Nicola Sturgeon has been moved from the role of Health Secretary in the Scottish Cabinet reshuffle.
The Deputy First Minister will take over the role of Infrastructure, Investment and Cities from Alex Neil.
Ms Sturgeon will also take the lead in Government Strategy and the Constitution, which includes preparing for the independence referendum.
Her junior ministers will be Keith Brown, who stays in his role as Transport Minister, and Margaret Burgess, MSP for Cunninghame South who will take up a new role of Minister for Housing and Welfare.
Mr Neil is taking over the role of Health Secretary.
Bruce Crawford is retiring from his role as Cabinet Secretary for Parliamentary Business and Government Strategy.
Also retiring is Brian Adam, Minister for Parliamentary Business, who will be replaced by Joe Fitzpatrick, MSP for Dundee City West.
Stewart Stevenson will also be stepping down as Minister for Environment and Climate Change – replaced by Paul Wheelhouse, MSP for South Scotland.
Humza Yousaf, MSP for Glasgow, joins the Government as Minister for External Affairs and International Development, a new role.
All other positions will remain the same.
The First Minister said the changes were being put in place both to prepared for the independence referendum and the programme of legislation which was presented to parliament on Tuesday.
He said: "This strong Ministerial team will take this Government forward in meeting the economic and social challenges we face while creating a better Scotland for future generations.
"As Health Secretary, Nicola Sturgeon has demonstrated what can be achieved when Scotland has responsibility for its own affairs. As Cabinet Secretary for Infrastructure, Investment and Cities, she will have a lead role in our programme for economic recovery. With responsibility for Government strategy and the constitution, she will also lead in making the positive case for Scotland's future.
"Alex Neil has delivered the biggest infrastructure investment programme in Scotland's history against a backdrop of budget cuts from Westminster. In taking forward Nicola Sturgeon's substantial achievements as Health Secretary, he will ensure that Scotland's health service continues to have the strongest possible leadership.
"In 2014, the people of Scotland will have the chance to seize the biggest opportunity in 300 years and ensure that Scotland's future is in Scotland's hands.
"Over the next two years, this Government will set out the positive case for independence and present the real choice facing Scotland's electorate between decisions about Scotland being taken by the people of Scotland or continued control from Westminster."
Mr Salmond also paid tribute to outgoing cabinet members Bruce Crawford, Stewart Setvenson and Brian Adam.
He also said the four new ministers would be bringing their "own unique talents" to the government.
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