Low noise 80–115 GHz quasiparticle mixer with small Nb/Al-Oxide/Nb tunnel junctions

Millimeter-wave characterization of a heterodyne receiver using (2 m²) Nb/Al-Ox/Nb Superconducting-Insulator-Superconducting (SIS) junctions arrays is reported. The fabrication of the Nb/Al-Ox/Nb SIS junction arrays as a heterodyne mixer is described. The leakage current of these junctions is below 2A at 4.2K and unmeasurable at 2.5K. The receiver gave a noise temperature Double Side Band (DSB) between 63K and 187K over the frequency range 80 to 115 GHz at the first conversion peak. The results are comparable to those obtained with SIS receivers using well researched lead junctions. Contrary to the lead junctions, our mixer using all Nb junctions have proven remarkably stable with respect to thermal cycling, characteristics which are required for space applications. To our knowledge, this is the most reliable low noise receiver operating in this frequency range.     

Optical reference geometry for stationary and static dynamics

Attention is drawn to the advantages of representing dynamical behavior in a stationary or static background spacetime in terms of a fixed reference 3-geometry that differs from the usual one by a certain conformal rescaling factor. The resulting Riemannian metric may be appropriately described as the optical geometry in recognition of the fact that line-of-sight trajectories are faithfully represented within it as geodesic, at least in the strictly static case for which such lines-of-sight are unambiguously defined. (In more general stationary examples the geodesies represent what amounts to the result of a cancellation between the Coriolis-type effects that would cause a physical light path to deviate to one side or the other depending on the sense of propagation.) The application to the particular case of the Schwarzschild solution is discussed: In this example the optical 3-geometry has a throat that occurs not on the horizon (as in the directly projected 3-geometry) but at the radius of the circular null geodesic orbit.     

Reactions of the ionized enol tautomer of acetanilide: elimination of HNCO via a novel rearrangement

The reactions of ionised acetanilide, C(6)H(5)NH(=O)CH(3)(.+), and its enol, C(6)H(5)NH(OH)=CH(2)(.+), have been studied by a combination of tandem mass spectrometric and computational methods. These two isomeric radical cations have distinct chemistries at low internal energies. The keto tautomer eliminates exclusively CH(2)=C=O to give ionised aniline. In contrast, the enol tautomer loses H-N=C=O, via an unusual skeletal rearrangement, to form predominantly ionised methylene cyclohexadiene. Hydrogen atom loss also occurs from the enol tautomer, with the formation of protonated oxindole. The mechanisms for H-N=C=O and hydrogen atom loss both involve cyclisation; the former proceeds via a spiro transition state formed by attachment of the methylene group to the ipso position, whereas the latter entails the formation of a five-membered ring by attachment to the ortho position. The behaviour of labelled analogues reveals that these two processes have different site selectivities. Hydrogen atom loss involves a reverse critical energy and is subject to an isotope effect. Surprisingly, attempts to promote the enolisation of ionised acetanilide by proton-transport catalysis were unsuccessful. In a reversal of the usual situation for ionised carbonyl compounds, ionised acetanilide is actually more stable than its enol tautomer. The enol tautomer was resistant to proton-transport catalysed ketonisation to ionised acetanilide, possibly because the favoured geometry of the encounter complex with the base molecule is inappropriate for facilitating tautomerisation.     

Application and validation of an ion-exchange high-performance liquid chromatographic method for measuring adenine nucleotides, creatine and creatine phosphate in mouse brain

We have modified and applied an ion-exchange high-performance liquid chromatographic method for measuring adenine nucleotides (adenosine monophosphate, adenosine diphosphate and adenosine triphosphate) as well as creatine and creatine phosphate in brain tissue. There was a linear relationship between the area of each peak and the amount of standard injected onto the column in the concentration range 0.5-25 nmol per 50 microliters. The concentrations of creatine phosphate and creatine were not stable in a standard mixture for 20 h at 4 degrees C unless the pH of the standard mixture was adjusted to neutral. We therefore strongly recommended the neutralization of all standard mixtures and samples before storage. The measurements of adenine nucleotides, creatine and phosphate in control mouse brain determined by this method agreed well with an enzymic method of nucleotide measurement. Furthermore, both methods detected similar decreases in the concentrations of adenosine triphosphate and creatine phosphate, together with concomitant increases in the concentrations of adenosine diphosphate, adenosine monophosphate and creatine when mice were placed under anoxic conditions (either 30 s or 2 min); these changes were greater after 2 min of anoxia than after 30 s of anoxia.     

The vibrational spectra of cyclobutanecarboxylic acid

The complete vibrational spectra of crystalline cyclobutanecarboxylic acid have been recorded. A tentative, approximate vibrational assignment is proposed based on these spectra and the infrared spectra of the potassium salt, cyclobutanecarboxylic acid-O-d, cyclobutanecarboxylic acid-α-d-O-d, cyclobutanecarboxylic acid-α-d and previous published results with other simple cyclobutane derivatives.     

Anionic-initiated polymerization of β-nitrostyrenes

β-Nitrostyrene and many of its derivatives have been shown to yield high polymers via anionic initiation with alkoxide ions in protic solvents, e.g., alcohols. A study was conducted to determine the effect of certain substituents on the polymerization characteristics of representative monomers of this series and the properties of their polymers. A kinetic study was conducted and the relative rates of propagation were unexpectedly found to correlate well with brown's σ⁺ values. The rates of initiation of two representative monomers, β-nitrostyrene and p-methoxy-β-nitrostyrene, with sodium ethoxide were found to be 3.51 and 2.86 liter/mole sec, respectively. The rate of chain transfer in ethanol was studied qualitatively by using gel-permeation chromatography (GPC) to obtain molecular weight distribution (MWD) curves. The low values of the M _w/M _n ratios indicated little chain transfer in the protic solvent.     

Ionization of aqueous toluic acids: Conductance and thermodynamics

Conductivities of aqueous solutions ofortho-, meta-, andpara-toluic acids have been measured for the concentration range 0.1–2 millimolar and at 5° intervals from 5 to 100°C. At each temperature pK _a(m) andA ₀ have been calculated using the paired ion model recently described by Fuoss. Thermodynamic parameters have been calculated for the ionization of each acid, and Walden products for the anions. Results are discussed in terms of contributions to acidity by enthalpy and entropy changes as well as by hydration of the various solute species.     

Synthesis and reactions of 4-isopropylidene-1-aryl-3-methyl-2-pyrazolin-5-ones

The reactions of 4-isopropylidene-1-aryl-3-methyl-2-pyrazolin-5-ones 4a-d were investigated under a variety of conditions. In the presence of thiols or piperidine, 4a-d failed to yield conjugate addition products, presumably due to the steric bulk provided by the two methyl substituents of the isopropylidene side chain. Reaction of 4a-d with hydrazine derivatives gave the 1-aryl-3-methyl-2-pyrazolin-5-ones 3a-d and isopropyl-hydrazones. Treatment of 4a with potassium cyanide yielded a stable conjugate addition product which exists as a mixture of tautomers in different solvents. Also, oxidation of 4a with hydrogen peroxide gave a spiroepoxide 22 , while m-chloroperbenzoic acid oxidation afforded both the spiroepoxide 22 , and a small quantity of a hydroxyspiroepoxide 23.     

Free-radical pathways in the decomposition of ketones over polycrystalline TiO(2): the role of organoperoxy radicals.

The oxidative decomposition of various ketones (including acetone, 2-butanone, 4-heptanone, cyclopentanone and cyclohexanone) over dehydrated TiO(2) (P25) powder is investigated by electron paramagnetic resonance (EPR) spectroscopy. For the first time, a series of thermally unstable radical intermediates are observed both on the activated and reduced TiO(2) surface, depending on the adopted experimental conditions. These radical intermediates are identified as organoperoxy-based species of general formula ROO(.-) and RCO(3) (.-). They are formed by reaction of photogenerated charge carriers (either trapped electrons or trapped holes) with the adsorbed ketones in the presence of molecular oxygen. The organoperoxy intermediates are thermally unstable and decompose at temperatures in the region of 180-250 K. This work demonstrates that free-radical pathways involving both organoperoxy and superoxide radicals can be responsible for the thermal- and photodecomposition of ketones over polycrystalline TiO(2) (P25).