Stretching effect of linearly polarized Ar+ laser single-beam on azo polymer colloidal spheres

This work shows that a linearly polarized Ar+ laser single-beam irradiation can cause stretching deformation of azo polymer colloidal spheres along the polarization direction of the laser beam. An epoxy-based polymer, containing 4-amino-4'-carboxyazobenzene at each repeat unit, was used to construct the colloidal spheres. The colloidal spheres were prepared by gradual hydrophobic aggregation of the polymeric chains in a THF/H2O dispersion medium, which was induced by a steady increase in the water content. When the obtained colloidal spheres were exposed to the spatially filtered and collimated Ar+ laser beam (488 nm, 150 mW/cm2), the colloids were stretched along the polarization direction of the laser beam. In the testing period (20 min), the colloids were deformed continuously as the irradiation time increased. When 2D close-packed arrays of the colloidal spheres were irradiated by the polarized laser single-beam, the colloidal spheres were all uniformly stretched along the polarization direction of the laser beam. On the contrary, when the arrays were irradiated by the interfering p-polarized laser beams, only the colloidal spheres in the bright regions of the interference pattern were significantly deformed.     

Azo polymer colloidal spheres containing different amounts of functional groups and their photoinduced deformation behavior

In this work, colloidal spheres composed of azo polymers with different chromophore loading densities were prepared, and their photoinduced deformation behavior was studied. The colloids were constructed by using a series of amphiphilic epoxy-based random copolymers containing 4-carboxylazobenzene functional groups with different degrees of functionalization (DFs). The colloidal spheres were fabricated through gradual hydrophobic aggregation of the polymeric chains in tetrahydrofuran-H2O dispersion media, which was induced by gradually adding water into the systems. The colloidal spheres were characterized by using transmission electron microscopy and dynamic light scattering. The photoinduced deformation behavior was studied by irradiating the colloidal spheres with a linearly polarized Ar+ laser beam. Results showed that the critical water content (CWC) for the colloid formation is related to the DF of the polymers, and CWC increases with the increase of DF. The hydrodynamic diameter of the colloidal spheres is also related to the DF of the polymers. When the DF of the polymers increases, the average size of the colloids gradually decreases. The hydrodynamic diameter of the colloidal spheres increases as the water dropping rate decreases. When the dropping rate is below 20 microL/s, the size of the colloidal spheres increases abruptly as the dropping rate further decreases. Upon the linearly polarized Ar+ laser beam irradiation, the colloids composed of polymers with different DFs can all be elongated along the polarization direction of the laser beam. As DF increases, the deformation degree characterized by the axial ratio (l/d) almost linearly increases. These observations can give some insight into the photoinduced deformation mechanism and can be used to construct colloids with different sizes and photoresponsive ability.     

Separation and detection of individual submicron particles by capillary electrophoresis with laser-light-scattering detection

Separation and detection of individual submicron polystyrene spheres using capillary electrophoresis with laser-light-scattering detection has been demonstrated. Electrophoretically separated particles were passed through a focused laser beam and light scattered from individual particles was collected at 90 degrees. Each diameter of polystyrene spheres injected (from 110 to 992 nm) resulted in the observation of a well-defined migration window containing multiple peaks, each arising from the light scattered by an individual particle. The migration time window for individual particles of a particular size corresponded well to the migration time of a peak from a population of particles of the same size detected using a UV absorbance detector. The electrophoretic mobility and scattered light intensity were determined for each particle detected. The average scattered light intensity for each particle size was consistent with Mie scattering theory. Particles as small as 110 nm in diameter were detected individually using this method, but particles with a diameter of 57 nm could not be individually detected. The number of single particle scattering events was counted and compared to the theoretical number of particles injected electrokinetically, and the detection efficiency determined ranged from 38 to 57% for polystyrene spheres of different sizes. The laser-light-scattering detection method was directly compared to laser-induced fluorescence detection using fluorescent polystyrene microspheres. The number of particles detected individually by each method was in agreement.     

双组分偶氮聚合物胶体球制备及其光致形变行为研究

研究了2种环氧树脂类含4-氨基-4′-硝基偶氮苯和4-氨基-4′-羧基偶氮苯生色团聚合物(BP-AZ-NT、BP-AZ-CA)双组分胶体球的制备和光致形变行为.通过在上述聚合物的四氢呋喃溶液中逐步加水诱导自组装的方法,得到了BP-AZ-CA/BP-AZ-NT双组分胶体球.在上述两种聚合物自组装形成胶体球过程中,较为疏水的BP-AZ-NT分子先发生聚集,而较亲水的BP-AZ-CA则在形成的胶体颗粒表面发生进一步聚集.在胶体球形成过程中,体系的临界水含量(CWC)主要由BP-AZ-NT发生聚集时的水含量决定,双组分胶体球的外层则含较多的BP-AZ-CA分子.比较单组分胶体球与双组分胶体球在线偏振Ar+激光(488nm,100mW/cm2)照射下的形变行为,进一步证实了通过上述方法可以制备BP-AZ-CA和BP-AZ-NT双组份的胶体球;胶体球形变时的初始拉伸速率由胶体球的外层聚合物分子的性质所决定。     

Crystallization kinetics of thermosensitive colloids probed by transmission spectroscopy

The kinetics of crystallization of poly-N-isopropylacrylamide (PNIPAM) particles has been investigated using the UV-visible transmission spectroscopy. Since the particle size decreases with the increase in temperature, microgel dispersions of different volume fractions have been obtained by varying the temperature of a single sample. It is found that the rates of the change in crystallinity, the average crystallite size, and the number density of crystallites at the most rapid stage over a certain time interval at various temperatures can be described by the power-law relations. At 19 degrees C, the PNIPAM system behaves as a hard sphere system under microgravity. The hard sphere theory based on Monte Carlo simulation has been used as a reference point to compare with conventional hard spheres, soft spheres, and PNIPAM spheres.     

Evaluation of physicochemical properties on the blending process of pharmaceutical granules with magnesium stearate by thermal effusivity sensor

Magnesium Stearate (MgSt) is a widely used lubricant for preventing tablet compression trouble. It is known that the powder characteristic of MgSt is different among MgSts manufactured by different methods and conditions. These differences affect blending efficiency with pharmaceutical additives. The purpose of this study is to evaluate the physicochemical properties of MgSt by thermal effusivity sensor for in-process monitoring of powder blending. MgSts having different physicochemical properties and granulated sugar spheres were used for model excipients. V-blender was used for powder blending. Thermal effusivity values of each of the ingredients in the blend were measured using one of the sensors prior to placing the ingredient in the blender. The effect of magnesium stearate addition to uniform ingredients can be clearly identified using the sensors. Compared to effusivity data and powder density, effusivity data correlated with the powder characteristics of magnesium stearate. These results suggested that effusivity can be used for end point detection of blending process for various magnesium stearates with sugar sphere. When various magnesium stearates were added to the granule, required time for achieving homogeneous powder blend was different. Blending behavior would be affected by the physicochemical characters. Blend uniformity and blended states of granules containing magnesium stearate can be detected nondestructively without intricate sampling process. Thermal effusivity sensors are an efficient tool to monitor the real time blending behavior of pharmaceutical ingredients.     

3D simulations of hydrodynamic drag forces on two porous spheres moving along their centerline

This paper numerically evaluates the hydrodynamic drag force exerted on two highly porous spheres moving steadily along their centerline through a quiescent Newtonian fluid over a Reynolds number ranging from 0.1 to 40. At creeping-flow limit, the drag forces exerted on both spheres were approximately identical. At higher Reynolds numbers the drag force on the leading sphere (sphere #1) was higher than the following sphere (sphere #2), revealing the shading effects produced by sphere #1 on sphere #2. At dimensionless diameter beta<2 (beta=d(f)/2k(0.5), d(f) and k are sphere diameter and interior permeability, respectively), the spheres can be regarded as "no-spheres" limit. At increasing beta for both spheres, the drag force on sphere #2 was increased because of the more difficult advective flow through its interior, and at the same time the drag was reduced owing to the stronger wake flow produced by the denser sphere #1. The competition between these two effects leads to complicated dependence of drag force on sphere #2 on beta value. These effects were minimal when beta became low.     

Colloidal crystals formed by aqueous suspensions of monodispersed silica, polystyrene, and poly(methyl methacrylate) colloidal spheres

Colloidal crystals consisted of silica, polystyrene, and poly(methyl methacrylate) monodispersed suspensions; deionized sufficiently in water at the same condition; were formed; and their properties were compared changing sphere diameter and volume fraction systematically. The size of these colloidal crystals was maximized at their critical sphere concentration irrespective of their sphere size. The Bragg peak wavelengths of these colloidal crystals were uniquely determined only by the sphere diameter and volume fraction for all kinds of colloidal spheres used in this work. The larger the sphere volume fraction, the larger the crystal growth rates, and there were no significant differences among the colloidal spheres. The rigidity of colloidal crystals increased in proportion to the number density of spheres. Consequently, the crystallization mechanism and properties of colloidal crystals formed by these spheres are not dependent on the kind of spheres, but they are dependent only on the sphere diameter and number density.     

Electrostatic interaction between two spherical colloidal particles

Explicit exact analytic expressions are obtained in the form of infinite series for the potential distribution and the potential energy of the electrostatic interaction for the system of two dissimilar spheres in an electrolyte solution on the basis of the linearized Poisson—Boltzmann equation without recourse to Derjaguin's approximation. The leading term of the expression for the interaction energy (the zeroth order approximation) corresponds to the interaction energy that would be obtained if both spheres were ion-penetrable spheres (“soft” spheres). This term is a screened Coulomb interaction due to a simple linear superposition of the unperturbed potentials of the respective spheres, which is proportional to the product of their unperturbed surface potentials. The first-order approximation corresponds to the interaction energy that would be obtained if either sphere were a soft particle (the other being hard). The first-order correction term consists of two sub-terms, each of which is proportional to the square of the unperturbed surface potential of either sphere and does not depend on the unperturbed surface potential of the other sphere, can be interpreted as the interaction between the soft sphere and its image with respect to the hard sphere. This image interaction is attractive if the surface potential of the hard sphere is constant and repulsive if the surface charge density of the sphere is constant. It is shown that Derjaguin's method as well as its extension to the interaction of unequal spheres by Hogg, Healy and Fuerstenau (HHF) is quite a good approximation.     

Photoinduced deformation of amphiphilic azo polymer colloidal spheres

Photoinduced shape deformation of colloidal spheres made of an amphiphilic azo polymer has been demonstrated in this work. The polymer contains the donor-and-acceptor-type azobenzene chromophores and can form uniform colloidal spheres by dropwise adding water into its THF solution. When the colloidal spheres obtained were exposed to the interfering p-polarized Ar+ laser beams (150 mW/cm2), the colloidal spheres changed to prolates (i.e., "rugby-balls"), "spindles", and finally "rods", depending on the irradiation times. The elongated direction of the spheres was observed to be the same as the polarization direction of the laser beam. The average major-to-minor ratio of the ellipsoids could be easily adjusted by controlling the irradiation time. The deformation effect observed in this work can offer a new way to prepare nonspherical colloids from colloidal spheres and will shed new light on the correlation between the photodriven shape deformation and photoinduced surface relief gratings for the same type of polymers.     

Investigation of the effects of beam divergence on the response of neutron voluminous detectors

In the present study, the Monte Carlo calculations were carried out to evaluate the effect of beam divergence on the response of a spherical thermal-neutron counter at the center of a spherical moderating assembly. A model of ³He detector surrounded with 10 in. diameter polyethylene sphere was utilized to calculate the point isotropic and plane-parallel beams responses of twelve different energies, and obtain the geometry factor and its parameters (a ₄ and a ₅) based on general formulations. Furthermore, for 2, 3, 5, 8, 10 and 15 in. spheres exposed to three different radionuclide neutron sources with various energy spectra, the parameters of geometry factor were quantified, as a function of moderator radius and neutron energy. Obtained results based on this method were compared with the experimental data for one specific source. Finally, by these parameters the obtained values of the geometry factor based on two formulations were compared to each other.     

Surface-enhanced Raman scattering from silver-coated opals

We describe surface-enhanced Raman scattering measurements from a benzenethiol monolayer adsorbed on a silver-coated film that is, in turn, deposited on an artificial opal, where the latter is a close-packed three-dimensional dielectric lattice formed from polystyrene spheres. Data for a range of sphere sizes, silver film thicknesses, and laser excitation wavelengths are obtained. Enhancement factors can be in the range of 10(7). To partially explain these large enhancements, we have performed model finite-difference time domain simulations of the position-dependent electric fields generated at the opal surfaces for several experimentally studied laser wavelengths and sphere diameters.     

LIGHT DOSIMETRY FOR PHOTODYNAMIC THERAPY BY WHOLE BLADDER WALL IRRADIATION

Abstract In Photodynamic Therapy (PDT) there is a need for accurate quantitative light dosimetry. This has become particularly apparent in the treatment of superficial bladder cancer, either by focal or by whole bladder wall irradiation. We have studied this problem using a spherical model of the bladder, consisting of two concentric thin-walled plastic spheres, 8 and 10 cm in diameter. The inner sphere was filled with water or with a light-scattering medium. The space between the spheres was filled with an optically tissue equivalent liquid. An isotropic light source was placed at the center of the spheres. Light energy fluence rates (light "dose rates") during PDT of the bladder simulated in this manner, were measured using a specially developed miniature light detector and were also calculated using a mathematical model. These data were confirmed by measurements in vivo (dog bladder). In the case of focal irradiation at a wavelength of 630 nm, the ratio (R) between the true light fluence rate at the bladder surface and the fluence rate due to the primary light beam is somewhat larger than 1, depending on the diameter of the primary beam. The maximum ratio is 2, for a beam diameter of several centimeters. In the case of whole bladder wall PDT, R is larger than 5. This is due to the strong scattering of (red) light by tissue and indicates that the intensity of the primary beam, which is usually reported, is not a good measure of the true fluence rate for whole bladder wall PDT. When the light source is moved away from the center of the spheres, the rate of change of the fluence rate at the bladder wall is more than a factor of 2 larger when the bladder cavity is filled with a light-scattering suspension, as compared with water. The use of a light-scattering medium may therefore not be advantageous to achieve a uniform light distribution across the bladder wall.     

Formation of ordered mesoporous films from in situ structure inversion of azo polymer colloidal arrays

This work shows that mesoporous polymeric films with spherical and elliptical pores can be obtained by in situ structure inversion of the azo polymer colloid arrays through selective interaction with solvent. The epoxy-based azo polymer contained both the pseudo-stilbene-type azo chromophores and the hydrophilic carboxyl groups. The colloidal spheres of the azo polymer were prepared by gradual hydrophobic aggregation of the polymeric chains in THF-H2O media, induced by a steady increase in the water content. Ordered 2D arrays of the hexagonally close-packed colloidal spheres were obtained by the vertical deposition method. After the solvent (THF) annealing, the ordered 2D arrays were directly transformed to mesoporous films through the sphere-pore inversion. Under the same condition, the 2D arrays composed of the ellipsoidal colloids, which were obtained by the irradiation of a polarized Ar+ laser beam on the colloidal sphere arrays, could be transformed to films with ordered elliptical pores. To our knowledge, this is the first example to demonstrate that mesoporous structures can be directly formed from the colloidal arrays of a homopolymer through structure inversion. This observation can shed new light on the nature of self-assembly processes and provide a feasible approach to fabricate mesoporous structures without the infiltration-removal step. By exploring the photoresponsive properties of the materials, mesoporous film with special pore structure and properties can be expected.     

Electrostatic Interaction between Two Dissimilar Spheres with Constant Surface Charge Density

Explicit exact analytic expressions are obtained in the form of infinite series for the potential energy of the electrostatic interaction for the system of two dissimilar hard spheres with constant surface charge density in an electrolyte solution on the basis of the linearized Poisson-Boltzmann equation. The effects of the particle polarization, that is, the internal fields induced within tim interacting spheres, which are found to be of the order of instead of 1/κa (where κ is the Debye-Hückel parameter and a is the sphere radius), are taken into account. As in the case of the interaction at constant surface potential, the zeroth-order approximation to the interaction energy corresponds to the interaction energy that would be obtained if both spheres were ion-penetrable spheres ("soft" spheres) and to that obtained by the linear superposition approximation. The first-order approximation corresponds to the interaction energy that would be obtained if either sphere were a soft sphere, with the other being a hard sphere with constant surface charge density. The first-order correction term can be interpreted as the image interaction between the soft sphere and its image with respect to the hard sphere.     

Colloidal crystallization of poly(n-butyl acrylate) spheres in deionized aqueous suspension and the melting during dryness

Colloidal crystallization of poly(n-butyl acrylate) spheres (ammonium persulfate-poly(n-butyl acrylate) (APS-PBA), 320?±?50 nm in diameter) was studied in deionized aqueous suspension. Coexistence of the crystal and distorted crystal structures was observed by the reflection spectroscopy. The critical concentrations of melting were ca. 0.01 and 0.03 in volume fraction in the presence of ion-exchange resins and in their absence, respectively. Crystal structures melted away during dryness by fusion of each spheres on the substrates, i.e., cover glass, watch glass, and Petri glass dish. Thickness profiles of the dried film changed sharply from the broad ring to the round hill as sphere concentration increased. The sharpness parameter S was evaluated from the ratio of the film size (diameter) against the full width at half maximum in the thickness profiles of the ring and/or the round hill. The S values decreased sharply from 30 to 1.2 as initial volume fraction of the spheres increased from 0.0005 to 0.1. The S values were significantly low compared with those of typical colloidal spheres, which supports the aggregate and/or fusion of the spheres resulting in their low convectional flow during dryness. The round hill profile at the high sphere concentration also supports that the fusion takes place easier during dryness. Microscopic observation of the dried film supports the formation of the homogeneous fused structures. It was clarified that colloidal crystallization of APS-PBA spheres takes place by the extended electrical double layers around the spheres like typical colloidal crystals of hard spheres. However, APS-PBA spheres are not so stable by the fusion especially at the high sphere concentrations and on the substrates.     

Long-Range Electrostatic Interaction between a Charged Wall and Two Similarly Charged Colloidal Spheres at Low Surface Potentials

The long-range electrostatic interaction between a pair of similarly charged colloidal spheres and a charged planar wall at low surface potentials is theoretically investigated. The linear Poisson-Boltzmann equation (PBE) and the point charge approximation of the charged sphere are used. The electrical potential distribution in the electrolyte solution is found from the PBE at the constant surface potentials using the image charge method. The electrostatic forces acting on the spheres are then calculated. The results show that the repulsive interaction between a pair of similarly charged colloidal spheres clearly decreases when a charged wall appears nearby, but it is impossible for an attractive force to emerge at the scaled surface potentials less than 1. There is, however, an attractive force between the charged wall and the similarly charged colloidal spheres, when the surface potential zetap on the wall is sufficiently higher than the surface potential zetas on the spheres to make zetap > zetasexp(kappah) (h is the distance from the wall to the sphere center). In this case, there are negative surface charges on the spheres at positive surface potential zetas. It is these negative charges that produce the above attraction. Copyright 1999 Academic Press.     

Sedimentation of spheres at small Reynolds number

The effect of fluid inertia on the settling of spheres in a viscous incompressible fluid is studied in the limit of small Reynolds number. The kinetic energy of flow depends on the positions of the spheres, and gives rise to forces on the spheres. In the dilute limit it suffices to study the corresponding pair interaction. The interaction is calculated from the Stokes flow for two spheres settling between plane walls in the point particle limit. The dissipative interaction between a pair of spheres is calculated from the Proudman-Pearson [I. Proudman and J. R. A. Pearson, J. Fluid Mech. 2, 237 (1957)] solution of the Navier-Stokes equations for flow about a sphere in unbounded geometry. The combination of kinetic and dissipative interaction gives rise to a repulsive force of range of the order of the sphere diameter divided by the Reynolds number.     

Isotropic–nematic phase separation and demixing in mixtures of spherical nanoparticles with length‐polydisperse nanorods

An extension of Onsager theory is developed to simulate isotropic–nematic phase separation in a mixture of spheres with length‐polydisperse system of rods. This work is motivated by recent experimental data on nanorod liquid crystals. Prior theoretical investigations indicate that both polydispersity and the presence of spheres should increase the biphasic–nematic phase transition, that is, the nematic cloud point. Results indicate that the phase diagrams undergo drastic changes depending upon both particle geometry and rod length polydispersity. The key geometric factor is the ratio between the sphere diameter and the rod diameter. In general, length fractionation is enhanced by the addition of spheres, which may be experimentally advantageous for separating short nanorods from a polydisperse population. Simulation results also indicate that the nematic cloud and shadow curves may cross one another because of the scarcity of spheres in the shadow phase. In general, these results do indicate that the nematic cloud point increases as a function of sphere loading; however, in certain areas of phase space, this relationship is nonmonotonic such that the nematic cloud point may actually decrease with the addition of spheres. This work has application to a wide range of nanoparticle systems, including mixtures of spherical nanoparticles with nanorods or nanotubes. Additionally, a number of nonspherical particles and structures may behave as spheres, including crumpled graphene and tightly coiled polymers. © 2012 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2012     

Convectional,sedimentation and drying dissipative patterns of colloidal crystals of poly(methyl methacrylate) spheres on a watch glass

Direct observation of the convectional dissipative patterns at room temperature was successful on a cover glass during the course of dryness of colloidal crystals of poly(methyl methacrylate) colloidal spheres. Formation processes of the convectional patterns of spoke-like lines were observed as a function of sphere size and also sphere concentration. During dryness of the suspensions, the brilliant iridescent colors changed beautifully. Macroscopic and microscopic drying patterns of the dried film were observed. Multiple broad ring-like patterns were observed especially at low sphere concentrations. The water evaporation accompanied with the convectional flow of water and the colloidal spheres played an important role for the dissipative structure formation.