Physical- and Bio-Organic Chemstry of Nonbonded Selenium· · ·Oxygen Interactions

Weak nonbonded interaction between a divalent selenium and an oxygen atom (i.e., Se···O interaction) frequently plays important roles in chemical and biological functions of selenium compounds. To establish that ⁷⁷ Se NMR is an easy experimental probe to diagnose the strength of an Se···O interaction, 3 series of 2-substituted benzeneselenenyl derivatives, which have an intramolecular Se···O interaction in solution, were employed. By comparing the ⁷⁷ Se NMR chemical shifts (δ _Se ) with those observed for other series of selenium compounds, which have an intramolecular Se···Y (Y = N, O, F, Cl, or Br) interaction, approximate linear correlation was found between the δ _Se values and the strengths of the nonbonded Se···Y interactions evaluated by natural bond orbital analysis at the B3LYP level. The correlation will be useful for estimating the strength of an Se···O interaction simply from the ⁷⁷ Se NMR chemical shift. By extending the chemistry of nonbonded Se···O interactions to structural biology, analogous S···O interactions have been discovered in protein architecture. The directional features were, however, different from those of Se···O and S···O interactions of small organic compounds.     

Quantitative visualization of temperature field in non-luminous flame by flame reaction technique

Abstract  

An experimental technique for measuring a temperature field in an axisymmetric non-luminous flame is developed using the flame reaction technique combined with the inverse Abel transformation. Flame visualization is carried out using alkali metal solution of Potassium (K), which is supplied to a premixed methane/air flame in a form of spray mist. The basic principle of this technique is based on the measurement of local emission intensity distribution visualized by the flame reaction, which is a function of temperature according to the Maxwell–Boltzmann statistics of thermodynamics. The relationship between the local intensity and the temperature is obtained from the calibration study, in which the local intensity is evaluated from the line of sight intensity by the inverse Abel transformation, and the temperature is measured by thermocouple. This technique is successfully applied to the measurement of local temperature distribution in steady and flickering premixed methane/air flame. The temperature field in the flickering flame indicates that the local temperature oscillates periodically with the flickering frequency, and the highest temperature is found along the flame front and in the merging region.     

Optical testing of star sensor (II): Alignment of star sensor from off-line pictures taken in orbital test

Alignment error of an image sensor relative to the optical axis of a star sensor head and alignment errors between four heads were calculated from pictures taken in an orbital experiment. When comparing the image sensor alignment parameters in the orbital test and a ground test, both values matched well. By determining the relative relationship of the four heads using four pictures taken at the same moment in orbit and uploading the parameters to the star sensor system in orbit, the estimated attitude error was improved from 0.29 to 0.17°, though the accuracy was limited by the ±0.2° determination accuracy of the satellite itself. We estimated the attitude determination accuracy from separation angles between boresights of the four heads, calculated from pattern matching between downloaded pictures and a star catalogue. The estimated accuracy, in terms of potential optical performance, was 0.60 arcmin at 3σ, which is sufficient to satisfy the specification of 1 arcmin.     

Nonequilibrium transport through a vertical quantum dot in the absence of spin-flip energy relaxation

We investigate nonequilibrium transport in the absence of spin-flip energy relaxation in a few-electron quantum dot artificial atom. Novel nonequilibrium tunneling processes involving high-spin states, which cannot be excited from the ground state because of spin blockade, and other processes involving more than two charge states are observed. These processes cannot be explained by orthodox Coulomb blockade theory. The absence of effective spin relaxation induces considerable fluctuation of the spin, charge, and total energy of the quantum dot. Although these features are revealed clearly by pulse excitation measurements, they are also observed in conventional dc current characteristics of quantum dots.     

A novel synthesis of (E)-3,7-dimethyl-2-octene-1,8-diol secreted by the african monarch using the ring-opening reaction of α-methyl-β-propiolactone

The regioselective ring-opening reaction of α-methyl-β-propiolactone with 3,3-ethylene-dioxybutylmagnesium bromide in the presence of copper(I) catalyst afforded 2-methyl-6-oxoheptanoic acid, which was easily converted into (E)-3,7-dimethyl-2-2-octene-1,8-diol in good yield.     

Sulfur-containing polymers. IV. Preparation and properties of poly(sulfenyl thiocarbonates)

Poly(sulfenyl thiocarbonates) have been prepared for the first time by the stepwise condensation of chlorocarbonylsulfenyl chloride with diols and dithiols. The polymers were obtained in high yield. Generally they were crystalline solids and were soluble in chlorinated hydrocarbons. On treatment with benzyl mercaptan in the presence of triethylamine, the polymers afforded a diol, carbonyl sulfide, and a disulfide compound. This reaction was extended to the preparation of alternating copolydisulfides.     

Doppler-limited dye laser excitation spectroscopy of HCCl

The cw dye laser excitation spectrum of the $\text{A}\text{?}{}^1\text{A″(050) ←}\text{X}\text{?}{}^1\text{A′(000)}$ vibronic band of HCCl was observed between 16 539 and 16 656 cm^?1 with the Doppler-limited resolution, 0.03 cm^?1. The HCCl molecule was generated by the reaction of discharged CF₄ with CH₃Cl. The observed spectra were assigned to c-type transitions with ΔK_a = ±1 and also to axis-switching transitions with ΔK_a = 0 or ?2, but all with K′_a = 0, both for HC³⁵Cl and HC³⁷Cl. A rotational analysis yielded the rotational constants and quartic centrifugal distortion constants for the ground vibronic state and the band origin. A weak vibronic band, about one-third as intense as the main band, was found at about 57 cm^?1 to the violet of the main band for both isotopic species, and was ascribed to a transition from the ground vibronic state to a vibrational level, possibly (041), of the à state. The rotational levels of HC³⁵Cl in the à state showed a large perturbation; the J′ = 8, 9, and 10 levels were found to be split into two components. A normal coordinate analysis was carried out to calculate the centrifugal distortion constants and the inertia defect, which were in fair agreement with the observed values. The molecular structure of HCCl in the ground vibronic state was recalculated from the rotational constants of the two isotopic species combined with the 0.75B₀ + 0.25C₀ value previously reported for DC³⁵Cl.