We developed a new sensing motif for the detection and quantification of creatinine, which is an important small molecule marker of renal dysfunction. This novel sensor motif is based on our intelligent polymerized crystalline colloidal array (IPCCA) materials, in which a three-dimensional crystalline colloidal array (CCA) of monodisperse, highly charged polystyrene latex particles are polymerized within lightly cross-linked polyacrylamide hydrogels. These composite hydrogels are photonic crystals in which the embedded CCA diffracts visible light and appears intensely colored. Volume phase transitions of the hydrogel cause changes in the CCA lattice spacings which change the diffracted wavelength of light. We functionalized the hydrogel with two coupled recognition modules, a creatinine deiminase (CD) enzyme and a 2-nitrophenol (2NPh) titrating group. Creatinine within the gel is rapidly hydrolyzed by the CD enzyme in a reaction which releases OH(-). This elevates the steady-state pH within the hydrogel as compared to the exterior solution. In response, the 2NPh is deprotonated. The increased solubility of the phenolate species as compared to that of the neutral phenols causes a hydrogel swelling which red-shifts the IPCCA diffraction. This photonic crystal IPCCA senses physiologically relevant creatinine levels, with a detection limit of 6 microM, at physiological pH and salinity. This sensor also determines physiological levels of creatinine in human blood serum samples. This sensing technology platform is quite general. It may be used to fabricate photonic crystal sensors for any species for which there exists an enzyme which catalyzes it to release H(+) or OH(-).

Zinc oxide ͑ZnO͒ nanoparticles ͑NPs͒ in the size range ϳ7-35 nm are synthesized by ball-milling technique, and microstructural and optical properties of the NPs are studied using varieties of techniques. Results from ball-milled NPs are compared with those of the commercially available ZnO nanopowder. X-ray diffraction pattern of the milled NPs indicates lattice strain in the NPs. High-resolution transmission electron microscopy analysis reveal severe lattice distortion and reduction in lattice spacing in some of the NPs. Optical absorption spectra of milled NPs show enhanced absorption peaked at 368 nm, which is blueshifted with reference to starting ZnO powder. Room-temperature photoluminescence spectra show five peaks consisting of ultraviolet and visible bands, and relative intensity of these peaks drastically changes with increasing milling time. Raman spectra of milled powders show redshift and broadening of the Raman modes of ZnO, and a new Raman mode evolve in the milled NPs. A correlation between the microstructure and optical properties of ZnO NPs is made on the basis of these results. Our results clearly demonstrate that commercially available ZnO nanopowders do not exhibit nanosize effects due to relatively large size of the ZnO NPs. Implications of these results are discussed.

Monodisperse, highly charged colloidal particles in low ionic strength solutions self-assemble into bcc or fcc crystalline colloidal arrays (CCAs) due to interparticle repulsive interactions. We demonstrate that a CCA of dyed particles embedded in a poly acrylamide hydrogel acts as a nanosecond optical Bragg diffraction switching device. Under low light intensities the CCA is refractive index matched to the medium and does not diffract. However, high intensity excitation within the dye absorption band heats the spheres within nanoseconds to decrease their refractive index. The array "pops up" to diffract light within 2.5 ns. These intelligent CCA hydrogels may have applications in optical limiting, computing, and nanosecond fast optical switching devices, etc. [S0031-9007(97)03099-8]

We characterized the diffraction and crystal structure of a crystalline colloidal array (CCA) photonic crystal composed of 270 nm diameter polystyrene spheres which have a nearest neighbor spacing of approximately 540 nm. This CCA diffracts light in first order at approximately 1200 nm and shows strong diffraction in the visible spectral region from higher order planes. We quantitatively examined the relative diffraction intensities of the putative fcc (111), (200), (220), and (311) planes. Comparing these intensities to those calculated theoretically we find that the crystal structure is fcc with significant stacking faults. Essentially, no light transmits at the Bragg angle for the fcc (111) planes even through thin approximately 40 microm thick CCA. However, much of this light is diffusely scattered about the Bragg angle due to crystal imperfections. Significant transmission occurs from thin samples oriented at the Bragg condition for the fcc (200), (220), and (311) planes. We also observe moderately intense two-dimensional diffraction from the first few layers at the crystal surfaces. We also examined the sample thickness dependence of diffraction from CCA photonic crystals prepared from approximately 120 nm polystyrene spheres whose fcc (111) planes diffract in the visible spectral region. These experimental observations, aided by calculations based upon a simple but flexible model of light scattering from an arbitrary collection of colloidal spheres, make clear that fabrication of three-dimensional photonic band gap crystals will be challenged by crystal imperfections.

Results obtained from the optical absorption and photoluminescence (PL) spectroscopy experiments have shown the formation of excitons in the silver-exchanged glass samples.These findings are reported here for the first time. Further, we investigate the dramatic changes in the photoemission properties of the silver-exchanged glass samples as a function of postannealing temperature. Observed changes are thought to be due to the structural rearrangements of silver and oxygen bonding during the heat treatments of the glass matrix.In fact, photoelectron spectroscopy does reveal these chemical transformations of silverexchanged soda glass samples caused by the thermal effects of annealing in a high vacuumatmosphere. An important correlation between temperature-induced changes of the PL intensity and thermal growth of the silver nanoparticles has been established in this Letter through precise spectroscopic studies.

We have developed photochemically controlled photonic crystals that may be useful in novel recordable and erasable memories and/or display devices. These materials can operate in the UV, visible, or near‐IR spectral regions. Information is recorded and erased by exciting the photonic crystal with ∼ 360 nm UV light or ∼ 480 nm visible light. The information recorded is read out by measuring the photonic crystal diffraction wavelength. The active element of the device is an azobenzene‐functionalized hydrogel, which contains an embedded crystalline colloidal array. UV excitation forms cis‐azobenzene while visible excitation forms trans‐azobenzene. The more favorable free energy of mixing of cis‐azobenzene causes the hydrogel to swell and to red‐shift the photonic crystal diffraction. We also observe fast nanosecond, microsecond, and millisecond transient dynamics associated with fast heating lattice constant changes, refractive index changes, and thermal relaxations.

Structural properties of copper phthalocyanine (CuPc) powder and its thin films coated on glass plate are investigated using X-ray diffraction, Raman scattering and optical absorption techniques. These experiments are carried out at room temperature on CuPc powder and as-coated, 320 C and 520 C annealed, CuPc thin films. From the X-ray diffraction (XRD), we find that the CuPc powder exists in monoclinic phase, as-coated film is in orthorhombic a-phase and the film annealed at 320 C exists in monoclinic b-phase with different lattice parameters as compared to those of the powder phase. The XRD peaks in 520 C annealed film do not show the presence of CuPc but indicate the presence of copper oxide (CuO) nanoclusters of approximately 15 nm size. The optical Raman phonon frequencies of CuPc powder, as-coated and 320 C annealed CuPc films show a slight shift in the intramolecular high frequency modes. Whereas, their low frequency Raman spectra from intermolecular modes are characteristically different indicating different phases. The different characteristic behavior of the optical absorption spectra of the as-coated and 320 C annealed CuPc films corroborate the structural changes in the annealed film.

Highly charged fluorinated monodisperse spherical particles of diameters between 50 and 250 nm were synthesized from 1H,1H-heptafluorobutyl methacrylate by emulsion polymerization. These particles have a low refractive index of 1.386. High particle surface charge densities were obtained by minimizing the polymer molecular weight. These colloids formed well-ordered crystalline colloidal arrays (CCAs), after dialysis and ion exchange, which Bragg diffract light at wavelengths from the near-IR down to 270 nm in the UV. The diffraction bandwidths in water are very narrow (<10 nm) due to the closeness of refractive index of the colloidal particles to that of water. These CCAs are excellent materials for narrow band notch optical filters. In addition, these fluorinated CCAs can be easily refractive index matched to a predominately aqueous medium. We have covalently attached dyes to the colloidal particles to prepare absorbing CCAs. We photopolymerized these dyed CCAs within a polyacrylamide matrix to form polymerized crystalline colloidal array (PCCA). These semisolid PCCAs can withstand vibrations, ionic impurity addition, and thermal shocks while maintaining the CCA ordering. The medium within the PCCA can easily be exchanged to exactly refractive index match the CCA. These refractive index matched dyed PCCAs may have applications in optical limiting, computing, and nanosecond fast optical switching devices as discussed in the accompanying paper.