Robust Chiral Organization of Cellulose Nanocrystals in Capillary Confinement.

We showed large area uniformly aligned chiral photonic bioderived films from a liquid crystal phase formed by a cellulose nanocrystal (CNC) suspension placed in a thin capillary. As a result of the spatial confinement of the drying process, the interface between coexisting isotropic and chiral phases aligns perpendicular to the long axis of the capillary. This orientation facilitates a fast homogeneous growth of chiral pseudolayers parallel to the interface. Overall, the formation of organized solids takes hours vs weeks in contrast to the slow and heterogeneous process of drying from the traditional dish-cast approach. The saturation of water vapor in one end of the capillary causes anisotropic drying and promotes unidirectional propagation of the anisotropic phase in large regions that results in chiral CNC solid films with a uniformly oriented layered morphology. Corresponding ordering processes were monitored in situ at a nanoscale, mesoscale, and microscopic scale with complementary scattering and microscopic techniques. The resulting films show high orientation order at a multilength scale over large regions and preserved chiral handedness causing a narrower optical reflectance band and uniform birefringence over macroscopic regions in contrast to traditional dish-cast CNC films and those assembled in a magnetic field and on porous substrates. These thin films with a controllable and well-identified uniform morphology, structural colors, and handedness open up interesting possibilities for broad applications in bioderived photonic nanomaterials.

Spectral manifestation of optical Tamm states in a metal-cholesteric liquid crystals stack.

The reflection spectrum of linearly polarized light by a system consisting of a metal film and two adjacent sequentially located cholesteric liquid crystals (CLCs) with opposite helical twists is theoretically studied. The system contains a dielectric index-matching layer (DIML) between the metal film and the CLC layers. It is shown that in such a system the excitation of optical Tamm states (OTSs) by linearly polarized light is possible. The influence of the CLC pitch, refractive indices, and thicknesses of the DIML and metal film on the OTS manifestation in the reflection spectrum of the system is studied. The strong influence of the DIML thickness on the OTS wavelength and the appearance of multiple OTSs with an increase in the DIML thickness is noted.

Release of Ammunition-Related Compounds from a Dutch Marine Dump Site.

After World War II, large amounts of ammunition were dumped in surface waters worldwide, potentially releasing harmful and toxic compounds to the environment. To study their degradation, ammunition items dumped in the Eastern Scheldt in The Netherlands were surfaced. Severe damage due to corrosion and leak paths through the casings were observed, making the explosives in the ammunition accessible to sea water. Using novel techniques, the concentrations of ammunition-related compounds in the surrounding seabed and in the seawater were analyzed at 15 different locations. In the direct vicinity of ammunition, elevated concentrations of ammunition-related compounds (both metals and organic substances) were found. Concentrations of energetic compounds ranged from below the limit of detection (LoD) up to the low two-digit ng/L range in water samples, and from below the LoD up to the one-digit ng/g dry weight range in sediment samples. Concentrations of metals were found up to the low microgram/L range in water and up the low ng/g dry weight in sediment. However, even though the water and sediment samples were collected as close to the ammunition items as possible, the concentrations of these compounds were low and, as far as available, no quality standards or limits were exceeded. The presence of fouling, the low solubility of the energetic compounds, and dilution by the high local water current were concluded to be the main causes for the absence of high concentrations of ammunition-related compounds. As a conclusion, these new analytical methods should be applied to continuously monitor the Eastern Scheldt munitions dump site.

Continuous wave mirrorless lasing in cholesteric liquid crystals with a pitch gradient across the cell gap.

Despite numerous efforts, continuous wave (CW) lasing in dye doped, one-dimensional (1D) photonic bandgap cholesteric liquid crystal (CLC) structures has not been previously reported, to our knowledge. Here we report on the observation of lasing in such structures under both coherent (laser) and incoherent (LED) CW light excitation. To achieve this effect, we used a 1D-photonic bandgap structure made of a polymer stabilized CLC with a pitch gradient across the cell thickness. A spectral reflectivity profile of such a CLC structure reveals local minima in the area within a photonic stopband and close to it. The realization of lasing pumped by low power CW light sources opens the possibility of all-organic, compact, tunable CW lasers for display and medical applications.

Periodic structures generated by light in chiral liquid crystals.

We discuss materials that reveal fundamental intercoupling of light and chirality in creation of complex structures. These materials are based on cholesteric liquid crystals (CLCs) photosensitized by azobenzene nematics. Transformation of the one-dimensional periodic structure of such CLCs into complex spatial patterns takes place on macroscopic scales, over the whole area of the CLC layer, under the influence of low power radiation including LED, ambient illumination, and sunlight. The obtained structures, with their origin in the strain of the CLC layers caused by trans-cis photoisomerization precede a shift in the bandgap position of the CLCs. The effect is observed both in red-shifting as well as blue-shifting CLCs.

Switchable orthorhombic F photonic crystals formed by holographic polymerization-induced phase separation of liquid crystal.

Electrically switchable photonic crystals are simply and rapidly formed by holographic polymerization-induced phase separation of liquid crystal from a monomer-liquid crystal mixture. We report the fabrication and electro-optical properties of liquid-crystal-filled polymer photonic crystals of orthorhombic F symmetry. Inverse opal and fcc structures can also be obtained. The crystals exhibit electrically switchable Bragg diffraction at ~8-10 V/microm with crystal structure in good agreement with theoretical expectations. These photonic crystals compare favorably with liquid-crystal-imbibed colloidal crystal arrays.

Noninvasive in vivo 13C-NMR spectroscopy of a 13C-labeled xenobiotic in the rat.

This study demonstrates that the xenobiotic product, 1-(o-chlorophenyl)-1-(p-chlorophenyl)-2,2-dichloro-3-13C-propane can be monitored in the liver of an intact animal by in vivo 13C surface coil NMR spectroscopy after intraperitoneal administration. The carbon-13 label could be detected after a single dose of only 200 mg/kg of the product. The intrahepatic changes of the signal intensity of the labeled product were monitored as a function of time. No signals corresponding to metabolites could be detected.

Droplet deformation and alignment for high-efficiency polarization-dependent holographic polymer-dispersed liquid-crystal reflection gratings.

Droplet deformation and alignment are achieved in holographic polymer-dispersed liquid-crystal reflection gratings by applying an in situ shear during recording. High diffraction efficiency (99%) is obtained for light polarized parallel to the shear, with nearly zero efficiency for perpendicular polarization, and no increase of incoherent scattering. Permanent polarization dependence is related to stress-induced morphology changes of liquid-crystal droplets that are frozen by polymerization. The system is studied by electron microscopy and modeled by anisotropic coupled-wave and scattering theory. The morphology is consistent with the theory of small deformations of liquid droplets in fluid flow. Diffraction efficiency measurements are in agreement with theory incorporating this morphology as well as concomitant orientation and alignment of liquid-crystal molecules.

Surface ultrastructure of pit organ, spectacle, and non pit organ epidermis of infrared imaging boid snakes: A scanning probe and scanning electron microscopy study.

Boid snakes possess unique infrared imaging pit organs. The ultrastructure of the surfaces of these organs scatter or reflect electromagnetic radiation of specific wavelengths. Pit organ epidermal surfaces of boid snakes are covered with arrays of pore-like structures called micropits. In order to determine the dimensions of this complicated surface structure, we have performed the first ultrastructural analysis on snake epidermis by high-resolution microscopy techniques. Using scanning probe microscopy and scanning electron microscopy, we found that the epidermis of pit organ, maxillary non pit organ, spectacle, and ventral scales contain arrays of micropits. These scale surfaces also contain major surface features of overlapping plate-like structures. Pit organ micropits averaged 319 nm in diameter and 46 nm in depth and were spaced an average of 808 nm from each other. These micropits were significantly deeper, of greater diameter, and spaced at greater distances apart than those of the other scales. Plate structures of the pit organs had a mean distance between plates of 3.5 microm and a mean plate step height of 151 nm. These differences serve to strengthen the argument that arrays of micropit and plate surface structures function as spectral filters or anti-reflective coatings with respect to incident electromagnetic radiation.

Volume holographic image storage and electro-optical readout in a polymer-dispersed liquid-crystal film.

We report storage and electrical switching of holographic image data in an economical polymer-dispersed liquidcrystal material. The hologram is recorded in a fast, single-step process and can be reversibly erased and restored repeatedly by the application of fields of approximately 10-15 V/ microm, with a response time of 22 micros and a relaxation time of 42 micros. Simple (quasi-sinusoidal) holographic transmission gratings also are studied with switching fields of <5 V/ microm and with response and relaxation times of 25 and 44 micros, respectively.

Optical limiting in solutions of diphenyl polyenes.

The optical-limiting behavior of a series of trans-alpha, omega-diphenyl polyene compounds was observed in solutions of chloroform. The influence of planarity, the substitution of donor and acceptor groups, and the extent of pi-electron delocalization on the nonlinear thresholds of the diphenyl polyenes in an optical-limiting geometry were examined. A saturation effect of optical-limiting nonlinear thresholds, consistent with the theoretical work, was observed at 10-11 pi-electron bonds. The temporal profiles of the transmitted laser pulses and the power dependence of the nonlinear thresholds as a function of spot size and wavelength were examined. These examinations led to the conclusion that the predominant nonlinear mechanism was quasi-steady-state self-focusing. Nonlinear thresholds an order of magnitude lower, and thus effective n(2) and X(3) values an order of magnitude higher, than the well-known self-focusing medium CS(2) were observed. Our studies demonstrate that this series of polyenes consists of efficient broadband nonresonant optical-limiting materials.

Contra-directional two-beam coupling by use of a single input beam in an iron-doped lithium niobate multimode fiber.

Experimental results are presented for 1,800 contra-directional two-beam coupling (TBC) measurements in a single crystal fiber of LiNbO8:Fe using a single incident beam and its Fresnel reflection off the back surface of the fiber. To our knowledge, this is the first time that volume gratings have been written in a fiber using this beam coupling geometry. At small f-numbers, the TBC efficiency has been predicted to decrease in bulk LiNbO3:Fe due to the erasure of the weak gratings by the dark conductivity. We present experimental results validating the published theory and show experimentally that confinement of the interfering beams in a fiber geometry overcomes this limitation.