Photopolymerization with high-order Bessel light beams.

We study photopolymerization with high-order Bessel light beams with phase singularities on-axis. Self-trapping and self-focusing of propagation-invariant light beams in a photopolymer allow the fabrication of extended helical microfibers with a length scale of a centimeter, which is more than an order of magnitude larger than the propagation distance of the Bessel light beams. We show the evolution of microfibers rotating at a rate proportional to the incident optical power, while the periodicity of the helical structures remains constant, irrespective of the laser power. This suggests that optical momentum transfer plays a predominant role in the growth and rotation of such fiber structures.

Optical vortex-induced forward mass transfer: manifestation of helical trajectory of optical vortex.

The orbital angular momentum of an optical vortex field is found to twist high viscosity donor material to form a micron-scale 'spin jet'. This unique phenomenon manifests the helical trajectory of the optical vortex. Going beyond both the conventional ink jet and laser induced forward mass transfer (LIFT) patterning technologies, it also offers the formation and ejection of a micron-scale 'spin jet' of the donor material even with an ultrahigh viscosity of 4 Pa·s. This optical vortex laser induced forward mass transfer (OV-LIFT) patterning technique will enable the development of next generation printed photonic/electric/spintronic circuits formed of ultrahigh viscosity donor dots containing functional nanoparticles, such as quantum dots, metallic particles and magnetic ferrite particles, with ultrahigh spatial resolution. It can also potentially explore a completely new needleless drug injection.

Crystal Structure of the 11-cis Isomer of Pharaonis Halorhodopsin: Structural Constraints on Interconversions among Different Isomeric States.

Like other microbial rhodopsins, the light driven chloride pump halorhodopsin from Natronomonas pharaonis (pHR) contains a mixture of all-trans/15-anti and 13-cis/15-syn isomers in the dark adapted state. A recent crystallographic study of the reaction states of pHR has shown that reaction states with 13-cis/15-syn retinal occur in the anion pumping cycle that is initiated by excitation of the all-trans isomer. In this study, we investigated interconversions among different isomeric states of pHR in the absence of chloride ions. The illumination of chloride free pHR with red light caused a large blue shift in the absorption maximum of the retinal visible band. During this "red adaptation", the content of the 11-cis isomer increased significantly, while the molar ratio of the 13-cis isomer to the all-trans isomer remained unchanged. The results suggest that the thermally activated interconversion between the 13-cis and the all-trans isomers is very rapid. Diffraction data from red adapted crystals showed that accommodation of the retinal chromophore with the 11-cis/15-syn configuration was achieved without a large change in the retinal binding pocket. The measurement of absorption kinetics under illumination showed that the 11-cis isomer, with a λmax at 565 nm, was generated upon excitation of a red-shifted species (λmax = 625 nm) that was present as a minor component in the dark adapted state. It is possible that this red-shifted species mimics an O-like reaction state with 13-cis/15-syn retinal, which was hypothesized to occur at a late stage of the anion pumping cycle.

Crystal structures of the L1, L2, N, and O states of pharaonis halorhodopsin.

Halorhodopsin from Natronomonas pharaonis (pHR) functions as a light-driven halide ion pump. In the presence of halide ions, the photochemical reaction of pHR is described by the scheme: K→ L1 → L2 → N → O → pHR' → pHR. Here, we report light-induced structural changes of the pHR-bromide complex observed in the C2 crystal. In the L1-to-L2 transition, the bromide ion that initially exists in the extracellular vicinity of retinal moves across the retinal Schiff base. Upon the formation of the N state with a bromide ion bound to the cytoplasmic vicinity of the retinal Schiff base, the cytoplasmic half of helix F moves outward to create a water channel in the cytoplasmic interhelical space, whereas the extracellular half of helix C moves inward. During the transition from N to an N-like reaction state with retinal assuming the 13-cis/15-syn configuration, the translocated bromide ion is released into the cytoplasmic medium. Subsequently, helix F relaxes into its original conformation, generating the O state. Anion uptake from the extracellular side occurs when helix C relaxes into its original conformation. These structural data provide insight into the structural basis of unidirectional anion transport.