Sinusoidal relief gratings for zero-order reconstruction of black-and-white images

The reconstruction of black-and-white images using the zero-order transmitted light from surface-relief sinusoidal phase gratings is discussed and a two-step recording technique for these structures is described. These recordings can be economically replicated by embossing into thermoplastic sheet and can be reconstructed in conventional projectors to form high quality images with full gray scale. The computed zero-order luminous density and color are compared with measured values for single and crossed grating structures of period 1.4 μm embossed in PVC. A maximum density of about 1.8 was obtained for optimized embossed structures with neutral gray scale and black, and a resolution capability of about 300 lines/mm.     

Silicon-29 NMR spectroscopy in carbohydrate chemistry: Galactose derivatives

²⁹Si NMR spectra of the O-trimethylsilyl (OTMS) derivatives of various methyl α- and β-D -galactopyranosides have been recorded. The effect of changes in the anomeric configuration provides a means of assigning the resonance of the 2-OTMS substituent. Whereas the signal of the OTMS group attached at the 6-position can be assigned readily, those of the OTMS group at the 3- or 4-position cannot be assigned unequivocally.     

Characterization of a microscale cyclical electrical field flow fractionation system

A microscale cyclical electrical field flow fractionation (CyElFFF) channel is characterized with regard to the effect of various operating parameters and comparison made to recent theoretical developments. Challenges associated with various operating conditions are reported along with some of the optimized operating parameters. The effect of retention wall choice, an offset voltage, relaxation steps, and flow rates, along with the basic operating parameters of voltage, frequency, and electrophoretic mobility are reported. Retention of polystyrene nanoparticle standards is accomplished and the first separations using this technique in a microscale system are also demonstrated. Relaxation steps and offset voltages are found to be effective in eliminating early peaks and in improving plate heights. Plate heights were also found to decrease with increasing flow rates, which is the opposite of the behavior seen in most existing chromatographic systems. The experimental results are compared to the analytical and empirical models of CyElFFF and found to be compatible. Suggestions are made for improving the separation and analysis methods used with CyElFFF.     

Anion binding vs. deprotonation in colorimetric pyrrolylamidothiourea based anion sensors

A pyrrolylamidothiourea deprotonates in the presence of one equivalent of not only fluoride, but also acetate, benzoate or dihydrogen phosphate in DMSO solution with structural studies using synchrotron radiation confirming thiourea deprotonation in the solid state.     

Anion-binding modes in a macrocyclic amidourea

A macrocyclic amidourea shows anion dependent binding modes with a variety of different putative anionic guests.     

Generation of intense highly coherent femtosecond pulses in the mid infrared

Highly coherent mid-infrared femtosecond pulses, tunable between 2.5 and 4.4 mum, and with an average energy and duration between 2.6 and 3.6 microm of 11 microJ and 200fs, respectively, have been produced by an optical parametric amplifier setup driven at 1kHz by a 400- microJ , 800-nm pulse from a Ti:sapphire amplifier. In this system, first tunable moderate-energy femtosecond pulses in the near infrared are produced by continuum amplification in beta -barium borate, and subsequently the near-infrared pulses are amplified and frequency mixed with 800-nm radiation in potassium titanyl phosphate to produce intense tunable mid-infrared pulses. The time-bandwidth product of the mid-infrared pulses is 0.28+/-0.02 over the whole high-energy tuning range. Experimental results are compared with numerical simulations and a simple model.     

Nanosecond electric pulse-induced calcium entry into chromaffin cells

Electrically excitable bovine adrenal chromaffin cells were exposed to nanosecond duration electric pulses at field intensities ranging from 2 MV/m to 8 MV/m and intracellular calcium levels ([Ca(2+)](i)) monitored in real time by fluorescence imaging of cells loaded with Calcium Green. A single 4 ns, 8 MV/m pulse produced a rapid, short-lived increase in [Ca(2+)](i), with the magnitude of the calcium response depending on the intensity of the electric field. Multiple pulses failed to produce a greater calcium response than a single pulse, and a short refractory period was required between pulses before another maximal increase in [Ca(2+)](i) could be triggered. The pulse-induced rise in [Ca(2+)](i) was not affected by depleting intracellular calcium stores with caffeine or thapsigargin but was completely prevented by the presence of EGTA, Co(2+), or the L-type calcium channel blocker nitrendipine in the extracellular medium. Thus, a single nanosecond pulse is sufficient to elicit a rise in [Ca(2+)](i) that involves entry of calcium via L-type calcium channels.     

Anion binding vs. sulfonamide deprotonation in functionalised ureas

Sulfonamide groups, commonly used as neutral hydrogen bond donors in a wide variety of anion receptors, deprotonate upon addition of certain basic anionic guests in two simple functionalised ureas.     

A configurational and conformational study of aframodial and its diasteriomers via experimental and theoretical VA and VCD spectroscopies

In this work we present the experimental and theoretical vibrational absorption (VA) and the theoretical vibrational circular dichroism (VCD) spectra for aframodial. In addition, we present the theoretical VA and VCD spectra for the diasteriomers of aframodial. Aframodial has four chiral centers and hence has 2⁴ = 16 diasteriomers, which occur in eight pairs of enantiomers. In addition to the four chiral centers, there is an additional chirality due to the helicity of the entire molecule, which we show by presenting 12 configurations of the 5S,8S,9R,10S enantiomer of aframodial. The VCD spectra for the diasteriomers and the 12 configurations of one enantiomer are shown to be very sensitive not only to the local stereochemistry at each chiral center, but in addition, to the helicity of the entire molecule. Here one must be careful in analyzing the signs of the VCD bands due to the ‘non-chiral’ chromophores in the molecule, since one has two contributions; one due to the inherent chirality at the four chiral centers, and one due to the chirality of the side chain groups in specific conformers, that is, its helicity. Theoretical simulations for various levels of theory are compared to the experimental VA recorded to date. The VCD spectra simulations are presented, but no experimental VCD and Raman spectra have been reported to date, though some preliminary VCD measurements have been made in Stephens’ lab in Los Angeles. The flexible side chain is proposed to be responsible for the small size of the VCD spectra of this molecule, even though the chiral part of the molecule is very rigid and has four chiral centers. In addition to VCD and Raman measurements, Raman optical activity (ROA) measurements would be very enlightening, as in many cases bands which are weak in both the VA and VCD, may be large in the Raman and/or ROA spectra. The feasibility of using vibrational spectroscopy to monitor biological structure, function and activity is a worthy goal, but this work shows that a careful theoretical analysis is also required, if one is to fully utilize and understand the experimental results. The reliability, reproduceability and uniqueness of the vibrational spectroscopic experiments and the information which can be gained from them is discussed, as well as the details of the computation of VA, VCD and Raman (and ROA) spectroscopy for molecules of the complexity of aframodial, which have multiple chiral centers and flexible side chains. Festschrift in Honor of Philip J. Stephens’ 65th Birthday.     

1,3-diindolylureas and 1,3-diindolylthioureas: anion complexation studies in solution and the solid state

1,3-Diindolylureas and thioureas have been synthesised and their anion complexation properties in solution studied. Whilst diindolylthioureas showed only moderate affinities and selectivities, diindolylureas show remarkably high affinity for dihydrogen phosphate in solution for an acyclic, neutral receptor in water/[D(6)]DMSO mixtures. These easy-to-make compounds adopt relatively planar conformations in the solid-state and are able to donate four hydrogen bonds and yet not fill the coordination sphere of carbonate or phosphate, allowing two or three receptors to bind to each anion in the solid-state.