. Untreated cotton and ramie

The Rayleigh-Gans theory of light scattering by a homogeneous cylinder has been applied to the case of scattering by a pad of fibers immersed in a liquid. The theory enables one to locate precisely the matching wavelength at which the mean refractive index of a sample of optically heterogeneous fibers coincides with that of an immersion medium. Thereby it offers a method of determining the mean refractive index. Besides, it facilitates a quantitative estimation of the variability of refractive index. The new technique has been used to study the birefringence of untreated cotton and ramie. The results are presented and discussed.     

Microwave Discharge in Liquid Hydrocarbons: Study of a Liquid Hydrocarbon after Exciting the Discharge

Changes in liquid hydrocarbons (hexane, cyclohexane, n-heptane, isooctane, decane, pentadecane, cetane, petroleum solvent, benzene, toluene, and o-xylene) have been studied after exciting a microwave discharge in their bulk. The experiments have been carried out at atmospheric pressure. For the analysis, GC/MS, IR spectroscopy, and dynamic light scattering methods have been used. It has been shown that new compounds and nanoparticles are formed in the hydrocarbons.     

Water in polymer membranes. Part II : Raman scattering from guided laser beams

Simultaneous application of integrated optics and Raman spectroscopy is used to investigate the hydrogen bonding of water in thin dense symmetric membranes of cellulose acetate (CA). A modified X-ray quarter circle goniometer is used to measure refractive index, film thickness, and Raman spectra using guided laser beams and the prism coupler technique. The film remains in a fixed position during all measurements thereby ensuring identical light collection geometries for Raman scattering observed from different wave-guiding modes. To illustrate the technique, Raman scattering of a 3.5 μm film of CA398-10 in the OH stretching region is shown as a function of relative humidity (RH). These spectra show that water sorbed at less than 50% RH is weakly hydrogen-bonded but above 50% RH, sorbed water has the strongly hydrogen-bonded properties of bulk water.     

Transparent and shape-memory cellulose paper reinforced by vitrimer polymer for efficient light management and sustainability

The functional paper holds significant potential in some special fields, which has achieved great development. Nevertheless, using cellulose paper to fabricate functional paper, which integrates transparency, robustness, flexibility, shape memory, and sustainability, remains a challenge. Herein, the vitrimer precursor was vacuum impregnated into cellulose paper and then in-situ polymerized to develop a vitrimer-cellulose paper (VCP) with transparency, shape manipulation, robustness, and sustainability. Taking advantage of the vitrimer’s dynamic performance, the resulting VCP demonstrated excellent optical transparency (transmittance of 84%, haze of 75%), enhanced mechanical strength (tensile strength of 80.5 MPa), chemical resistance, thermal-triggered shape manipulation, and reprocessing. Noteworthily, VCP possessed outstanding light management capability with effective light propagating and scattering performance. Furthermore, VCP laminate showed increased mechanical property with the increased layers, and it can be reprocessed to a bulk composite after crushing. These incorporated merits of VCP make a promising candidate for light management and sustainable building application.

     

Light scattering from coloured systems: an example of polyaniline dispersions

Static light scattering of highly diluted dispersions in 0.005 M H₂SO₄ was used to determine particle parameters of polyaniline dispersions stabilized with colloidal silica. The refractive index of polyaniline n = 1.8 and the refractive index increment (dn/dc) = 0.22 cm³g⁻¹ at λ = 532 nm were determined. The light scattering data are affected by the absorption of the green polyaniline and by a small amount of aggregates. The absorption has a negligible effect on the results. The influence of the aggregates was corrected by using the intensity‐weighed size distributions determined by dynamic light scattering at different angles and by the two‐component separation in static light scattering. Both procedures yield the same result.     

Analysis of the kinetics of diffraction efficiency during the holographic grating recording in azobenzene functionalized polymers

The laser-assisted holographic grating recording process in films of azobenzene functionalized polymers is usually studied by observation of the efficiency of light scattering on a developing in time diffraction grating. Various possible mechanisms contributing to grating formation as well as the bulk or surface origin (bulk refractive index and/or relief grating) of light scattering make the analysis of kinetics of grating recording, from the light scattering data only, difficult and ambiguous. To fully explain experimentally observed various and complex (frequently nonexponential) kinetics of the first-order light diffraction intensity, we considered a simple single-exponential growth of the two phase gratings in the same polymer film. In modeling we assumed that the bulk refractive index grating Deltan(t) and the surface relief grating Deltad(t) differ considerably in their growth rates and we allowed for a nonstationary phase shift Deltaphi(t) between them which was experimentally observed during the recording process. The origin of the nonstationary phase shift is a result of a slow shift of interference pattern due to delicate symmetry breaking in illumination conditions (e.g., difference in beam intensities and deviation of exact symmetrical beam incidence angles on the sample). Changing only such parameters as stationary amplitudes of refractive index and relief gratings for a span of phase shifts (0-pi) between them, we obtained a series of kinetic responses which we discuss and interpret. The various examples of temporal evolution of diffraction efficiency for the same grating formation kinetics, modeled in our work, supply evidence that great care must be taken to properly interpret the experimental results.     

Light scattering behaviour of low-molecular-weight polymers in mixed solvents with very high selective sorption

Some low-molecular-weight polymers (poly(butyl methacrylate), nylon 6, nylon 12) in the solvent system m-cresol/n-heptane, with effective refractive index increments (?n/?c)_μ in the range 0.34?0.81 ml/g, have been studied by light scattering. These extremely large values, measured by differential refractometry of solutions in the state of dialysis equilibrium, are mainly due to very great selective sorption of one solvent component (m-cresol) on the polymers studied. The effect inherent to these systems, viz. that of the free solvent composition change, has been discussed and exemplified by the light scattering behaviour of solutions of oligomers of butyl methacrylate. The light scattering anomalies observed with solutions of some nylons in m-cresol/n-heptane have been interpreted as due to interaction of polymer end-groups. It has been demonstrated that the determination of $\text{M}{}_{\mathrm{w}}$ of the order of 10³ by light scattering in systems with large (?n/?c)_μ values, i.e. with large scattering power, is possible with good accuracy.     

Selection of solvents for the determination of the parameters P and Q for chemically heterogeneous copolymers by light scattering

A calculation method has been developed which makes possible, by using the refractive index values, the choice of solvents for a sufficiently accurate determination of the copolymer heterogeneity parameters (P and Q) by light scattering. If the expected P and Q values are estimated from other data (e.g. copolymerization kinetics), the method can be used to find out if (and where) there exist(s) such interval(s) or discrete point(s) on the scale of the refractive index of the solvents for which the following two conditions are met simultaneously: (i) the excess Rayleigh factor is so large, even at the lowest copolymer concentration used and the angle of measurement: 90°, that the apparent molecular weight of the copolymer. M_ap, can be determined with sufficient accuracy: (ii) mutual position of experimental points (three, at least) on the parabolic dependence M_ap vs optical variable (the ratio of the difference of refractive index increments of parent homopolymers to the refractive index increment of the copolymer) is such that the determination of parameters of this parabola is sufficiently accurate. The application of the method is demonstrated for three examples (block copolymer, random copolymer, and a mixture of homopolymers).     

A light scattering and fluorescence emission coupled ratiometry using the interaction of functional CdS quantum dots with aminoglycoside antibiotics as a model system

Any signals, if their intensities have simple functional relationship with analyte concentration, can be applied to analytical purposes. Rayleigh light scattering signals and fluorescence signals are twins in flurospectroscopy, so the light scattering signals are the major interference when the Stokes shift is small. Herein, we propose a light scattering and fluorescence emission (LS-FL) coupled ratiometry using CdS quantum dots (QDs) as a fluorescence probe to detect aminoglycoside antibiotics (AGs). As model analytes, AGs, when attached to the surface of CdS-QDs via electrostatic interaction in aqueous medium, result in strong enhanced light scattering (LS) emission characterized at 376 nm and fluorescence quenching of CdS-QDs at 500 nm. Thus, a ratiometry using the coexistent light scattering and fluorescent emission signals has been proposed. Based on the linear relationship between logarithm of light scattering and fluorescence emission ratio (R) and logarithm of AGs concentration, a novel assay of AGs is established with the limits of detection (3σ) being 58-190 nmol l⁻¹, and applied successfully to detect AGs injection and serum samples.     

Characterization of lignin using multi-angle laser light scattering and atomic force microscopy

Small differences in the isolation techniques of lignin can result in significant changes in its molecular structure and configuration. Light scattering (evaluated at 18 different angles in a plane), Atomic Force Microscopy (AFM) and Near Infrared Spectroscopy (NIR) proved very effective for evaluating the characteristics of lignin. Zimm plots were generated using Zimm, Debye and Berry formalisms to evaluate the weight average molecular weight (MW), radius of gyration (r_g), hydrodynamic radius (r_h) and second virial coefficient (A₂). Two types of lignin and nine different solvents were used for the study, to analyze the conformation of lignin molecules in different solvents expected to be used in lignin degradation and subsequent analysis. Absolute MW and r_g decreased and the dn/dc increased when the solvent used for lignin was changed from water to sodium hydroxide. The two types of lignin also exhibited different values for all the above estimated parameters. This study also highlighted the differences between the unlyophilized and lyophilized lignin in terms of aggregation, pH dependence and stability over time. This aggregation has never been seen on a ultraviolet (UV) or refractive index (RI) detector that has been used so far for liquid chromatography (LC) reducing the reliability of lignin depolymerization data obtained without light scattering.     

In situ SAXS investigation of dibromomethane adsorption in ordered mesoporous silica

A SAXS/WAXS apparatus with the aid of a specially designed sample cell capable for performing both SAXS and WAXS experiments was used for adsorption studies in nanoporous materials. The applicability of the instrument for structural investigations and its ability for adsorption experiments because of the advanced sample environment were demonstrated by carrying out in situ SAXS measurements during gas physisorption. SAXS profiles of ordered mesoporous silica were measured at selected equilibrium points alongside a dibromomethane (CH₂Br₂) adsorption isotherm at 293 K. SBA-15 was the adsorbent of choice because it consists of a regular 2D hexagonal array of cylindrical mesopores that gives rise to Bragg reflections in the small-angle regime. CH₂Br₂ was selected as a contrast-matching fluid because it has almost the same electron density as silica. We obtained high-quality data comparable to those resulting from experiments performed in synchrotron light sources which produce intense beams of x-rays and support advanced instrumentation for high-resolution diffraction and SAXS studies. The Bragg peaks of the pore lattice are clearly visible for the evacuated sample and at the early stages of the adsorption process. The intensity decrease and the elimination of the Bragg peaks for the saturated sample suggest that an almost perfect contrast matching was achieved. A model has been used for monitoring the fluid condensation and evaporation regime in SBA-15 by taking into account both the Bragg scattering and the diffuse scattering for spatially random pore filling. The results show the absence of spatial correlations between filled pores suggesting random pore filling.     

pH-responsive non-surface-active/surface-active transition of weakly ionic amphiphilic diblock copolymers

The weakly ionic amphiphilic diblock copolymer polystyrene-b-poly(acrylic acid) was synthesized by nitroxy radical-mediated living radical polymerization with precise control of block length, block ratio, and polydispersity. Systematical surface tension experiments and foam formation observations revealed that this polymer was non-surface active under neutral and alkaline (pH 10) conditions, while it was surface active under an acidic condition (pH 3). This result supports our proposed origin of non-surface activity; the image charge repulsion at the air/water interface is essential in addition to very stable micelle formation in the bulk solution. At a higher pH (pH 12), the polymer showed slight surface activity since the added NaOH played a role as an added salt. The critical micelle concentration (cmc) was estimated by static light scattering. Cmc increased with increasing added salt (NaCl) concentration as was observed for other strongly ionic non-surface-active polymers. Hence, this trend is characteristic for non-surface-active polymers. The pH dependence of cmc was minimum at pH 8–10. Since the acrylic acid block is fully ionized under this condition, the strong image charge repulsion at this condition accelerated micelle formation at a low polymer concentration, which consequently decreased cmc. Micelles in bulk solution were confirmed by dynamic light scattering, and the salt concentration and pH dependencies of the hydrodynamic radius of the micelles were also estimated. The pH-responsive non-surface-active/surface-active transition observed in this study strongly supports the fact that the image charge repulsion is an essential factor for non-surface activity in addition to stable micelle formation in solution.     

Determination of several thermophysical properties of toluene using a single experimental setup

Dynamic light scattering can be used for the determination of several thermophysical properties of interest using one single experimental setup. Light scattering from bulk fluids allows the measurement of thermal diffusivity and sound velocity. Results are presented for toluene, an important reference fluid, over a wide temperature range up to the critical point at saturation conditions for both the liquid and the vapour phase. Furthermore, it is demonstrated that the same setup can be used for the determination of surface tension and kinematic viscosity of the liquid phase from light scattering by surface waves on a vertical liquid layer. All experiments are based on a heterodyne detection scheme and signal analysis by photon correlation spectroscopy. The results are discussed in comparison with literature data.     

A particle-hole model for light scattering by simple fluids

The intensity, I, of depolarized light scattered by simple fluids is calculated by modeling the fluid as a dilute gas of dielectric spheres at low density and as a dilute gas of spherical holes in a dielectric continuum at high density. It is shown that a pair of spheres has more inherent scattering power than a pair of holes. Thus, at liquid density, I is smaller than would be predicted by using gas-phase scattering theory plus liquid-state statistics, as has generally been done in the past; the implications of our result for existing theories are discussed.     

Solution properties of poly p-isopropyl α-methylstyrene

Two series (S and F) of poly p-isopropyl α-methylstyrene were characterized by viscometry, light scattering (LS), osmometry and gel permeation chromatography (GPC). S-samples were prepared by bulk anionic polymerization whereas F-samples were obtained on fractionation by preparative GPC of a polymer also prepared in bulk but with a different initiator. The K parameter in the Mark-Houwink relation was 5.55 × 10^?4 for series-S and 4.50 × 10^?4 for series-F, whereas the exponent a was 0.55 for both series. The Mark-Houwink equations for series-S and -F hold good at 25 and 30° for both toluene and tetrahydrofuran as solvents and have been corrected for polydispersity. The chain dimensions obtained with LS were much higher than those computed from the viscosity data indicating that the hydrodynamic theories in their present state should not be used for the calculation of chain dimensions. The deviations from the GPC universal calibration curve of polystyrene observed with some samples were attributed to structural differences among the polymers and to their high polydispersity.     

Evanescent Wave Light Scattering A Fusion of the Evanescent Wave and Light Scattering Techniques to the Study of Colloids and Polymers Near the Interface

The evanescent wave light scattering technique, which is produced by a fusion of the evanescent wave technique and light scattering technique, is a very powerful and useful tool for investigation of colloidal particles and polymers near the surface and interfaces. We have developed two kinds of evanescent wave light scattering apparatuses. One is the evanescent wave dynamic light scattering (EVDLS) technique and the other is the evanescent wave light scattering microscope (EVLSM). By EVDLS, the diffusion behavior of a colloidal particle near the interface can be extracted quantitatively as a function of the distance from the interface. The diffusion coefficient was smaller than those for particles in bulk, reflecting electrostatic and hydrodynamic interactions. By EVLSM, the interaction potential profile between a colloidal particle and the surface in dispersion can be evaluated directly. EVLSM will play an important role in colloidal interaction studies, especially at a low ionic strength. It is also pointed out that a particle dynamics study is also possible by the EVLSM technique. A new field will be developed in colloid science and polymer science by application of the evanescent wave light scattering technique, i. e. a fusion of the evanescent light and a light scattering techniques.     

Toward room-temperature optical manipulation of small molecules

Room-temperature optical manipulation of small molecules is a challenging issue in the field of material science. To increase optical force for a single molecule trapping, it has been recognized that resonant excitation of molecules should be controlled under the light illumination. Strongly interacting molecules with solid surfaces at electrified interfaces show the exotic behavior of electronic excitation by localized surface plasmon. In this review, we emphases that surface-enhanced Raman scattering can be used to evaluate the resonant excitation of target molecules at interfaces. Under such excitation, the diffusion of small molecules can be controlled by the optical force generated by the intensity gradient of a highly localized electric field.     

Polymer cosolvent system—II. Preferential adsorption of binary solvent acetone/cyclohexane by poly(p-tert-butylphenyl methacrylate)

The cosolvent system poly(p-tert butylphenyl methacrylate) (3)/acetone(1)/cyclohexane (2) has been studied at 298 K by light scattering, refractive index increment of dialysis equilibrium and viscometry. The preferential adsorption coefficient, λ1, for the whole composition range of the binary mixture acetone (1)/cyclohexane(2) has been determined. The values have been compared with the theoretically calculated values. The results indicate that in this system it is necessary to take into account the tertiary interaction parameters χ₁₂₃, χ₁₂₂ and χ₂₃₃.     

On relationships between molecular structure, interaction and surface behavior in mixture: small-molecule surfactant+protein

We report on the effect of distinct in nature small-molecule surfactants (model, a sodium salt of capric acid, Na-caprate; and commercially important, a citric acid ester of monoglyceride, CITREM; a sodium salt of stearol-lactoyl lactic acid, SSL (Na(+)); polyglycerol ester, PGE (080)) on molecular properties in a bulk and at the air-water interface of globular legumin and random-coiled micellar sodium caseinate. The role of the structure of both proteins and small-molecule surfactants in the effect studied has been elucidated by measurements in a bulk aqueous medium of the enthalpy of their interaction from mixing calorimetry, the change in value of weight average molecular weight of the proteins and the thermodynamics of the pair protein-protein interactions from laser static light scattering as well as, in addition, by measurements of the change in hydrodynamic radius for micellar sodium caseinate from laser dynamic light scattering. The effect of the small-molecule surfactants on the thermodynamics of the protein heat denaturation and thereby on the protein conformational stability has been studied by differential scanning calorimetry in the case of globular legumin. The interrelation between the effects of the small-molecule surfactants on the properties of the proteins in a bulk and at the planar air-water interface has been elucidated by tensiometry. The combined data of mixing calorimetry, differential scanning calorimetry and laser light scattering suggest some complex formation between the small-molecule surfactants and the proteins in a bulk aqueous medium. Predominantly hydrophobic interaction along with electrostatic and hydrogen bonding form the basis of the complex formation. The found effect of the small-molecule surfactants on the surface activity of their mixtures with proteins is governed primarily by both the extent of the protein association, resulting in specific hydrophobicity/hydrophilicity of the surface of the protein associates, and the specific protein conformational stability, for the globular protein, produced by the interaction between the proteins and the small-molecule surfactants.     

ADDITIVE-INDUCED ENHANCEMENT OF OPTICAL CLARITY OF POLYACRYLAMIDE HYDROGEL

The aqueous polymerization of acrylamide and crosslinking with N,N-methylenebisacrylamide afforded hydrogelsdisplaying high levels of light scattering (poor optical clarity). Enhancement of the optical clarity within a polyacrylamide(PAm) hydrogel was accomplished through the implementation of "refractive index matching". Water-soluble additives wereutilised to better match the refractive index inhomogeneities throughout a given hydrogel. This resulted in lower lightscattering within the system and hence improved clarity. Amino acids, sugars, polymers, and other water-soluble additivessuch as glycerol were investigated by this methodology. Most additives investigaed displayed potential for effectivelyreducing the light scattering within a PAm hydrogel as a function of increased additive concentration. On increasing therefractive index of the water medium, the overall refractive index of a PAm hydrogel was also observed to increase. Thisprovided a quantitative means of determining the effectiveness of a given additive for improving the optical clarity within ahydrogel.