Investigation of antirelaxation coatings for alkali-metal vapor cells using surface science techniques

Many technologies based on cells containing alkali-metal atomic vapor benefit from the use of antirelaxation surface coatings in order to preserve atomic spin polarization. In particular, paraffin has been used for this purpose for several decades and has been demonstrated to allow an atom to experience up to 10?000 collisions with the walls of its container without depolarizing, but the details of its operation remain poorly understood. We apply modern surface and bulk techniques to the study of paraffin coatings in order to characterize the properties that enable the effective preservation of alkali spin polarization. These methods include Fourier transform infrared spectroscopy, differential scanning calorimetry, atomic force microscopy, near-edge x-ray absorption fine structure spectroscopy, and x-ray photoelectron spectroscopy. We also compare the light-induced atomic desorption yields of several different paraffin materials. Experimental results include the determination that crystallinity of the coating material is unnecessary, and the detection of C[Double Bond]C double bonds present within a particular class of effective paraffin coatings. Further study should lead to the development of more robust paraffin antirelaxation coatings, as well as the design and synthesis of new classes of coating materials.     

An enyne metathesis/(4 + 2)-dimerization route to (+/-)-differolide

[formula: see text] A concise total synthesis of (+/-)-differolide (1) has been achieved. 2-Vinylbutenolide (2) was prepared by enyne metathesis of allyl propynoate (3) using the Grubbs initiator 4. This reaction was examined by 1H NMR spectroscopy, which led to the hypothesis that low concentration of ruthenium species and high concentration of enyne substrate would be advantageous. Accordingly, slow addition of 4 to solutions of enyne 3 was found to be beneficial. Spontaneous dimerization of 2 gave (+/-)-differolide (1) and an isomer.     

Intensity discrimination and increment detection in cochlear-implant users

Intensity difference limens (DLs) were measured in users of the Nucleus 22 and Clarion v1.2 cochlear implants and in normal-hearing listeners to better understand mechanisms of intensity discrimination in electric and acoustic hearing and to evaluate the possible role of neural adaptation. Intensity DLs were measured for three modes of presentation: gated (intensity increments gated synchronously with the pedestal), fringe (intensity increments delayed 250 or 650 ms relative to the onset of the pedestal), and continuous (intensity increments occur in the presence of a pedestal that is played throughout the experimental run). Stimuli for cochlear-implant listeners were trains of biphasic pulses; stimuli for normal-hearing listeners were a 1-kHz tone and a wideband noise. Clarion cochlear-implant listeners showed level-dependent effects of presentation mode. At low pedestal levels, gated thresholds were generally similar to thresholds obtained in the fringe and continuous conditions. At higher pedestal levels, however, the fringe and continuous conditions produced smaller intensity DLs than the gated condition, similar to the gated-continuous difference in intensity DLs observed in acoustic hearing. Nucleus cochlear-implant listeners did not show consistent threshold differences for the gated and fringe conditions, and were not tested in the continuous condition. It is not clear why a difference between gated and fringe thresholds occurred for the Clarion but not the Nucleus subjects. Normal-hearing listeners showed improved thresholds for the continuous condition relative to the gated condition, but the effect was larger for the 1-kHz tonal carrier than for the noise carrier. Findings suggest that adaptation occurring central to the inner hair cell synapse mediates the gated-continuous difference observed in Clarion cochlear-implant listeners and may also contribute to the gated-continuous difference in acoustic hearing.     

Spectrophotometric determination of tungsten in ores and steel by chloroform extraction of the tungsten-thiocyanate-diantipyrylmethane complex

A method for determining up to about 6% of tungsten in ores and mill products is described. It is based on the extraction of the yellow tungsten(V)-thiocyanate-diantipyrylmethane ion-association complex into chloroform from a 2.4M sulphuric acid-7.8M hydrochloric acid medium containing ammonium hydrogen fluoride as masking agent for niobium. The molar absorptivity of the complex is 1510 1. mole(-1).mm(-1) at 404 nm, the wavelength of maximum absorption. Moderate amounts of molybdenum and selenium may be present in the sample solution without causing appreciable error in the result. Interference from large amounts is avoided by separating these elements from tungsten by chloroform extraction of their xanthate complexes. Large amounts of copper interfere during the extraction of tungsten because of the precipitation of cuprous thiocyanate. Common ions, including uranium, vanadium, cobalt, titanium, arsenic and tellurium, do not interfere. The proposed method is also applicable to steel.     

Iron-mediated preparation of vinylcyclopropanecarboxylates: scope,mechanism, and applications

The addition of stabilized carbon nucleophiles to tricarbonyl(1-methoxycarbonylpentadienyl)iron(1+) cation (1a) proceeds via attack at C2 on the face of the ligand opposite the Fe(CO)(3) group to generate tricarbonyl(pentenediyl)iron complexes 2. Oxidation of complexes 2 affords vinylcyclopropanecarboxylates in good yield. In general, the relative stereochemistry about the cyclopropane ring reflects reductive elimination with retention of configuration. In cases where the C2 substituent is bulky (i.e., 2b) the major cyclopropane product 9b represents ring closure with inversion at C3. A mechanism involving pi-sigma-pi rearrangement of the initially oxidized (pentenediyl)iron species is proposed to account for these results. Experiments which probe the stereochemistry of deuterium labeling in the vinyl group of the vinylcyclopropanecarboxylate products were carried out, and these results are consistent with the proposed mechanism. This methodology for the preparation of vinylcyclopropanecarboxylates was applied to the synthesis of 2-(2'-carboxycyclopropyl)glycines (+)-22 and (-)-23 and the cyclopropane triester (-)-26.     

An Equation for the Optimal Value of <Emphasis Type="Italic">T</Emphasis>, the Inventory Replenishment Review Period when Demand is Normal

Differentiation of the expression for cost per unit time in a (T, Z) inventory control model with Normal demand leads to an equation which may be solved iteratively for the optimal value of T. Examples show that the deterministic (square root) solution is in most cases adequate.     

Crystal and molecular structure of N-(bicyclo[5.1.0]octa-3,5-dien-2-yl)phthalimide, C16H13NO2

Single crystal X-ray diffraction analysis of the title compound revealed that the phthalimide substituent was endo with respect to the bicyclic ring system.