Linear and Nonlinear Optical Properties Of Racemic (±)2-(α-Methylbenzylamino)-5-Nitropyridine Single Crystals

Linear and nonlinear optical properties of racemic (±)2-(α-methylbenzylamino)-5-nitropyridine ((±)MBANP) single crystals have been comprehensively investigated and compared with those of the enantiomorph (–)2-(α-methylbenzylamino)-5-nitropyridine ((–)MBANP) crystals. (±)MBANP crystal exhibits very high chemical and physical stability, but relatively small nonlinear optical coefficients (d₃₁ = 6.8 pm/V, d₃₂ = 4.7 pm/V, d₃₃ = 0.84 pm/V). A comparison between the nonlinear optical coefficients of (±)MBANP and (–)MBANP demonstrates the validity of the oriented-gas model in molecular crystals that neglects all the contributions from intermolecular interaction.     

Chromium- and tungsten-triggered valence isomerism of cis-1-acyl-2-ethynylcyclopropanes via [3,3]sigmatropy of (2-acylcyclopropyl)vinylidene-metal intermediates.

The reaction of cis vicinal acetylethynylcyclopropanes 1 with a catalytic amount of M(CO)5(THF) (M = Cr or W) in the presence of Et3N at room temperature gave ortho-substituted phenols 7 in good yields as valence isomerized products. In the absence of Et3N the reactions did not work at all. The reaction of a cyclopropane having an ester or an amide instead of an acetyl moiety with M(CO)5(THF) did not take place, whereas an ethynylvinylcyclopropane gave a mixture of 1- and 2-substituted 1,3,5-cycloheptatrienes. These valence isomerization reactions are assumed to proceed via the formation of vinylidene-metal intermediates 2 from terminal alkynyl moieties followed by [3,3]sigmatropy of 2 to give seven-membered carbene complexes 3.     

Pre-fibrillation of pulps to manufacture cellulose nanofiber-reinforced high-density polyethylene using the dry pulp direct kneading method

The dry pulp direct kneading method is an industrially viable, low-energy process for manufacturing cellulose nanofiber (CNF)-reinforced polymer composites, where the chemically modified pulps are nanofibrillated and uniformly dispersed in the polymer matrix during melt compounding. In the present study, cellulose fibers of various sizes ranging from surface-fibrillated pulps (20 μm in width) to fine CNFs (20 nm in width) were prepared from softwood bleached kraft pulps using a refiner and a high-pressure homogenizer. These cellulose fibers were modified with alkenyl succinic anhydride and dried. The dried fibers were used as a feed material for melt compounding in the dry pulp direct kneading method to fabricate CNF-reinforced high-density polyethylene (HDPE). When surface-fibrillated pulps were employed as a feed material, the pulps were nanofibrillated and dispersed uniformly in the HDPE matrix during melt compounding. The resulting composites had much better properties—i.e., much higher tensile modulus and strength values, and much lower coefficient of thermal expansion values—than the composites produced using pulps without pre-fibrillation. However, when CNFs were used as a feed material, they were shortened and agglomerated during melt compounding, and the properties of the composites consequently deteriorated. The study concludes that surface-fibrillated pulp, which can be produced cost-effectively using a refiner on an industrial scale, is more suitable as a feed material than CNFs for melt compounding in the dry pulp direct kneading method. This finding enables the elimination of a preliminary step in the preparation of CNFs from pulps, which is a time-consuming and energy-intensive process.

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Construction of an asymmetric quaternary carbon via an asymmetric aza-Claisen rearrangement and its application in the total synthesis of (+)-α-cuparenone

Excess lithium hexamethyldisilazide (LHMDS) with LiCl prompted the asymmetric aza-Claisen rearrangement of carboxamide and retarded the decomposition of its amide enolate. The addition of these two reagents was a key step that led to the total synthesis of (+)-α-cuparenone with a stereogenic quaternary center.     

Tomographic implementation of astronomical speckle imaging from bispectra

A bispectral method for astronomical speckle imaging utilizes an average speckle bispectrum of an object to derive its Fourier phase. There has been, however, a problem in conventional bispectral algorithm owing to difficulty in processing bispectral data in a four-dimensional (4D) space. In this paper, we propose an implementation to overcome this problem, where a one-dimensional (1D) object projection is reconstructed from a two-dimensional (2D) average bispectrum of speckle projections, and object projections so obtained at various angles are then tomographically combined into a 2D object image. In this tomographic approach, processes are separable into those for individual projection angles, implying that bispectral data required to be stored at a time are from 4D to 2D and computation time can be substantially reduced by parallelizing angle-by-angle processes. We have performed experiments using simulated and observed data, and have demonstrated the feasibility of the present approach with an achievable accuracy comparable to that of a conventional approach.     

A Regularly Preemptive Model and its Approximations

A regularly preemptive model D,MAP/D ₁,D ₂/1 is studied. Priority customers have constant inter-arrival times and constant service times. On the other hand, ordinary customers' arrivals follow a Markovian Arrival Process (MAP) with constant service times. Although this model can be formulated by using the piecewise Markov process, there remain some difficult problems on numerical calculations. In order to solve these problems, a novel approximation model MAP/MR/1 with Markov renewal services is proposed. These two queueing processes become different due to the existence of idle periods. Thus, a MAP/MR/1 queue with a general boundary condition is introduced. It is a model with the exceptional first service in each busy period. In particular, two special models are studied: one is a warm-up queue and the other is a cool-down queue. It can be proved that the waiting time of ordinary customers for the regular preemption model is stochastically smaller than the waiting time of the former model. On the other hand, it is stochastically larger than the waiting time of the latter model.     

A novel migrative addition reaction of hydrazines to the diketone derivative of C60

A novel addition reaction of an aromatic hydrazine to the diketone derivative of C60 occurs highly regioselectively with an unusual migration of two hydrogen atoms from the hydrazine to the fullerene and affords a fluorescent product having a methylene carbon along the orifice.     

Preparations of regioselectively methylated cellulose acetates and their 1H and 13C NMR spectroscopic analyses

Seven possible regioselectively methylated cellulose acetates (RS‐MCAs)—2,3,6‐tri‐O‐methyl cellulose acetate, 3,6‐di‐O‐methyl cellulose acetate, 2,6‐di‐O‐methyl cellulose acetate, 2,3‐di‐O‐methyl cellulose acetate, 6‐O‐methyl cellulose acetate, 3‐O‐methyl cellulose acetate, and 2‐O‐methyl cellulose acetate—were prepared for the first time from chemically synthesized cellulose derivatives obtained by cationic ring‐opening polymerization and then were analyzed by ¹H and ¹³C NMR spectroscopy. The chemical shifts of ring protons and carbons were influenced by substituent groups (methyl or acetyl) and clearly reflected the pattern of substituent distribution in anhydroglucose units. These data may conveniently be used for the determination of the substituent distribution of methyl cellulose. The synthesized RS‐MCAs also may be used for the elucidation of the structure–property relationship. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 4167–4179, 2002