Living cationic polymerization of vinyl monomers by organoaluminum halides

Summary Well-defined living polymers of isobutyl vinyl ether were obtained in the polymerization initiated with ethylaluminum dichloride (EtAlCl₂) in conjunction with a stoichiometric excess of dioxane (5–10 vol%) in n-hexane at 0°C. Under these conditions, the number-average molecular weight of the polymers increased in direct proportion to monomer conversion, while the molecular weight distribution stayed narrow (M_w/M_n = 1.1–1.25). In sharp contrast, the EtAlCl₂-initiated polymerization in the absence of dioxane led to non-living polymers with a broad molecular weight distribution. It was concluded that the propagating carbocation is stabilized not by the counteranion but by an externally added basic compound (dioxane) that strongly interacts with the active end.     

Infrared absorption enhancement of C60 by overlaying thin silver island films

Normal-incidence infrared absorption has been observed for silver overlaid C(60) thin films formed on surface-oxidized Si(111) substrates as a function of the silver or C(60) film thickness. The absorption spectra exhibit bands at 1429 and 1180 cm(-1) due, respectively, to the infrared active T(lu) (4) and T(lu) (3) modes of C(60) in multi-layers. Additionally, two bands appear at 1442 and 1370 cm(-1). The former band is caused by activation of the infrared inactive (Raman active) A(g) (2) mode via electron transfer from the silver to adsorbed C(60), and the latter is assigned to the T(1u) (4) mode red-shifted by the charge transfer. These bands are all enhanced in intensity dependent either upon the silver or C(60) thickness, i.e., the largest absorption enhancement is obtained for 25-monolayers-thick silver and 12-nm-thick C(60). Under atomic force microprobe inspection, the average size and height of the islands in the overlaid 25-monolayers-thick silver change with underlying C(60) film thickness. The influence of the C(60) film structure upon the silver film and in turn the absorption intensity is strongly suggested.     

Antioxidative and anti-hydrogen peroxide activities of various herbal teas

Herbal teas, i.e., extracts of herbs, are popular because of their fragrance and antioxidative activity. Since the antioxidative activity comes mainly from polyphenols, total polyphenol concentrations and 1,1-diphenyl-2-picrylhydrazyl (DPPH) radical-scavenging activities in herbal teas were measured and compared. Levels of H₂O₂ in the teas were also examined, since the production of H₂O₂ in beverages such as coffee and green tea, has been reported. Only a small amount of H₂O₂ was detected in the herbal teas just after their preparation with hot water. However, H₂O₂ was gradually produced during incubation at 25 °C after extraction with hot water, especially when the teas were incubated in phosphate buffer at pH 7.4. To examine the anti-H₂O₂ activity of herbal teas, various teas were added to a catechin-enriched green tea, which produce much H₂O₂, and they were incubated at 25 °C for one day. Addition of hibiscus and thorn apple tea decreased the production of H₂O₂ in the catechin-enriched green tea, possibly because of a lowering of the pH of the mixture.     

All solid-state Cr:LiSAF laser

Many kinds of experiments about all solid-state Cr:LiSAF lasers have been reported. A tunable all solid-state cw laser having tunability over more than 100 nm was developed by using the spectrum selection self-injection locking (SSSIL) method in 1992. The authors realize tunable picosecond radiation from an all solid-state laser with 146-200 ps pulses in an 88 nm range. Also, 70 fs pulse generation was achieved using a Kerr-lens mode-locking pumped with an Ar⁺ laser     

Living cationic polymerization of vinyl monomers by organoaluminium halides

Summary Living cationic polymerization of isobutyl vinyl ether was achieved by EtAlCl₂ in the presence of ethyl acetate at rather high temperatures up to +25°C in toluene. In the absence of the ester additives, neither living nor long-lived propagating species were formed under these conditions. Similarly, living propagating species of vinyl ethers with an ester unit in the pendant (2-vinyloxyethyl benzoate and methacrylate) were obtained with EtAlCl₂ alone. The obtained polymers showed a very narrow molecular weight distribution (¯M_w/¯M_n<1.2) and the ¯M_n was directly proportional to the monomer conversion.     

Living cationic polymerization of vinyl ethers with a functional group

Summary Vinyl ethers having oxyethylene units [CH₂=CHO-(CH₂CH₂O)-_nC₂H₅, n=1–4] were cleanly polymerized by the HI/I₂ initiator in a nonpolar solvent (toluene) at low temperatures (–15 and –40°C) to yield living-like polymers with a very narrow molecular weight distribution (Mw/Mn 1.2); the oxyethylene units in the monomers hardly disturbed the polymerization. The number-average molecular weight of the polymers increased proportionally to monomer conversion and the monomer-to-HI feed ratio. The polymerization rates of the (poly)ether-containing vinyl ethers were much greater than those of alkyl vinyl ethers under similar conditions, and it is presumed that the pendant ether oxygens intramolecularly activate the growing end. The polymers were soluble in methanol (with n1) and in water (with n2), depending on the number of oxyethylene units in the pendant.     

Living cationic polymerization of vinyl ethers with a functional group

Summary Living polymerizations of 2-vinyloxyethyl methacrylate and 2-vinyloxyethyl cinnamate were successfully performed with a mixture of hydrogen iodide and iodine (HI/I₂) as an initiating system in toluene at –15 to –40 °C, Although the two monomers have an unsaturated ester pendant group, their living polymerizations proceeded exclusively via the vinyloxyl group without undesirable side reactions of the pendant group. The product polymers had a very narrow molecular weight distribution (Mw/Mn 1.1), and {Mn} directly proportional to monomer conversion. For both vinyloxyethyl monomers, the addition of a new feed of monomer to a polymerization mixture led to an increase in polymer molecular weight which was again proportional to the conversion.     

Second-Order Efficiency for Two-Stage Estimation of a Linear Function of Normal Mean Vectors when Covariance Matrices Have Some Structures

Abstract

We consider two-stage estimation for a fixed-span confidence region about a linear function of mean vectors from π _i : N _p (μ _i , Σ _i ), i = 1,…,k (≥2), when Σ _i 's have some structures. The purpose of this article is to investigate asymptotic efficiency of the estimation up to the second order in terms of the sample size. An adjustment of the design constant and a proper choice of the initial sample size appearing in the two-stage estimation are proposed to have asymptotic second-order efficiency. Some simulations are carried out to see moderate sample size performances of the proposed two-stage estimation. An example is given for a demonstration.