Development of Highly Selective Process for Mono-Ethylene Glycol Production from Ethylene Oxide via Ethylene Carbonate Using Phosphonium Salt Catalyst

A new process for the production of mono-ethylene glycol (MEG; HOCH₂CH₂OH) was developed by Mitsubishi Chemical Corporation (MCC) to meet its growing demand in the world. While the MEG selectivity of conventional non-catalyzed process is around 89% under typical conditions, that of the new process exceeds 99%. The key of the high selectivity is the two-step synthesis via ethylene carbonate. The first step reaction is catalyzed by phosphonium salts and generates ethylene carbonate as an intermediate. This is followed by hydrolysis of ethylene carbonate in the second step. Several commercial plants of the new process have already been operated world-wide.     

A topological splitting theorem for sub-Riemannian manifolds

We prove an analogue of the Cheeger–Gromoll splitting theorem for sub-Riemannian manifolds with the measure contraction property instead of the nonnegativity of the Ricci curvature. If such a sub-Riemannian manifold contains a straight line, then the manifold splits diffeomorphically, where the splitting is not necessarily isometric. We prove that such a sub-Riemannian manifold containing a straight line cannot split isometrically under some typical condition in sub-Riemannian geometry. Heisenberg groups are such examples.     

Application of 28Mg to the kinetic study of Mg uptake by rice plants

The time course of Mg uptake and release using intact rice plants and ²⁸Mg as a tracer is presented. Since there is no conventional Mg tracer available, ²⁸Mg was produced via ²⁷Al(α, 3p)²⁸Mg reaction using a cyclotron. Using the purified ²⁸Mg tracer, it was found that the uptake amount of ²⁸Mg by the rice plants increased linearly during 30 min of application. After ²⁸Mg treatment for 90 min, the roots were sequentially washed with iced solution for 120 min. Within about 10 min, almost all of the ²⁸Mg, that was thought to be weakly bound to the apoplast, was washed away.     

Enantioselective reductive aldol reaction using tertiary amine as hydride donor

An efficient method was developed for the enantioselective reductive aldol reaction of α,β-unsaturated ketones with aldehydes in the presence of a Lewis base catalyst; conjugate reduction using a tertiary amine and trichlorosilyl triflate, followed by an aldol reaction with BINAP dioxide (BINAPO) as an organocatalyst, gave the corresponding product in high yield with high stereoselectivity.     

Elimination of the uninformative calibration sample subset in the modified UVE(Uninformative Variable Elimination)-PLS (Partial Least Squares) method.

In order to increase the predictive ability of the PLS (Partial Least Squares) model, we have developed a new algorithm, by which uninformative samples which cannot contribute to the model very much are eliminated from a calibration data set. In the proposed algorithm, uninformative wavelength (or independent) variables are eliminated at the first stage by using the modified UVE (Uninformative Variable Elimination)-PLS method that we reported previously. Then, if the prediction error of the ith (1 < or =i< or = n) sample is larger than 3sigma, the corresponding sample is eliminated as uninformative, where n is the total number of calibration samples and sigma is the standard deviation calculated from the other n(-1) samples. Calculation of sigma by the leave-one-out manner enhances the ability to identify the uninformative samples. The final PLS model is constructed precisely because both uninformative wavelength variables and uninformative samples are eliminated. In order to demonstrate the usefulness of the algorithm, we have applied it to two kinds of mid-infrared spectral data sets.     

Structure and morphology of the aliphatic polyester poly(δ‐valerolactone) in solution‐grown,chain‐folded lamellar crystals

Poly(δ‐valerolactone) (PVL) crystals in the form of chain‐folded lamellae were prepared by isothermal crystallization from a 2‐methylbutane‐2‐ol solution. Wide‐angle and small‐angle X‐ray diffraction data, obtained from PVL lamellae sedimented to form oriented mats, were supplemented with morphological and structural data from electron microscopy, both imaging and diffraction. The diffraction signals index on an orthorhombic unit cell with the parameters a = 0.747 ± 0.002 nm, b = 0.502 ± 0.002 nm, and c (chain axis) = 0.742 ± 0.002 nm. Similar unit cell parameters were obtained from crystals grown from 1‐octanol and also from drawn melt‐pressed films. The evidence supports a model containing two antiparallel chain segments in the unit cell. The c value of 0.742 nm is appropriate for an all‐trans or onefold helical backbone conformation for the straight stems. Possible slight perturbations at the ester units from the all‐trans backbone conformation are discussed. Computerized modeling was used to optimize the adjacent‐reentry folded structure. The setting angles, with respect to the a axis, are ±58° for the corner and center chains. The lamellae are 7.26 ± 0.05 nm thick, and the chains run orthogonal to the lamellar surface. The chains fold in the diagonal (110) and (11¯0) planes in an alternating fashion. The X‐ray diffraction data suggest that a proportion of adjacent paired antiparallel entities, or hairpin units, are c‐axis‐sheared, and a relationship to the results obtained from drawn films is discussed. A brief comparison is also made with related polymer structures. © 2001 John Wiley & Sons, Inc. J Polym Sci Part B: Polym Phys 39: 2622–2634, 2001     

A descent method for submodular function minimization

We show a descent method for submodular function minimization based on an oracle for membership in base polyhedra. We assume that for any submodular function f: ?→R on a distributive lattice ?⊆2 ^V with ?,V∈? and f(?)=0 and for any vector x∈R ^V where V is a finite nonempty set, the membership oracle answers whether x belongs to the base polyhedron associated with f and that if the answer is NO, it also gives us a set Z∈? such that x(Z)>f(Z). Given a submodular function f, by invoking the membership oracle O(|V|²) times, the descent method finds a sequence of subsets Z ₁,Z ₂,···,Z _k of V such that f(Z ₁)>f(Z ₂)>···>f(Z _k )=min{f(Y) | Y∈?}, where k is O(|V|²). The method furnishes an alternative framework for submodular function minimization if combined with possible efficient membership algorithms. Received: September 9, 2001 / Accepted: October 15, 2001?Published online December 6, 2001     

Measurement of the G asymmetry for the γp↦Nπ channels in the Δ(1232) resonance region

The G asymmetry of the γp↦Nπ reaction has been measured for the first time for E_γ = 340±14 MeV. This observable, for which very scarce published data exist, plays an important role to disentangle the contributions of the various nucleon resonances. The experiment, performed at the Mainz microtron MAMI, used a 4π-detector system, a linearly polarized, tagged photon beam, and a longitudinally polarized proton target.