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The first successful synthesis of 4-arm ABCD asymmetric star-branched polymer by the coupling of living anionic polymers with
$SiCl_4$ was reported by Hadjichristidis's group in 1993 (ref. 20(b)). In this star, the A, B, C, and D segments were polystyrene, poly(4-methylstyrene), polyisoprene, and poly(1,3-butadiene), respectively. We have recently synthesized two structural similar 4-arm ABCD asymmetric star-branched polymers whose A, B, C, and D segments are polyisoprene, poly(4-methoxystyrene), polystyrene, and poly(4-trimethylsilylstyrene) (ref. 40), and polystyrene, poly($\alpha$ -methylstyrene), poly(4-methylstyrene), and poly(methyl methacrylate) (ref. 41). Furthermore, the synthesis of more complex well-defined 7-arm$A_2B_2C_2D$ and 13-arm$A_4B_4C_4D$ asymmetric stars has also been successfully achieved by our research group (refs. 37 and 38). Very recently, we have successfully synthesized a 5-arm ABCDE asymmetric star-branched polymer for the first time. The A,B,C,D, and E segments in this star are polystyrene, poly($\alpha$ -methylstyrene), poly(4-trimethylsilylstyrene), poly(4-methoxystyrene), and poly(4-methylphenyl vinyl sulfoixe), respectively (ref. 44)