Living β-selective cyclopolymerization using Ru dithiolate catalysts

Cyclopolymerization (CP) of 1,6-heptadiyne derivatives is a powerful method for synthesizing conjugated polyenes containing five- or six-membered rings via α- or β-addition, respectively. Fifteen years of studies on CP have revealed that user-friendly Ru-based catalysts promoted only α-addition; however, we recently achieved β-selective regiocontrol to produce polyenes containing six-membered-rings, using a dithiolate-chelated Ru-based catalyst. Unfortunately, slow initiation and relatively low catalyst stability inevitably led to uncontrolled polymerization. Nevertheless, this investigation gave us some clues to how successful living polymerization could be achieved. Herein, we report living β-selective CP by rational engineering of the steric factor on monomer or catalyst structures. As a result, the molecular weight of the conjugated polymers from various monomers could be controlled with narrow dispersities, according to the catalyst loading. A mechanistic investigation by in situ kinetic studies using ^1H NMR spectroscopy revealed that with appropriate pyridine additives, imposing a steric demand on either the monomer or the catalyst significantly improved the stability of the propagating carbene as well as the relative rates of initiation over propagation, thereby achieving living polymerization. Furthermore, we successfully prepared diblock and even triblock copolymers with a broad monomer scope

Hypofractionated High-Dose Intensity-Modulated Radiotherapy (60 Gy at 2.5 Gy per Fraction) for Recurrent Renal Cell Carcinoma: A Case Report

A patient with renal cell carcinoma (RCC) developed synchronous bone metastasis with metachronous relapses to the bone and renal fossa. The primary lesion was initially removed surgically, and the metastatic bone lesions and locally recurrent tumours were treated by a high-fractional dose and high-total-dose intensity-modulated radiotherapy (IMRT, 60 Gy at 2.5 Gy per fraction) without significant side effects. All the grossly relapsed tumors underwent complete remission (CR) within a short time after IMRT. To date, CR has been maintained for more than two years. This case study reports the successful treatment of radioresistant RCC using a new scheme that involves a fractionation regimen with a high precision radiotherapy

DUALISM IN JOB STABILITY OF THE KOREAN LABOUR MARKET: THE IMPACT OF THE 1997 FINANCIAL CRISIS

This paper measures the dynamic changes in job stability in the Korean labour market during the period between the 1997 financial crisis and the recovery. Drawing on the Korean Labor and Income Panel Study data, our empirical research shows that the sharp decline in job stability experienced by Korean workers during the 1997 financial crisis never bounced back to the previous level. The recovery process was much slower for irregular, short-tenured or less educated workers than the other comparison groups, aggravating the polarization of job stability. Copyright 2009 The Authors. Journal compilation 2009 Blackwell Publishing Asia Pty Ltd

Living β-selective cyclopolymerization using Ru dithiolate catalysts

Cyclopolymerization (CP) of 1,6-heptadiyne derivatives is a powerful method for synthesizing conjugated polyenes containing five- or six-membered rings via α- or β-addition, respectively. Fifteen years of studies on CP have revealed that user-friendly Ru-based catalysts promoted only α-addition; however, we recently achieved β-selective regiocontrol to produce polyenes containing six-membered-rings, using a dithiolate-chelated Ru-based catalyst. Unfortunately, slow initiation and relatively low catalyst stability inevitably led to uncontrolled polymerization. Nevertheless, this investigation gave us some clues to how successful living polymerization could be achieved. Herein, we report living β-selective CP by rational engineering of the steric factor on monomer or catalyst structures. As a result, the molecular weight of the conjugated polymers from various monomers could be controlled with narrow dispersities, according to the catalyst loading. A mechanistic investigation by in situ kinetic studies using 1H NMR spectroscopy revealed that with appropriate pyridine additives, imposing a steric demand on either the monomer or the catalyst significantly improved the stability of the propagating carbene as well as the relative rates of initiation over propagation, thereby achieving living polymerization. Furthermore, we successfully prepared diblock and even triblock copolymers with a broad monomer scope.ISSN:2041-6520ISSN:2041-653