The rotational spectrum and geometrical structure of thiozone, S3

The rotational spectrum of thiozone, S3, has been observed for the first time. From the rotational constants of the normal and 34S isotopic species, a precise geometrical structure has been derived: S3 is a bent chain with a bond to the apex S of length 1.917(1) A and an apex angle of 117.36(6) degrees . The derived structural parameters indicate substantial double-bonding character in S3 and sp2 hybridization of the central sulfur atom. Thiozone is an excellent candidate for astronomical detection in the atmosphere of Io, the innermost Galilean moon of Jupiter, and in rich interstellar sources.     

Continuous production of butanol from starch-based packing peanuts

Acetone, butanol, ethanol (ABE, or solvents) were produced from starch-based packing peanuts in batch and continuous reactors. In a batch reactor, 18.9 g/L of total ABE was produced from 80 g/L packing peanuts in 110 h of fermentation. The initial and final starch concentrations were 69.6 and 11.1 g/L, respectively. In this fermentation, ABE yield and productivity of 0.32 and 0.17 g/(L·h) were obtained, respectively. Compared to the batch fermentation, continuous fermentation of 40 g/L of starch-based packing peanuts in P2 medium resulted in a maximum solvent production of 8.4 g/L at a dilution rate of 0.033 h⁻¹. This resulted in a productivity of 0.27 g/(L·h). However, the reactor was not stable and fermentation deteriorated with time. Continuous fermentation of 35 g/L of starch solution resulted in a similar performance. These studies were performed in a vertical column reactor using Clostridium beijerinckii BA101 and P2 medium. It is anticipated that prolonged exposure of culture to acrylamide, which is formed during boiling/autoclaving of starch, affects the fermentation negatively.     

Morphology of a phase-separated and a molecular composite PBT/ABPBI polymer blend

The structure and morphology of homopolymers and blends of rigid-rod poly(p-phenylene benzobisthiazole) (PBT) and semiflexible coil poly[2,5(6)benzimidazole] (ABPBI) were examined by wide-angle x-ray diffraction and scanning and transmission electron microscopy. When samples were processed from a solution where the total polymer concentration of 30% PBT/70% ABPBI blend was greater than a critical concentration, large-scale phase separation occurred and 0.1–4 μm ellipsoidal particles were present in a ductile matrix. The ellipsoids were chiefly composed of aggregates of well-oriented 10-nm PBT crystallites, while the matrix material was chiefly ABPBI. When the concentration was less than a critical concentration, the solution was optically homogeneous. In processing of fiber and film samples from the homogeneous solution, large-scale phase separation was inhibited by rapid coagulation in a water bath. After heat treatment, these samples were found to contain crystallites of both PBT and ABPBI with lateral dimensions of ordered regions no larger than 3 nm. The PBT homopolymer was dispersed in the matrix at the molecular level in ordered regions at a scale no larger than 3 nm, resulting in a rigid-rod molecular composite. In the rigid-rod molecular composite fiber both the molecular-level dispersion and high orientation contributed to higher values of strength and modulus compared to the properties of a phase-separated fiber. The strength and modulus of highly oriented fiber were only 25% higher than those of planar isotropically oriented film, suggesting that the level of dispersion of rod molecules is more important than orientation of the reinforcing phase in rigid-rod molecular composites.     

Massively Parallel Nonparametric Regression,With an Application to Developmental Brain Mapping

A penalized approach is proposed for performing large numbers of parallel nonparametric analyses of either of two types: restricted likelihood ratio tests of a parametric regression model versus a general smooth alternative, and nonparametric regression. Compared with naïvely performing each analysis in turn, our techniques reduce computation time dramatically. Viewing the large collection of scatterplot smooths produced by our methods as functional data, we develop a clustering approach to summarize and visualize these results. Our approach is applicable to ultra-high-dimensional data, particularly data acquired by neuroimaging; we illustrate it with an analysis of developmental trajectories of functional connectivity at each of approximately 70,000 brain locations. Supplementary materials, including an appendix and an R package, are available online.     

Thermal Cleavage of Oxazolidine-4,5-diones to Imines: A Short Synthesis of 3,4-Dihydro-3,3-dimethyl-7-trifluoromethylisoquinoline-2-oxide

A series of oxazolidine-4,5-diones 2 was thermally cleaved to cyclic imines 3 in excellent yield. This reaction was utilized in an efficient synthesis of a 3,4-dihydroisoquinoline-based nitrone 1b.     

The rotational spectrum of HC8N, a linear molecule with a triplet ground state

By means of Fourier transform microwave spectroscopy of a supersonic molecular beam, we report here the laboratory detection of HC₈N, a carbon chain with a triplet electronic ground state. A total of 71 hyperfine components from six rotational transitions between 8 and 13 GHz were measured to an uncertainty of 5 kHz or better. Eight spectroscopic constants, including six fine and hyperfine coupling constants, were determined to high accuracy, despite a complex spectrum which consists of many closely spaced lines. Like the shorter HC_2nN chains, the linear triplet isomer detected here is highly polar and is almost certainly the ground state of HC₈N; in our molecular beam discharge source, it is 10 times less abundant than triplet HC₆N, but more than 100 times less abundant than the well-studied closed-shell cyanopolyyne HC₇N. Owing to the collapse of the hyperfine structure with increasing chain length, still longer chains may be detectable.     

Rotational spectra of vibrationally excited CCH and CCD

The millimeter-wave rotational spectra of the lowest bending and stretching vibrational levels of CCH and CCD were observed in a low pressure discharge through acetylene and helium. The rotational, centrifugal distortion, and fine structure constants were determined for the (02(0)0) and (02(2)0) bending states, the (100) and (001) stretching levels, and the (011) combination level of CCH. The same pure bending and stretching levels, and the (110) combination level were observed in CCD. Apparent anomalies in the spectroscopic constants in the bending states were shown to be due to l-type resonances. Hyperfine constants, which in CCH are sensitive to the degree of admixture of the A 2Pi excited electronic state, were determined in the excited vibrational levels of both isotopic species. Theoretical Fermi contact and dipole-dipole hyperfine constants calculated by Peric et al. [J. Mol. Spectrosc. 150, 70 (1991)] were found to be in excellent agreement with the measured constants. In CCD, new rotational lines tentatively assigned to the (100) level largely on the basis of the observed hyperfine structure support the assignment of the C-H stretching fundamental (nu1) by Stephens et al. [J. Mol. Struct. 190, 41 (1988)]. Rotational lines in the excited vibrational levels of CCH are fairly intense in our discharge source because the vibrational excitation temperatures of the bending vibrational levels and the (110) and (011) combination levels are only about 100 K higher than the gas kinetic temperature, unlike the higher frequency stretching vibrations, where the excitation temperatures are five to ten times higher.     

Quantum computers based on electron spins controlled by ultrafast off-resonant single optical pulses

We describe a fast quantum computer based on optically controlled electron spins in charged quantum dots that are coupled to microcavities. This scheme uses broadband optical pulses to rotate electron spins and provide the clock signal to the system. Nonlocal two-qubit gates are performed by phase shifts induced by electron spins on laser pulses propagating along a shared waveguide. Numerical simulations of this scheme demonstrate high-fidelity single-qubit and two-qubit gates with operation times comparable to the inverse Zeeman frequency.