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Purushothaman was taken to KIMS hospital in the morning due to some health problems, a party leader said.
Apart from Mizoram, the veteran leader also served as Lieutenant Governor of Andaman and Nicobar Islands.
Kerala Assembly Speaker A N Shamseer, Chief Minister Pinarayi Vijayan and Leader of Opposition in the assembly V D Satheesan condoled the death of the Congress stalwart.
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Vijayan, in a statement, said that Purushothaman made his mark as a Governor, Speaker, parliamentarian and a minister handling various departments.
The Chief Minister said that the Congress stalwart always stuck to his stand and decisions even in the face of controversy.
Satheesan, in a Facebook post, remembered Purushothaman as a strong and commanding leader and legislator who was an exemplary role model for politicians as he never succumbed to any pressure.
He also said that the former Kerala assembly Speaker’s demise was also a personal loss to him.
Purushothaman was a cabinet minister in the Kerala government between 1971-1977, 1980 to 1981 and 2004 to 2006.
He was the speaker of Kerala legislative assembly from 1982-1984 and 2001-2004.
According to the Kerala assembly website, Purushothaman started his political life as an active worker of the Students Congress in 1946.