A novel group transfer polymerization of 1-trimethylsiloxy-benzocyclobutene via hetero Diels-Alder reaction

A novel group transfer polymerization via hetero-Diels-Alder reaction is described. When 1-trimethylsiloxybenzocyclobutene ( 1 ) was treated with a catalytic amount of p-anisaldehyde (4-methoxybenzaldehyde) and TASF (tris(dimethylamino)sulfonium difluorotrimethylsilanide) at room temperature for 0.5 h, poly[1,2-phenylene-1-(trimethylsiloxy)ethylene] was obtained quantitatively. The number-average molecular weight of the polymer was M̄_n = 2000 and the molecular weight distribution was narrow (ratio of weight-to number-average molecular weights M̄_w/M̄_n = 1.18). Structural characteristics suggested a polymerization mechanism involving isomerization of 1 to o-quinodimethane and successive hetero-Diels-Alder reaction leading to poly[1,2-phenylene-1-trimethylsiloxy ethylene]. The living-like nature of the polymerization was supported by a monomer addition experiment in which the molecular weight increased according to the increase of the added monomer.     

Molecular orbital study on the mechanism of radical polymerization of spiro-orthocarbonates bearing exo-methylene groups

Molecular orbital studies were carried out to compare the easiness of ring-opening in the radical polymerization of spiro-orthocarbonates bearing exo-methylene groups at α-position of the ether oxygen, spiro[2,4-benzodioxepine-4′-methylene-3,2′-[1,3]-dioxolane] ( 1 ), and at β-position of the ether oxygen, spiro[2,4-benzodioxepine-5′-methylene-3,2′-[1,3]-dioxane] ( 2 ). The formation energy suggests that 1 would show a degree of ring-opening larger than 2 , contrary to the experimental result. Therefore, a reverse relation in activation energy was suggested, i. e., the kinetic factor surpasses the thermodynamic factor in the ring-opening reaction of 1 and 2 . Although the calculation of the activation energy of the radical ring-opening reaction was not successful, the result extracted from the perturbation energy calculations of vinyl polymerizations of 1 and 2 agree well with their radical vinyl polymerizability. Namely, 1 was confirmed to have a larger vinyl polymerizability than 2 , which agrees well with the smaller ring-opening polymerizability of 1 compared with 2 . The real HOMO and LUMO (highest occupied and lowest unoccupied molecular orbitals) of 1, 2 and their intermediates for the radical addition were confirmed not to correspond to the apparent HOMO and LUMO from the detailed analysis of their coefficients of atomic orbitals (AOs). The frontier electron density of 1 and 2 agrees well with the fact that the β-carbon of their exo-methylene group has a higher reactivity toward radical species than the α-carbon.     

On set systems with a threshold property

For n,k and t such that 1<t<k<n, a set F of subsets of [n] has the (k,t)-threshold property if every k-subset of [n] contains at least t sets from F and every (k-1)-subset of [n] contains less than t sets from F. The minimal number of sets in a set system with this property is denoted by m(n,k,t). In this paper we determine m(n,4,3)exactly for n sufficiently large, and we show that m(n,k,2) is asymptotically equal to the generalized Turán number T_k-1(n,k,2).     

Development of palladium(II)-catalyzed oxidative cyclization of olefinic keto and/or lactone esters

A highly efficient palladium-catalyzed oxidative cyclization of olefinic keto and/or lactone esters, which features a catalytic cyclization employing one atmosphere of oxygen as a reoxidizing agent, is developed.     

A new isoelectric focusing system for fast two-dimensional gel electrophoresis using a low-concentration polyacrylamide gel supported by a loose multifilament string.

A new isoelectric focusing (IEF) system for two-dimensional polyacrylamide gel electrophoresis (2-D PAGE) has been proposed. In this system, a super-soft and tough IEF gel was achieved by casting polyacrylamide gel down to 2.0% T using a loose multifilament string (LMS) of nylon as a gel support. The IEF apparatus for the LMS-gel, fabricated from acrylic boards, had a cooling water chamber, and eliminated the need of electrode solutions by directly connecting the two ends of individual gels to platinum electrodes. The carrier ampholyte-generated pH gradients using the new IEF system was stable over a long duration of time and a wide range of voltages, and the IEF time became shorter using a 2.0% T gel than using a 4.0% T gel. Also, the LMS-gels prepared in different runs exhibited excellent reproducibility. The new IEF system was applied to 2-D PAGE of a chicken skeletal muscle extract, and it was found that the protein loading capacity, protein entry into the LMS-gels, and protein transfer efficiency from the first-dimensional to the second-dimensional gels were significantly improved by using a low-concentration (2.5% T) gel. Also, proteins of high molecular weight of more than 200 kDa were observed in the 2-D maps, and therefore the new IEF system has a very good potential to be applied for fast 2-D PAGE of high molecular-weight proteins.     

Matrix Projection Exposure Using an Analogue Liquid Crystal Display Panel in Place of a Reticle

The most serious problems for the matrix projection exposure using a liquid crystal display (LCD) panel in place of a reticle are largely solved by a new breakthrough method. LCD matrix exposure is effective for small volume productions of print circuits, screen masks, micromachine parts, and other items. Since no reticles are needed, all reticle costs are saved, and turnaround times required for changing the patterns are greatly shortened. However, in the conventional method, pattern widths and positions were strictly restricted depending on the geometric size and pitch of the liquid crystal cells. In this paper, a new concept appointing the cell brightness grades continuously using an analogue interface LCD panel is proposed. Calculating the image intensity distributions for various appointments of cell brightness balances to print same wide patterns, it is clarified that the pattern widths and positions are not much different if the pattern widths are wider than 2 cell pitches of the LCD panel. Maximum width and position variations are less than ± 10% even when the patterns are printed at arbitrary positions, of course including halfway ones. The calculated results are proved by experiments using an analogue LCD panel with a cell pitch of 15 μm. Though the cell size are 13 × 10 μm², and different in x and y directions, almost same wide line-and-space patterns are successfully printed at all positions by only one exposure. It is not necessary to shift the reticle for overlapping exposures to print smooth patterns. Oblique patterns and complicated Chinese character patterns are also printed at arbitrary positions. The new breakthrough technology will make the LCD matrix exposure promising for wide uses of printing various rough patterns easily at small costs.     

End-cap exchange of rotaxane by the Tsuji-Trost allylation reaction

[reaction: see text] Rotaxanes possessing a cinnamyl ester group at the axle terminal were prepared. The terminal end-cap was modified with a bulky malonate ester in excellent yield by the Tsuji-Trost allylation reaction, which was carried out in the presence of a palladium catalyst.