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People aged 65 to 69 and those who are clinically vulnerable against Covid will start receiving vaccines tomorrow.
More than a million people have already been invited to book a jab at mass vaccine hubs or pharmacy services.
In Kent, the large-scale vaccine centres have been set up at a cinema in Maidstone, the Angel Centre in Tonbridge, Woodville Halls in Gravesend and the former Debenhams in Folkestone.
Another has been confirmed for the Medway Towns, according to the area's MPs.
Almost 1.2 million letters were due to land on doorsteps by yesterday (Saturday) asking people to log on to the national booking service at www.nhs.uk/covid-vaccination with another 1.2 million due to arrive this week.
Anyone unable to book online can call 119 free of charge, anytime between 7am and 11pm seven days a week.
Meanwhile, GP-led vaccination sites will focus initially on the clinically vulnerable aged under 65 because of the relationship between general practice and those with long term conditions, and continuity of care.
Should somebody aged 65 to 69 want to wait to be called by their local GP vaccination service - or if they have already received the jab - they do not need to respond to their invitation.
More high street pharmacists are being invited to take part as the programme continues to accelerate.
The latest phase of the roll-out comes as the Government looks set to hit its target of vaccinating the most vulnerable by mid-February. These groups comprise care home residents, healthcare workers, those aged over 70, and the clinically extremely vulnerable.
Latest figures - published on Thursday but for the period up to last Sunday - showed just under 350,000 first doses of the coronavirus vaccine had been administered in Kent.
That left about 64,000 people needing to receive the vaccine over the past seven days in order to meet the target.
Meanwhile, more details are emerging about how and when lockdown measures might be lifted, as cases in Kent continue to fall.
Sir Simon Stevens, NHS chief executive, said: “After a strong start the NHS vaccination programme, the biggest and fastest in Europe, is entering a new phase tomorrow.
“Thanks to the hard work of staff the NHS has protected more than 12 million of the most vulnerable people against Covid people in a matter of weeks.
“This is an exciting moment as we now move on to those aged 65 and over and the clinically vulnerable as part of our plan to vaccinate as many people as possible who can benefit from it.
“However, if you have already been offered a jab but have not taken it up it is not too late. Please come forward and help us to help you.”
Health and Social Care Secretary Matt Hancock said: “The vaccination programme is continuing at an unprecedented speed and, as we’re on target to offer vaccines to all those in the first four priority groups by Monday, we are determined to keep up the momentum by expanding it even further.
“The NHS is doing everything it can to offer vaccines to the most vulnerable as quickly as possible, and today’s news will mean millions more at-risk individuals will be able to access a jab from next week.
“We will continue to accelerate the vaccination programme even further and I want to thank everyone in the NHS, volunteers and the armed forces for their tireless dedication.”
Vaccine Minister Nadhim Zahawi said: “The NHS is working tirelessly to protect our loved ones from this terrible virus and I’m delighted the majority of people who are most at risk have now been offered a vaccine.
“Every jab in the arm is another step closer to returning to normality in the future and that’s why we are now inviting the next priority group to book their appointments.
“If you are aged 65 and over, sit tight and you will be contacted by the NHS soon to book an appointment. I encourage everyone invited to book their jab as soon as they’re contacted, so they can protect themselves and others from the virus.”
People aged 70 or over should contact the national booking service while health and care workers should speak to their employers.
Residents who book into a vaccine centre will be greeted by volunteers who will marshal car parks and register them when they arrive.
They will receive a health status check and a pre-vaccination assessment before they have their jab.
Appointments are staggered to allow for social distancing and people who do book are being asked not to turn up early to avoid creating queues.
GPs are contacting those who are housebound to jab them at home.