The dose on the label says to give 2 capsules per day in cats over 10 lbs. From the product information on Amazon:
Your cats are very large – they will be fine with 150 mg per day. In fact, your male cat exceeds the cat dose range and would probably be fine with the 225 mg capsules (however, as we dose to healthy body weight, you should stick with your vet's prescribed 75 mg capsules). You can open the capsules and sprinkle them on a little food to make it easier to administer.
Zylkene is a very safe supplement. It is a non-prescription product. Supplements in general are not as closely regulated as drugs, probably due to their generally wide margin of safety. It does not appear that the manufacturer has published any safety data. Anecdotally (as a vet), I have never encountered any adverse effects from this product other than the occasional one with an allergy or sensitivity, and even this is uncommon as the main ingredient is a hydrolysed protein.
Zylkene is simply a milk-protein (alpha-casozepine) product that may have some calming effect. It is not a sedative, but it may help with stress.
It is best to start at least 2 days before (longer if possible). Many medications and supplements take more than one dose to reach therapeutic levels. Zylkene works by binding benzodiazepine receptors in the brain to help with calming effects without the sedation of benzodiazepines. A single dose may not do much, but given over the course of several days you may see better response.
A couple of studies on Zylkene:
Now, regarding the travel itself – the cats will be fine. They may be nervous for a few hours, but it doesn't take long for most cats to settle down during a long plane or train journey. Perhaps cover their carriers in a blanket so that they are less sensitive to their surroundings, and make use of pheromone products such as Feliway.
Cats are very perceptive little creatures, and the more stressed you are stressed about it, the more stressed they will be. So, relax, and Zylkene for all (that's a joke, please don't consume any Zylkene yourself).