Optical response of mesoporous synthetic opals to the adsorption of chemical species

We have demonstrated the fabrication of a colloidal crystalline array (synthetic opal) from monodispersed mesoporous silica spheres (MMSS) and the control of its optical response simply by changing the amount of benzene vapor adsorbed into the pores of MMSS. It was revealed that the refractive index of the colloidal crystal of MMSS showed an 11.7% increase by taking advantage of benzene adsorption, and thereby, the structural color changed reversibly. We also conducted the same measurement on silica spheres without mesopores and observed no change in the refractive index or the structural color. This optical response gives rise to the possibility of using MMSS colloidal crystals not only for controlling light reflection but also as sensing devices based on color change due to vapor adsorption. We have also incorporated an organic dye, the porphyrin derivative alpha,beta,chi,delta,-tetrakis(1-methylpyridinium-4-yl)porphyrin rho-toluenesulfonate (TMPyP), into the pores of MMSS. By adopting an electrophoretic deposition process in ethanol, periodic arrays fabricated from TMPyP-MMSS conjugates with absolute zeta-potentials near zero were obtained. The Bragg diffraction peak of the colloidal crystalline array shifted to longer wavelengths due to an increase in the refractive index with increasing amounts of TMPyP adsorbed in the pores. The current work demonstrates the new possibility of creating colloidal crystals from MMSS with mesopores filled with various kinds of adsorbates to control the optical response effectively.     

Fluid biomembranes supported on nanoporous aerogel/xerogel substrates

Planar supported lipid bilayers have attracted immense interest for their properties as model cell membranes and for potential applications in biosensors and lab-on-a-chip devices. We report the formation of fluid planar biomembranes on hydrophilic silica aerogels and xerogels. Scanning electron microscopy results showed the presence of interconnected silica beads of approximately 10-25 nm in diameter and nanoscale open pores of comparable size for the aerogel and grain size of approximately 36-104 nm with approximately 9-24 nm diameter pores for the xerogel. When the aerogel/xerogel was prehydrated and then allowed to incubate in l-alpha-phosphatidylcholine (egg yolk PC) unilamellar vesicle (approximately 30 nm diameter) solution, lipid bilayers were formed due to the favorable interaction of vesicles with the hydroxyl-abundant silica surface. Lateral mobility of labeled lipid N-(7-nitrobenz-2-oxa-1,3-diazol-4-yl)-1,2-dihexadecanoyl-sn-glycero-3-phosphoethanolamine was retained in the membranes. A diffusion coefficient of 0.61 +/- 0.22 microm(2)/s was determined from fluorescence recovery after photobleaching analysis for membranes on aerogels, compared to 2.46 +/- 0.35 microm(2)/s on flat glass. Quartz crystal microbalance-dissipation was utilized to monitor the kinetics of the irreversible adsorption and fusion of vesicles into bilayers on xerogel thin films.     

Colloidal woodpile structure: three-dimensional photonic crystal with a dual periodicity

With planar photolithography and self-assembly techniques, multilayer colloidal crystals with a woodpile structure were fabricated. They represent a new kind of photonic crystals, that is, three-dimensional (3D) photonic crystals with a dual periodicity; one comes from the face-centered cubic (fcc) structure within the colloidal crystal strips and the other one results from the periodic arrangement of the colloidal crystal strips.     

Interaction thresholds for adsorption of quantum gases on surfaces and within pores of various shapes

Adsorption within pores and on surfaces occurs because of the attractive potential provided by the adsorbent. If the attraction is too weak, however, adsorption does not occur to any significant extent. This paper evaluates the criterion for such adsorption, at zero temperature, of the quantum gases 4He and H2. This criterion is expressed as a relationship between a threshold value of the well-depth (D) of the adsorption potential (on a semi-infinite planar surface) and the hard-core diameter (sigma) of the gas-surface pair potential. Six geometries are considered, of which two result in two-dimensional (2D) adsorbed phases, two result in one-dimensional (1D) phases, and two result in zero-dimensional phases. These are monolayer films on semi-infinite substrates or within a slit pore, linear or axial phases within cylindrical pores (within bulk solids) or cylindrical tubes, and single-particle adsorption within spherical pores or hollow spherical cavities, respectively. The criteria for film adsorption are consistent with analogous criteria for film wetting to occur, evaluated with a simple thermodynamic model.     

Water in extremely narrow planar pores with crystalline walls. 2. Thermodynamics

The free energy, entropy, and work of water vapor adsorption in planar pores with widths of 0.62 and 1.25 nm located in a silver iodide crystal parallel to its basal face have been computed at the molecular level. In contrast to adsorption on a free surface, the adsorption in the pores proceeds in three stages, i.e., the formation of molecular films on the walls, coalescence of the films, and densification of the fluid in the pore volume. At the second stage, the equilibrium between the fluid in the pore and the vapor over the pore at temperatures corresponding to normal conditions is thermodynamically unstable and accompanied by the development of a free energy barrier and the existence of metastable states. As temperature is elevated, the instability is gradually evened out; however, its signs remain preserved even at the boiling temperature of water. Extremely narrow pores with widths smaller than 1 nm are always filled with water under conditions of even a rather dry natural atmosphere. The filling of pores several nanometers wide in strongly unsaturated water vapors overcomes the free-energy barrier; however, the fluid that has filled the pore remains stable with respect to evaporation in vapors with densities lower than the density of saturated vapor by several orders of magnitude. The existence of the free-energy barrier and metastable states in nanosized breaks in crystals creates conditions for hysteresis of adsorption-desorption cycles.     

A class of supported membranes: formation of fluid phospholipid bilayers on photonic band gap colloidal crystals

We report the formation of a new class of supported membranes consisting of a fluid phospholipid bilayer coupled directly to a broadly tunable colloidal crystal with a well-defined photonic band gap. For nanoscale colloidal crystals exhibiting a band gap at the optical frequencies, substrate-induced vesicle fusion gives rise to a surface bilayer riding onto the crystal surface. The bilayer is two-dimensionally continuous, spanning multiple beads with lateral mobilities which reflect the coupling between the bilayer topography and the curvature of the supporting colloidal surface. In contrast, the spreading of vesicles on micrometer scale colloidal crystals results in the formation of bilayers wrapping individual colloidal beads. We show that simple UV photolithography of colloidal crystals produces binary patterns of crystal wettabilities, photonic stopbands, and corresponding patterns of lipid mono- and bilayer morphologies. We envisage that these approaches will be exploitable for the development of optical transduction assays and microarrays for many membrane-mediated processes, including transport and receptor-ligand interactions.     

Layer transfer approach to opaline hetero photonic crystals

By taking advantage of the hydrophobicity of dry polystyrene colloidal crystal (opal) films and the large surface tension of water, a convectively self-assembled polystyrene opal film on a hydrophilic glass substrate can be peeled off from the substrate and floated on the water surface. A layer transfer technique was developed to sequentially stack floating opal films of different sphere sizes, resulting in opaline hetero photonic crystals. The feasibility of this technique to planar defect engineering in a self-assembled colloidal photonic crystal was also demonstrated. Both structural observation and optical characterization confirmed the crystalline integrity of the resultant opaline heterostructures.     

Thermodynamic model of surfactant adsorption on soft liquid crystal interfaces

The Gibbs adsorption isotherm for planar liquid crystal/fluid interfaces is derived using the anisotropic Gibbs-Duhem equation. The Gibbs adsorption isotherm for planar interfaces is used to analyze the adsorption-driven orientation transition in aqueous solutions of anionic surfactants in contact with rodlike uniaxial nematic liquid crystal films. In qualitative agreement with experiments, the model predicts that, as the surfactant concentration increases, the tangential (planar) average molecular orientation of the liquid crystal with respect to the interface undergoes a transition to a normal (homeotropic) orientation. The anchoring coefficient or strength of anisotropic component of the interfacial tension is shown to depend on the surfactant's concentration. Analyzing the response to addition of a co-cation, the model reveals that, as the fractional coverage of the surfactant's chains increases, the interpenetration of liquid crystal molecules between the adsorbed surfactant tails promotes the orientation transition; at even higher surfactant chain concentrations, interpenetration is hindered because of lack of available space and a random surface orientation emerges. Thus, for aqueous surfactant solutions in contact with nematic liquid crystals, increasing the surfactant concentration leads to the following interfacial liquid crystal orientation transition cascade, planar orientation --> homeotropic orientation --> random orientation, which can lead to new sensor capabilities and surface structuring processes.     

Assembly of lipid bilayers on silica and modified silica colloids by reconstitution of dried lipid films

A method is presented for the assembly of lipid bilayers on silica colloids via reconstitution of dried lipid films solvent-cast from chloroform within packed beds of colloids ranging from 100 nm to 10 μm in diameter. Rapid solvent evaporation from the packed bed void volume results in uniform distribution of dried lipid throughout the colloidal bed. Fluorescence measurements indicate that significant, if not quantitative, retention of DOPC or DPPC films cast between sub-bilayer and multilayer quantities occurs when the colloids are redispersed in aqueous solution. Phospholipid bilayers assembled in this manner are shown to effectively passivate the surface of 250 nm colloids to nonspecific adsorption of bovine serum albumin. The method is shown to be capable of preparing supported bilayers on colloid surfaces that do not generally support vesicle fusion such as poly(ethylene glycol) (PEG) modified silica colloids. Bilayers of lipids that have not been reported to self-assemble by vesicle fusion, including gel-phase lipids and single-chain diacetylene amphiphiles, can also be formed by this method. The utility of the solid-core support is demonstrated by the facile assembly of supported lipid bilayers within fused silica capillaries to generate materials that are potentially suitable for the analysis of membrane interactions in a microchannel format.     

Magnetic porous ferrospinel NiFe2O4: A novel ozonation catalyst with strong catalytic property for degradation of di-n-butyl phthalate and convenient separation from water

The fluorescence-based sensing capability of ultrathin ZnO-SiO(2) nanoplatforms, deposited by an integrated approach of colloidal lithography and metal organic chemical vapor deposition, has been investigated upon adsorption of fluorescein-labeled albumin, used as model analyte biomolecule. The protein immobilization process after spontaneous adsorption/desorption significantly enhances the green emission of the different ZnO-based films, as evidenced by scanning confocal microscopy, corresponding to a comparable protein coverage detected by X-ray photoelectron spectroscopy. Moreover, experiments of fluorescence recovery after photobleaching evidence that the protein lateral diffusion at the biointerface is affected by the chemical and/or topographical patterning of hybrid ZnO-SiO(2) surfaces. The used approach is very promising for biomolecular detection applications of these ZnO-SiO(2) nanoplatforms, by simple sizing of the 2D vs. 3D patterning design, which in turn is accomplished by the fine tuning of the integrated colloidal lithography-chemical vapor deposition processes.     

Effects of liquid bridge between colloidal spheres and evaporation temperature on fabrication of colloidal multilayers

For the application of colloidal crystal films as "photonic band gap" materials, their domain size and thickness are significant. The substrate withdrawing speed, the colloidal suspension volume fraction, and the colloidal suspension temperature have been studied for the domain size and thickness controls of colloidal crystals in this study. Stable dispersions of monodispersed polystyrene spheres with a diameter of 245 nm were synthesized according to a general emulsion polymerization for colloidal crystal films. By experimental results and the theoretical relationship between the number of layers and other parameters, we could know that the water bridge between colloidal spheres (which is formed by capillary force) influences the number of colloidal crystal layers significantly.     

Inverse opals of molecularly imprinted hydrogels for the detection of bisphenol A and pH sensing

Inverse opal films of molecularly imprinted polymers (MIP) were elaborated using the colloidal crystal template method. The colloidal crystals of silica particles were built by the Langmuir-Blodgett technique, allowing a perfect control of the film thickness. Polymerization in the interspaces of the colloidal crystal in the presence of bisphenol A (BPA) and removal of the used template provides 3D-ordered macroporous methacrylic acid-based hydrogel films in which nanocavities derived from bisphenol A are distributed within the thin walls of the inverse opal hydrogel. The equilibrium swelling properties of the nonimprinted (NIPs) and molecularly imprinted polymers (MIPs) were studied as a function of pH and bisphenol A concentration, while the molecular structures of the bulk hydrogels were analyzed using a cross-linked network structure theory. This study showed an increase in nanopore (mesh) size in the MIPs after BPA extraction as compared to NIPs, in agreement with the presence of nanocavities left by the molecular imprints of the template molecule. The resulting inverse opals were found to display large responses to external stimuli (pH or BPA) with Bragg diffraction peak shifts depending upon the hydrogel film thickness. The film thickness was therefore shown to be a critical parameter for improving the sensing capacities of inverse opal hydrogel films deposited on a substrate.     

Nonspherical colloidal crystals fabricated by the thermal pressing of colloidal crystal chips

Nonspherical colloids and their ordered arrays may be more attractive in applications such as photonic crystals than their spherical counterparts because of their lower symmetries, although such structures are difficult to achieve. In this letter, we describe the fabrication and characterization of colloidal crystals constructed from nonspherical polyhedrons. We fabricated such nonspherical colloidal crystals by pressing spherical polymer colloidal crystal chips at a temperature slightly lower than the glass-transition temperature (T(g)) of these polymer colloids. During this process, the polymer microspheres were distinctively transformed into polyhedrons according to their crystal structures, whereas the long-range order of the 3D lattice was essentially preserved. Because a working temperature lower than T(g) effectively prevented the colloidal crystals from fusing into films, the spherical colloidal crystals were transformed greatly under pressure, which lead to obvious change in the optical properties of colloidal crystals. Besides their special symmetry and optical properties, these nonspherical colloidal crystals can be used as templates for 2D or 3D structures of special symmetry, such as 2D nano-networks. We anticipate that this fabrication technique for nonspherical colloidal crystals can also be extended to nonspherical porous materials.     

Fabrication of photonic crystals with nigrosine-doped poly(MMA-co-DVB-co-MAA) particles

A convenient approach was developed to fabricate monodisperse nigrosine-doped poly(methyl methacrylate-co-divinylbenzene-co-methacrylic acid) nanoparticles with different cross-linkage by soap-free emulsion polymerization at boiling status and swelling process. The dye-doped nanoparticles were used for the fabrication of colloidal crystal films and beads. It was found that nigrosine dye in the nanoparticles can efficiently depress the light scattering inside the colloidal crystal films and eliminate the iridescent effect in the photonic beads. These results make the colloidal crystals useful in photonic paper, bioassay, and so on.     

QCM-D on mica for parallel QCM-D-AFM studies

Quartz crystal microbalance with dissipation monitoring (QCM-D) has developed into a recognized method to study adsorption processes in liquid, such as the formation of supported lipid bilayers and protein adsorption. However, the large intrinsic roughness of currently used gold-coated or silica-coated QCM-D sensors limits parallel structural characterization by atomic force microscopy (AFM). We present a method for coating QCM-D sensors with thin mica sheets operating in liquid with high stability and sensitivity. We define criteria to objectively assess the reliability of the QCM-D measurements and demonstrate that the mica-coated sensors can be used to follow the formation of supported lipid membranes and subsequent protein adsorption. This method allows combining QCM-D and AFM investigations on identical supports, providing detailed physicochemical and structural characterization of model membranes.     

Incorporation of block copolymer micelles into multilayer films for use as nanodelivery systems

This work demonstrates the potential application of stimulus responsive block copolymer micelles as triggerable delivery systems for use within multilayer films. Cationic, pH-responsive micelles of poly[2-(dimethylamino)ethyl methacrylate-block-poly(2-(diethylamino)ethyl methacrylate)] (PDMA-PDEA) were deposited on anionic polystyrene latex particles. The charge reversal of the surface and the amount of adsorbed polymer were monitored by zeta potential measurements and colloidal titrations, respectively. Prior to adsorption, the PDMA-PDEA micelles were loaded with a hydrophobic dye, and UV-vis spectroscopy was used to determine the amount of dye encapsulated within a monolayer of micelles. It was found that subtle chemical modification of the PDMA-PDEA diblock copolymer via permanent quaternization of the PDEA block results in micelles with tunable loading capacities. Multilayers of cationic micelles of partially quaternized PDMA-PDEA and anionic polyelectrolyte (poly(sodium 4-styrene sulfonate)) were deposited on the surface of polystyrene latex particles by sequential adsorption. UV-vis analysis of the dye present within the multilayer after the addition of each layer demonstrates that the micelles are sufficiently robust to retain encapsulated dye after multiple adsorption/washing cycles and can thus create a film that can be increasingly loaded with dye as more micelle layers are adsorbed. Multiple washing cycles were performed on micellar monolayers of PDMA-PDEA to demonstrate how such systems can be used to bring about triggerable release of actives. When performing several consecutive washing steps at pH 9.3, the micelle structure of the PDMA-PDEA micelles in the monolayer is retained, resulting in only a small reduction in the amount of encapsulated dye. In contrast, washing at pH 4, the structure of the micelle layers is severely disrupted, resulting in a fast release of the encapsulated dye into the bulk. Finally, if a sufficient number of micelle/homopolyelectrolyte layers are adsorbed, it is possible to selectively dissolve the latex template, resulting in hollow capsules.     

流动控制沉积法制备PMMA叠层光子晶体薄膜及其光学性能研究

采用流动控制沉积法,通过调控泵速和聚甲基丙烯酸甲酯(PMMA)胶体微球溶液的浓度,制备出微球排列高度有序且薄膜紧密附着于基底的高质量光子晶体薄膜。获得了制备高质量PMMA光子晶体薄膜的组装条件范围,发现在该条件范围内,当泵速或胶体微球溶液浓度一定时,PMMA光子晶体薄膜的厚度随胶体微球溶液浓度的增加或泵速的降低而增加。研究了组装条件对PMMA光子晶体薄膜光学性能的影响,发现光子禁带位置随光子晶体薄膜厚度增加或减少而红移或蓝移。在此基础上,控制组装条件得到了不同尺寸微球堆叠而成的叠层光子晶体薄膜,并研究了其光学性能的变化规律。结果显示,叠层光子晶体薄膜的光子禁带峰为各层叠层光子晶体禁带峰的简单叠加,且峰强度受光入射角方向影响。     

Polymer coatings for improved protein crystal growth

The ability to grow quality protein crystals is necessary to analyze protein structure by X-ray diffraction and related techniques. As such it plays a key role in enzymology, structure-based drug design, molecular biology, and other biomedical areas. It is also required for macromolecule purification by crystallization. Protein crystal growth (PCG) may be negatively influenced by various factors related to nonspecific adsorption and adherence at growth chamber surfaces. Such factors include nucleation and growth of flawed crystals at chamber walls, or wall growth blockage of optical monitoring paths. Surface localized poly(ethylene glycol) (PEG) and other neutral, hydrophilic polymers are known to significantly reduce nonspecific adsorption of biological macromolecules and particles. Preliminary studies, involving various PCG methods (temperature induction, vapor diffusion), apparatii (test tubes, cuvettes, and specialized PCG hardware), growth chamber materials (glass, polystyrene, polysulfone), chamber volumes (0.1–10 ml) and protein samples (lysozyme, thaumatin, insulin) indicate the potential of PEG coatings to significantly reduce problems related to adsorption in PCG. The results, which match the ability of such coatings to reduce protein adsorption as evaluated by both ellipsometry and enzyme linked immunoassay, are discussed in relation to colloidal stabilization theory and properties of PEG coated surfaces.     

Capillary condensation hysteresis in overlapping spherical pores: a monte carlo simulation study

The mechanisms of hysteretic phase transformations in fluids confined to porous bodies depend on the size and shape of pores, as well as their connectivity. We present a Monte Carlo simulation study of capillary condensation and evaporation cycles in the course of Lennard-Jones fluid adsorption in the system of overlapping spherical pores. This model system mimics pore shape and connectivity in some mesoporous materials obtained by templating cubic surfactant mesophases or colloidal crystals. We show different mechanisms of capillary hysteresis depending on the size of the window between the pores. For the system with a small window, the hysteresis cycle is similar to that in a single spherical pore: capillary condensation takes place upon achieving the limit of stability of adsorption film and evaporation is triggered by cavitation. When the window is large enough, the capillary condensation shifts to a pressure higher than that of the isolated pore, and the possibility for the equilibrium mechanism of desorption is revealed. These finding may have important implications for practical problems of assessment of the pore size distributions in mesoporous materials with cagelike pore networks.     

Connected open structures from close-packed colloidal crystals by hyperthermal neutral beam etching

We report the fabrication of connected open structures from close-packed colloidal crystals by hyperthermal neutral beam etching. Colloidal crystal films of polystyrene microspheres were prepared by a vertical deposition method. Exposure of the colloidal crystal films to hyperthermal neutral beam made isolated microspheres in the face-centered cubic lattice, each of which was connected with its twelve nearest neighbors through very thin cylinders. Due to the charge neutrality of impinging gas molecules of the hyperthermal neutral beam, the spherical shape of polymer microspheres was almost maintained during the etching process. The Bragg reflection peaks were modulated by the etched volume of colloidal crystals. Finally, the inverse structures of such open structures were replicated by a simple room-temperature chemical vapor deposition and subsequently burning out polymer template spheres.