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Ouchi, Makoto,Ito, Makoto,Kamemoto, Satoshi,Sawamoto, Mitsuo Wiley (John WileySons) 2008 Chemistry - An Asian Journal Vol. No.
<P>The systematic search and design of phosphine ligands (PR(3)) and amine cocatalysts resulted in obtaining pentamethyl-cyclopentadienyl (Cp*) ruthenium(II) phosphine complexes [RuCp*Cl(PR(3))(2)], which are highly active and removable catalysts, for transition-metal-catalyzed living radical polymerization of methyl methacrylate (MMA). The catalysts are conveniently prepared in situ from a tetrameric precursor [RuCp*(mu(3)-Cl)](4) and a selected phosphine (PR(3)). The combination of the meta-tolyl phosphine [P(m-Tol)(3)] ligand and a primary diamine cocatalyst [NH(2)(CH(2))(6)NH(2)] provides a highly active catalytic system with precision control of the molecular weight of the polymer. The high activity enables a low catalyst dose and a high turn-over frequency without deteriorating the controllability. A hydrophilic amine cocatalyst (amino alcohol) in place of the diamine, further forms an active and removable catalyst; simple treatment with acidic water gave colorless polymers visually free from metal residues (>97 % removal; <64 ppm).</P>
Ida, Shohei,Ouchi, Makoto,Sawamoto, Mitsuo American Chemical Society 2010 JOURNAL OF THE AMERICAN CHEMICAL SOCIETY - Vol.132 No.42
<P>Surprisingly high monomer selectivity was demonstrated in competitive radical addition with two kinds of methacrylates carrying sodium and ammonium cation. Crucial is size-specific recognition by a lariat crown ether embedded close to the reactive halide in a designer template initiator. Especially, a combination with an active ruthenium catalyst led to outstanding selectivity at low temperature. This template system will open the way to unprecedented sequence-regulated polymerization.</P><P><B>Graphic Abstract</B> <IMG SRC='http://pubs.acs.org/appl/literatum/publisher/achs/journals/content/jacsat/2010/jacsat.2010.132.issue-42/ja1070575/production/images/medium/ja-2010-070575_0008.gif'></P><P><A href='http://pubs.acs.org/doi/suppl/10.1021/ja1070575'>ACS Electronic Supporting Info</A></P>
Ida, Shohei,Terashima, Takaya,Ouchi, Makoto,Sawamoto, Mitsuo American Chemical Society 2009 JOURNAL OF THE AMERICAN CHEMICAL SOCIETY - Vol.131 No.31
<P>A ruthenium(II)-catalyzed, highly selective, quantitative radical addition of an alkene, methacrylic acid (MAA), has been achieved by using a template halide (2) containing a built-in amine group as a recognition site for the carboxyl group of the substrate. The specific ionic binding of MAA by the amine template (1:1 molar ratio) led to preferential formation of the 1:1 MAA-2 adduct, whereas a similar halide without a template induced MAA oligomerization even in the presence of an externally added amine. A competitive radical addition of MAA versus its ester form [methyl methacrylate (MMA)] on the halide further demonstrated that the substrate selectivity [k'(MAA)/k'(MMA)] for 2 is enhanced more than 10 times by the intramolecular introduction of the template relative to the result for the nontemplate halide. These specificities are most likely triggered by the specific interaction (recognition) of the carboxyl group in MAA via the acid-selective template amine, which is implanted in the close vicinity of the radical addition site in 2. These results intimate possibility of control over the repeat-unit sequence in precision polymerization.</P>
2Department of Orthopaedic Surgery, Myungeun Hospital, Busan, Korea
Takato Aihara,Tomoaki Toyone,Yasuaki Murata,Kazuhide Inage,Makoto Urushibara,Juntaro Ouchi 대한척추외과학회 2018 Asian Spine Journal Vol.12 No.1
Study Design: Retrospective review of prospectively collected outcome data. Purpose: To compare 5-year outcomes following decompression with fusion (FU) and microendoscopic decompression (MED) in patients with degenerative lumbar spondylolisthesis (DLS) and to define surgical indication limitations regarding the use of MED for this condition. Overview of Literature: There have been no comparative studies on mid- or long-term outcomes following FU and MED for patients with DLS. Methods: Forty-one consecutive patients with DLS were surgically treated. Sixteen patients first underwent FU (FU group), and 25 then underwent MED (MED group). The 5-year clinical outcomes following the two surgical methods were compared using the Japanese Orthopaedic Association Back Pain Evaluation Questionnaire. Results: The degree of improvement (DOI) for social life function was significantly greater in the MED group than in the FU group. Although not statistically significant, DOIs for the other four functional scores were also greater in the MED group than in the FU group. However, patients with a large percentage of slippage in the neutral position might experience limited improvement in low back pain, those with a large percentage of slippage at maximal extension might experience limited improvement in three functional scores, and those with a small intervertebral angle at maximal flexion might have limited improvement in three functional scores after MED for DLS. Therefore, we statistically compared the DOIs between the FU and MED groups regarding the preoperative percentage of slippage in the neutral position among patients with greater than 20% slippage, the preoperative percentage of slippage at maximal extension among patients with greater than 15% slippage, and the intervertebral angle at flexion among patients with angles lesser than −5°; however, there were no statistically significant differences between the two groups. Conclusions: MED is a useful minimally invasive surgical procedure that possibly offers better clinical outcomes than FU for DLS.