Elimination of dimer formation in InIIIporphyrin-based anion-selective membranes by covalent attachment of the ionophore

The spontaneous hydroxy-bridged dimer formation of metalloporphyrins in ion-selective membranes gives rise to a short sensor lifetime (typically days), triggered by solubility problems, the occurrence of a super-Nernstian response slope, and a pH cross response. This dimer formation is eliminated here by covalent attachment of the ionophore to the polymer matrix. Specifically, two different indium(III)porphyrins containing polymerizable groups, the chloride-selective chloro(3-[18-(3-acryloyloxypropyl)-7,12-bis(1-methoxyethyl)-3,8,13,17-tetramethylporphyrin-2-yl]propyl ester)indium(III) and the nitrite-selective Chloro(5-(4-acryloyloxyphenyl)-10,15,20-triphenylporphyrinato)indium(III), were synthesized and copolymerized with methyl methacrylate and decyl methacrylate. The covalent attachment of the ionophore to the polymer matrix indeed prevents the metalloporphyrin from forming dimeric species, as confirmed by UV/visible spectroscopy. The ion-selective membranes with grafted indium porphyrin showed Nernstian response slopes to chloride, nitrite, perchlorate, and thiocyanate anions, with a selectivity comparable to membranes with freely dissolved or underivatized metalloporphyrin. The membranes containing grafted ionophores showed a lifetime of at least two months, apparently since crystallization of the poorly soluble dimeric species may no longer occur. This is one of the first examples where the covalent attachment of an ionophore drastically improves on a number of important sensor characteristics.     

Effects of fiber-optic probe design and probe-to-target distance on diffuse reflectance measurements of turbid media: an experimental and computational study at 337 nm

Fiber-optic probes are widely used in optical spectroscopy of biological tissues and other turbid media. Only limited information exists, however, on the ways in which the illumination-collection geometry and the overall probe design influence the interrogation of media. We have investigated both experimentally and computationally the effect of probe-to-target distance (PTD) on the diffuse reflectance collected from an isotropically (Lambertian) scattering target and an agar-based tissue phantom. Studies were conducted with three probes characterized by either common (single-fiber) or separate (two bifurcated multifiber probes) illumination and collection channels. This study demonstrates that PTD, probe design, and tissue scattering anisotropy influence the extent of the transport of light into the medium, the light-collection efficiency, and the sampling volume of collected light. The findings can be applied toward optimization of fiber-optic probe designs for quantitative optical spectroscopy of turbid media including biological tissues.     

Fabrication and measurement of low-stress membrane mirrors for adaptive optics

We have fabricated low-stress membranes from single-crystal silicon for use as deformable mirrors in adaptive optics. These membranes have lower stress than membranes made from silicon nitride or other materials and therefore are capable of greater deformation than previously used membrane mirrors. Membranes were assembled into devices by flip chip bonding to electrode chips with either 256 or 1024 electrodes. We have characterized devices with static and dynamic tests and compared their performance with an analytical model. We tracked the evolution of strain in the membrane during the device's fabrication and assembly and identified sources of stress and strain in this process. We identified boron dopant concentration as a critical determinant of intrinsic stress in the membrane.     

Diffraction effects on broadband radiation: formulation for computing total irradiance

I present a formulation for treating diffraction effects on total irradiance in the case of a Planck source; earlier work generally depended on calculating diffraction effects on spectral irradiance followed by summation over spectral components. The formulation is derived and demonstrated for Fraunhofer diffraction by circular apertures, rectangular apertures and slits, and Fresnel diffraction by circular apertures. The prospects for treating other sources and optical systems are also discussed.     

High-transfer-rate high-capacity holographic disk data-storage system

We describe the design and implementation of a high-data-rate high-capacity digital holographic storage disk system. Various system design trade-offs that affect density and data-rate performance are described and analyzed. In the demonstration system that we describe, high-density holographic recording is achieved by use of high-resolution short-focal-length optics and correlation shift multiplexing in photopolymer disk media. Holographic channel decoding at a 1-Gbit/s data rate is performed by custom-built electronic hardware. A benchmark sustained optical data-transfer rate of 10 Gbits/s has been successfully demonstrated.     

Frequency-shifted optical feedback in a pumping laser diode dynamically amplified by a microchip laser

Compared with conventional optical heterodyne detection, laser optical feedback imaging (LOFI) allows for a several orders of magnitude higher intensity modulation contrast. The maximum contrast amplification is typically 10(3) for a diode laser in the gigahertz range and 10(6) for a microchip laser in the megahertz range. To take advantage of the wavelength tunability of a laser diode and of the lower resonant detection frequency of a microchip laser, we used LOFI modulation induced by the frequency-shifted optical feedback in a laser diode as a modulated pumping power for a microchip laser for resonant dynamic amplification. In this way, we were able to transfer the optical feedback sensitivity of the laser diode to the megahertz range. Application to telemetry is also reported.     

Photophysics of laser dye-doped polymer membranes for laser-induced fluorescence photogrammetry

Laser-induced fluorescence target generation in dye-doped polymer films has recently been introduced as a promising alternative to more traditional photogrammetric targeting techniques for surface profiling of highly transparent or reflective membrane structures. We investigate the photophysics of these dye-doped polymers to help determine their long-term durability and suitability for laser-induced fluorescence photogrammetric targeting. These investigations included experimental analysis of the fluorescence emission pattern, spectral content, temporal lifetime, linearity, and half-life. Results are presented that reveal an emission pattern wider than normal Lambertian diffuse surface scatter, a fluorescence time constant of 6.6 ns, a pump saturation level of approximately 20 microJ/mm2, and a useful lifetime of more than 300,000 measurements. Furthermore, two demonstrations of photogrammetric measurements by laser-induced fluorescence targeting are presented, showing agreement between photogrammetric and physically measured dimensions within the measurement scatter of 100 microm.     

Practical implications of neutron survey instrument performance

Improvements have been made to the Monte Carlo modelling used to calculate the response of the neutron survey instruments most commonly used in the UK, for neutron energies up to 20 MeV. The improved modelling of the devices includes the electronics and battery pack, allowing better calculations of both the energy and angle dependence of response. These data are used to calculate the response of the instruments in rotationally and fully isotropic, as well as unidirectional fields. Experimental measurements with radionuclide sources and monoenergetic neutron fields have been, and continue to be made, to test the calculated response characteristics. The enhancements to the calculations have involved simulation of the sensitivity of the response to variations in instrument manufacture, and will include the influence of the user and floor during measurements. The practical implications of the energy and angle dependence of response, variations in manufacture, and the influence of the user are assessed by folding the response characteristics with workplace energy and direction distributions.